JPH06242316A - Liquid crystal high polymer film for optical element - Google Patents

Abstract

PURPOSE:To improve the productivity and economical efficiency of liquid crystal high polymer by executing rubbing processing in an oblique direction having a prescribed angle from the MD direction of a long orientation base. CONSTITUTION:Rubbing processing is executed in an oblique direction having a prescribed angle from the MD direction of a long continuous film 12. The rubbing processing can be executed by an optional method. For instance, the film 12 and a rubbing roll 10 made oblique from the MD direction of the film 12 at an optional angle are arranged on a stage 11 for carrying the film 12 to be an orientation base in the MD direction and the surface of the film 12 is rubbed by rotating the roll 10 while carrying the film 12. This mechanism can optionally adjust an angle formed by the roll 10 and the carrying direction of the film 12. Since a liquid crystal high polymer film can be continuously produced to obtain a long size film, the productivity and economical efficiency of the film can be improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display element color compensating plate, a liquid crystal display element viewing angle compensating plate, an optical retardation plate, 1
The present invention relates to a continuous liquid crystal polymer oriented film in the form of a continuous film oriented at an arbitrary angle used for optical elements such as a 1/2 wavelength plate, a 1/4 wavelength plate, and an optical rotatory optical element.

[0002]

2. Description of the Related Art In a liquid crystal display device, a surface of an alignment substrate which is in contact with a liquid crystal is rubbed in order to physically or physically regulate liquid crystal molecules as a display element.

This rubbing treatment is carried out, for example, by rubbing an appropriate polyimide film formed on the alignment substrate with a cloth or the like.

However, since the conventional oriented substrate may be a rigid substrate such as a glass substrate, the rubbing process has been performed on a substrate that has been cut into a rectangular shape in advance. Therefore, it is necessary to form a polyimide film or the like on the alignment substrate by using a printing machine or a spin coater for each sheet, which requires an expensive apparatus. For example, the spin coater is uneconomical due to its mechanism that a considerable amount of the coating material is scattered. Even when the rubbing process is performed, a mechanism for positioning and fixing the substrate on the table by shuttle transfer or the like is necessary for the rubbing process, and a great amount of transfer time is required. Therefore, there is a problem in productivity and economy.

Further, since the polarizing plate, the optical retardation plate and the like have been conventionally manufactured by a polymer stretching operation, their orientations have been set only in a fixed direction. That is, the polarizing plate is polyvinyl alcohol, PET
The optical retardation plate uses a film obtained by uniaxially stretching and orienting polycarbonate or the like. Therefore, since the orientation direction is fixed, for example, in the case of a long film, the orientation direction is determined by the MD direction and it is difficult to set the orientation direction arbitrarily.

On the other hand, an optical element made of a liquid crystal polymer, such as an optical retardation plate, needs to have a structure oriented at a predetermined angle with respect to the substrate. Then, such alignment is performed by the alignment substrate which is also rubbed. That is, the conventional optical element such as an optical retardation plate is fixed in the orientation of the liquid crystal polymer by the glass substrate which is cut into a predetermined shape and then subjected to the orientation treatment. Therefore, there is a problem in productivity and economy as in the above.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the productivity and economy of liquid crystal polymers.

[0008]

That is, the first aspect of the present invention
Relates to a long liquid crystal polymer film which is oriented obliquely with respect to the MD direction at a predetermined angle.

A second aspect of the present invention relates to a long laminated sheet for an optical element, which comprises a liquid crystal polymer film layer and a polarizing film layer which are oriented at an angle of at least a predetermined angle with respect to the MD direction. .

The present invention will be further described below. Since the orientation of the liquid crystal polymer is regulated by the orientation substrate, the rubbing treatment is characterized in that the rubbing treatment is performed on a long orientation substrate in the present invention. The rubbing process is also characterized by being performed in an oblique direction having a predetermined angle with respect to the MD direction of the long alignment substrate.

The alignment substrate is a substrate that regulates the alignment of the liquid crystal polymer, and it may be a polymer film formed on an appropriate base material. The long film means a continuous film having a certain length, and industrially means a continuous film that can be supplied in a rolled form. Of course, the form of roll winding is not essential, and it may be a continuous film appropriately folded. In some cases, the length may reach as long as 10,000 m.

As the polymer constituting the alignment substrate, the surface may be physically or physicochemically aligned by rubbing treatment, and then the liquid crystal polymer contacted with the rubbing treatment surface may be aligned corresponding to the rubbing treatment. Any of these may be used, and either thermosetting resin or thermoplastic resin may be used. For example, polyimide, epoxy resin, thermosetting resin such as phenol resin, polyamide such as nylon; polyether imide;
Polyether ketone; Polyether ether ketone (P
EEK); polyketone; polyether sulfone; polyphenylene sulfide; polyphenylene oxide;
Examples thereof include polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyacetals; polycarbonates; poly (meth) acrylates; cellulosic resins such as triacetyl cellulose; and thermoplastic resins such as polyvinyl alcohol.

The polymer film itself may be subjected to a rubbing treatment, or the polymer film may be used as a base material and an organic thin film made of the other polymer exemplified above may be formed on the surface thereof. It is illustrated. In addition to the polymer film, the base material of such an organic thin film may be a metal foil such as copper, stainless steel or steel.

In addition, the oriented substrate itself may be a metal foil of copper, stainless steel, steel or the like.

The method for forming an organic thin film as an orientation substrate on a base material on a continuous film is a cheap continuous method such as a die coater because the base material is a continuous film. it can. For example, a method of coating a thermosetting resin solution such as polyimide and then heat curing to obtain an organic thin film, or a method of coating a thermoplastic resin solution such as polyvinyl alcohol and then removing the solvent to obtain an organic thin film. Can be adopted.

As the polymer constituting the organic thin film as the alignment substrate to be subjected to the rubbing treatment, particularly preferable are thermosetting resins such as polyimide or thermoplastic resins such as polyethylene terephthalate, polyphenylene sulfide, PEEK and polyvinyl alcohol. These are preferable because they have high heat resistance and the rubbing treatment is stably stored even in the heating operation for thermally fixing the liquid crystal phase of the liquid crystal polymer described later.

In the present invention, what is subjected to the rubbing treatment is particularly preferable because it is obtained by rubbing the long self-supporting polymer film itself, and does not use a base material to be laminated. is there. As a long film suitable for such purpose, a film made of a thermoplastic resin among the films exemplified above, for example, polyethylene terephthalate, polyphenylene sulfide, PE
It is a thermoplastic resin such as EK or polyvinyl alcohol.

Such a film can be easily obtained as a long continuous film by a usual molding method such as a T-die extrusion method. The thickness can be appropriately selected, but can be adopted, for example, in the range of 10 μm to 10 mm. Although the width is also appropriate, it is usually selected from the range of 1 to 500 cm.

Further, such a thermoplastic resin film is a film appropriately stretched uniaxially or biaxially with respect to the MD direction by a known method within a range not hindering the effect of the rubbing treatment described later. be able to.

The rubbing treatment is carried out by using a long continuous film M
The rubbing is performed in an oblique direction at a predetermined angle with respect to the D direction.

The angle in the oblique direction with respect to the MD direction is separately set so as to correspond to a predetermined angle of each liquid crystal in the liquid crystal display element. For example, the angle may be set to 45 ° or more with respect to the MD direction.

The rubbing process can be performed by any method. For example, referring to FIG. 1 as one of the methods, a long continuous film (12) as an alignment substrate.
A long film (12) and a rubbing roll (10) are arranged obliquely at an arbitrary angle with respect to the MD direction on a stage (11) that conveys the long film (12). While rubbing the rubbing roll (10), the surface of the film (12) is rubbed. The angle formed by the rubbing roll (10) and the moving direction of the stage (11) is a mechanism that can be freely adjusted.

An appropriate rubbing material is attached to the surface of the rubbing roll. The rubbing material is appropriately selected according to the type of the alignment substrate to be rubbed, a woven fabric,
Felt, rubber, brush, etc. are used and not particularly limited, but woven fabric such as nylon or cotton is usually selected. A rubbing material such as sandpaper or leather can also be used when the oriented substrate itself is a metal foil.

In the rubbing treatment, it is important to consider the hardness of the surface of the alignment substrate and rub the surface of the alignment substrate in a certain direction. From this point of view, the rubbing pressure, the number of revolutions of the rubbing roll, and the like are set appropriately. Usually, the alignment substrate is transferred at a speed of 0.5 to 100 m / min, preferably 1 to 30 m / min, and the rubbing roll rotation speed is 1 as a peripheral speed ratio.
To 1000, preferably 5 to 200. The rubbing pressure may be such that the rubbing material is slightly in contact with the rubbing material. When the rubbing material is a cloth, the degree of pushing of the hair tips is 100 μm to 5000 μm, preferably 1
It can be set to about 00 μm to 2000 μm.

The rubbing-treated oriented substrate is then laminated so that the rubbing surface is in contact with the liquid crystal polymer. The liquid crystal polymer is aligned according to the rubbing of the rubbing-treated alignment substrate.

The liquid crystal polymer to be laminated is a polymer exhibiting liquid crystallinity and is a thermotropic liquid crystal polymer exhibiting liquid crystallinity when melted. The structure of the liquid crystal phase when molten is
It can be a smectic, nematic, twisted nematic (cholesteric) or discotic molecular array structure. The thermotropic liquid crystal polymer selected here is a liquid crystal polymer in which the molecular alignment state of the liquid crystal phase is maintained when the temperature is lowered to a temperature lower than the glass transition temperature from the time of melting.

Since it has such a so-called self-memory property, if a rubbing-treated alignment substrate is laminated with the liquid crystal polymer and the liquid crystal polymer is melted to develop a liquid crystal phase, it is expressed. The liquid crystal phase is aligned corresponding to the rubbing surface. When this is cooled to a temperature lower than the glass transition temperature of the liquid crystal polymer, the orientation in the liquid crystal phase is preserved and the orientation is fixed.

As the thermotropic liquid crystal polymer to be laminated with the rubbing-treated oriented substrate, when it is lowered to a temperature lower than the glass transition temperature of the polymer,
Any liquid crystal polymer can be selected as long as it maintains the molecular alignment of the liquid crystal phase. That is, the liquid crystal polymer is in a glass state at a temperature below the liquid crystal transition temperature.

When used as an optical element such as an optical retardation plate or an optical rotator, a liquid crystal polymer showing a uniform and monodomain nematic phase in liquid crystal is preferable.

The molecular weight of these liquid crystal polymers can be determined in various solvents such as phenol / tetrachloroethane (60/4).
0) The logarithmic viscosity measured at 30 ° C. in the mixed solvent is 0.05.
To 3.0, preferably 0.07 to 2.0. When the logarithmic viscosity is less than 0.05, the strength of the obtained liquid crystal polymer is lowered, while when it exceeds 3.0, the viscosity at the time of liquid crystal formation is too high and the alignment property is lowered or the time required for the alignment is lowered. This is not preferable because problems such as increase in

The glass transition temperature of these polymers is also important and affects the orientation stability after orientation fixing. That is, although it depends on the temperature in the application state, generally when used at room temperature, the glass transition temperature is preferably room temperature or higher, and particularly preferably 50 ° C. or higher. When the glass transition temperature is lower than room temperature, it is expected that the orientation state once fixed will change when used at room temperature. Since the glass phase appears after the liquid crystal phase, the alignment can be fixed by cooling without impairing the alignment state.

On the other hand, used as an optical element such as a color compensator for eliminating coloring of the liquid crystal display element or an optical element for rotating the azimuth of linearly polarized light or the azimuth of elliptically polarized light. A suitable liquid crystal polymer that is used is one that contains an optically active unit, exhibits a uniform and monodomain nematic orientation, and has a predetermined amount of nematic liquid crystal polymer that can easily fix the orientation state. A composition prepared by mixing an optically active substance or an optically active group in the molecular chain such as side chain or main chain, showing a uniform monodomain twisted nematic alignment and easily fixing the alignment state. It is selected from possible liquid crystalline polymers.

Therefore, it is not always essential that the liquid crystal polymer phase contains an optically active unit depending on the usage of the optical element.

Here, the twist angle or the twist direction of the liquid crystal polymer phase can be adjusted by adjusting the ratio of the optically active units in the polymer or the type and amount of the optically active compound to be mixed. The ratio of the optically active unit is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, based on the whole composition. The optically active unit as used herein may be an optically active compound separately blended, or may be an optically active group present in the main chain or side chain of a liquid crystal polymer. By thus imparting optical activity and adjusting the ratio thereof, the twist angle or the twist direction of the liquid crystal polymer phase can be adjusted to any angle of 0 ° or more.

Therefore, when it is used as an optical element such as a color compensating plate for eliminating the coloring of the liquid crystal display element and an optical rotator for rotating the azimuth of linearly polarized light or the azimuth of elliptically polarized light. Is a polymer having an optically active group itself and exhibiting twisted nematic liquid crystallinity as a suitable liquid crystal polymer, or a composition of a base polymer having nematic liquid crystallinity itself having no optically active group and an optically active compound. There are two ways.

As a color compensator for a liquid crystal display device, strict control of optical parameters of a liquid crystal polymer layer is required to obtain a high quality black and white display, and molecules of the liquid crystal polymer are perpendicular to the substrate. It has a helical structure with a helical axis, and its twist angle is in the range of 30 degrees to 300 degrees.
The product Δ of the birefringence Δn and the film thickness d of the layer made of liquid crystal polymer
It is necessary that n · d is in the range of 0.01 to 3.0 μm. Especially for TN, the twist angle is usually 30 to 15
0 °, preferably 40 to 120 °, and Δn · d is usually 0.
05-3.0 μm, more preferably 0.1-2.8 μm
Is suitable, and in the case of STN, the twist angle is usually 150 to 300 °, preferably 170 to 280 °, Δ
n · d is usually 0.1 to 1.5 μm, more preferably 0.
A range of 3 to 1.2 μm is suitable. If the above-mentioned liquid crystal polymer or a composition thereof is used, the above-mentioned orientation can be easily fixed to a predetermined film thickness.

In the present invention, M is set at a predetermined angle.
A long liquid crystal polymer film is provided which is oriented obliquely with respect to the D direction. In this case, when the orientation directions are different from each other on the front and back surfaces of the liquid crystal polymer layer, one of the two surfaces is provided. In the above, any orientation may be used as long as it is oriented obliquely with respect to the MD direction at a predetermined angle. When the liquid crystal state of the liquid crystal polymer is simply nematic and monodomain aligned, the alignment direction does not differ between the front and back of the liquid crystal polymer film, and the rubbed direction and the alignment direction of the liquid crystal polymer match. . Therefore, MD with a predetermined angle
In order to obtain a long liquid crystal polymer film that is oriented obliquely with respect to the direction, the oriented substrate must be rubbed obliquely with respect to the MD direction at the same predetermined angle.

However, when the liquid crystal polymer is nematic having twist and has a monodomain orientation, the orientation direction may be different between the front and back of the liquid crystal polymer film. That is, the alignment of the liquid crystal polymer layer on the surface in contact with the rubbed alignment substrate is certainly in the same direction as the rubbing direction of the alignment substrate. However, the orientation on the opposite surface changes direction by an angle determined by the thickness of the liquid crystal polymer layer and the ratio of the optically active units, and as a result, it may not always match the rubbing direction of the alignment substrate. Become.

Therefore, in the case of a twisted nematic liquid crystal polymer having a monodomain alignment, the rubbing direction of the alignment substrate does not necessarily have to be oblique to the MD direction. For example, the alignment substrate may be aligned by rubbing parallel to the MD direction.

Besides, as the viewing angle compensating plate for liquid crystal display and the cholesteric filter, a polymer liquid crystal layer having a twist angle of 360 ° or more is used. 1/2 wave plate, 1/4
A nematic liquid crystal polymer having no twist structure is used for a wave plate and an optical retardation plate that does not need to have optical activity, but strict control of optical parameters is required. As the optical parameter, Δn of the polymer liquid crystal layer
-D is 0.01 to 10 m, preferably 0.1 to 5 m
Must be within the range.

In any case, if polymer liquid crystals are used, such strict control of optical parameters can be easily performed.

In the following, materials suitable for use in the present invention will be exemplified. That is, a liquid crystal polymer that does not have an optically active group and exhibits nematic liquid crystallinity, an optically active compound that should be blended with a base polymer that is a liquid crystal polymer that does not have an optically active group and exhibits nematic liquid crystallinity, and A liquid crystal polymer having an optically active group and exhibiting a twisted nematic liquid crystal property will be sequentially described.

As the polymer to be used, it is preferable to use any polymer that is twisted nematically aligned in the liquid crystal state and is in the glass state at the liquid crystal transition point or lower. For example, a main chain of optically active polyester, polyamide, polycarbonate, polyesterimide or the like. Examples thereof include type liquid crystal polymers, side chain type liquid crystal polymers such as polyacrylate, polymethacrylate, polymalonate, and polysiloxane. In addition, the main chain type liquid crystal polymer such as polyester, polyamide, polycarbonate, polyesterimide which is not optically active, or the side chain type liquid crystal polymer such as polyacrylate, polymethacrylate, polymalonate, polysiloxane, etc. The polymer etc. which added the active compound can be illustrated. Among them, polyester is preferable from the viewpoint of easiness of synthesis, orientation, glass transition point and the like. The polyester used is most preferably a polymer containing an ortho-substituted aromatic unit as a constituent, but an aromatic having a bulky substituent in place of the ortho-substituted aromatic unit, or an aromatic having a fluorine- or fluorine-containing substituent, etc. Polymers containing as a constituent can also be used. The ortho-substituted aromatic unit referred to in the present invention is
It means a structural unit in which the bonds forming the main chain are ortho to each other. Examples of these are

[Chemical 1] (X represents hydrogen, halogen such as Cl and Br, an alkyl group or an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and k is 0 to 2). Among these, the following can be exemplified as particularly preferable examples.

[Chemical 2] (Me; methyl group, Et; ethyl group, Bu; butyl group)

As the polyester used in the present invention,
(A) a structural unit derived from a diol (hereinafter referred to as a diol component) and a structural unit derived from a dicarboxylic acid (hereinafter referred to as a dicarboxylic acid component) and / or (b) a carboxylic acid and a hydroxyl group in one unit. Polymers containing structural units derived from oxycarboxylic acids containing at the same time (hereinafter referred to as oxycarboxylic acid component) as constituent components, and preferably further containing the ortho-substituted aromatic unit can be exemplified.

Among these, the following aromatic and aliphatic diols can be mentioned as the diol component.

[Chemical 3] (Y is hydrogen, halogen such as Cl and Br, and has 1 to 4 carbon atoms.
Represents an alkyl group, an alkoxy group, or a phenyl group. 1 is 0 to 2. )

[Chemical 4] (N represents an integer of 2 to 12)

[Chemical 5] Above all

[Chemical 6] Etc. are preferably used.

The following can be exemplified as the dicarboxylic acid component.

[Chemical 7] (Z represents hydrogen, halogen such as Cl and Br, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a phenyl group. M is 0 to 2),

[Chemical 8]

[Chemical 9] Above all,

[Chemical 10] Are preferred.

Specific examples of the oxycarboxylic acid component are the following units.

[Chemical 11]

The molar ratio of the dicarboxylic acid to the diol is approximately 1: 1 as in the case of general polyesters (in the case of using oxycarboxylic acid, the ratio of carboxylic acid group and hydroxyl group). The ratio of ortho-substituted aromatic units in the polyester is usually preferably 5 mol% to 40 mol%, more preferably 10 mol% to 30 mol%. When it is less than 5 mol%, a crystal phase tends to appear below the nematic phase, which is not preferable. Again 40
When it is more than mol%, the polymer tends to lose liquid crystallinity, which is not preferable. The following polymers can be illustrated as a typical polyester.

[Chemical 12] A polymer composed of structural units of

[Chemical 13] A polymer composed of structural units of

[Chemical 14] A polymer composed of structural units of

[Chemical 15] A polymer composed of structural units of

[Chemical 16] A polymer composed of structural units of

[Chemical 17] A polymer composed of structural units of

[Chemical 18] A polymer composed of structural units of

[Chemical 19] A polymer composed of structural units of.

Polymers having an aromatic unit containing a bulky substituent as shown below instead of an ortho-substituted aromatic unit or an aromatic unit containing a fluorine- or fluorine-containing substituent as a constituent component are also preferably used.

[Chemical 20]

[Chemical 21]

[Chemical formula 22]

The molecular weight of these polymers can be determined in various solvents such as phenol / tetrachloroethane (60/40).
(Weight ratio) The logarithmic viscosity measured at 30 ° C. in a mixed solvent is usually preferably 0.05 to 3.0, more preferably 0.07 to 2.0. Logarithmic viscosity is 0.05
When it is smaller, the strength of the obtained polymer liquid crystal becomes weak, which is not preferable. On the other hand, when it is more than 3.0, the viscosity at the time of forming the liquid crystal is too high, which causes problems such as deterioration of alignment property and increase of time required for alignment.

The method for synthesizing these polymers is not particularly limited, and they can be synthesized by a polymerization method known in the art, for example, a melt polymerization method or an acid chloride method using a corresponding acid chloride of dicarboxylic acid. In the case of synthesizing by a melt polymerization method, it can be produced, for example, by polymerizing an acetylated product of a corresponding dicarboxylic acid and a corresponding diol at high temperature under high vacuum, and the molecular weight can be easily controlled by controlling the polymerization time or controlling the charging composition. .
In order to accelerate the polymerization reaction, a conventionally known metal salt such as sodium acetate can be used. When the solution polymerization method is used, a desired amount of dicarboxylic acid dichloride and diol are dissolved in a solvent and heated in the presence of an acid acceptor such as pyridine to easily obtain the target polyester.

The optically active compound which is mixed to impart twist to these nematic liquid crystalline polymers will be described. First, a typical example is an optically active low molecular weight compound. Any compound having optical activity can be used in the present invention, but an optically active liquid crystal compound is preferable from the viewpoint of compatibility with the base polymer. Specifically, the following compounds can be exemplified.

[Chemical formula 23]

[Chemical formula 24] Cholesterol derivatives, etc.

Examples of the optically active compound used in the present invention include the following optically active polymer compounds. Any polymer compound having an optically active group in the molecule can be used, but a polymer compound having liquid crystallinity is preferable from the viewpoint of compatibility with the base polymer. Examples thereof include liquid crystalline polyacrylates, polymethacrylates, polymalonates, polysiloxanes, polyesters, polyamides, polyesteramides, polycarbonates having an optically active group, polypeptides, celluloses and the like. Among them, an optically active polyester mainly containing an aromatic compound is most preferable because of its compatibility with the nematic liquid crystal polymer as the base. Specifically, the following polymers can be exemplified.

[Chemical 25] A polymer composed of structural units of

[Chemical formula 26] A polymer composed of structural units of

[Chemical 27] A polymer composed of structural units of (n = 2-12),

[Chemical 28] A polymer composed of structural units of

[Chemical 29] A polymer composed of structural units of

[Chemical 30] A polymer composed of structural units of

[Chemical 31] A polymer composed of structural units of

[Chemical 32] A polymer composed of structural units of

[Chemical 33] A polymer composed of structural units of

[Chemical 34] A polymer composed of structural units of

[Chemical 35] A polymer composed of structural units of.

The proportion of the optically active group in these polymers is usually 0.5 mol% to 80 mol%, preferably 5 mol% to 60 mol%.

The molecular weight of these polymers is preferably, for example, in the range of 0.05 to 5.0 in logarithmic viscosity measured at 30 ° C. in phenol / tetrachloroethane. When the logarithmic viscosity is more than 5.0, the viscosity is too high, resulting in a decrease in orientation, which is not preferable, and when it is less than 0.05, the composition is difficult to control, which is not preferable.

The optical element of the present invention also uses a polymer liquid crystal which itself has a uniform and monodomain twisted nematic alignment without using other optically active compounds, and can easily fix the alignment state. Can also be manufactured. It is essential that these polymers have an optically active group in the main chain and are themselves optically active. Specifically, the main chain type liquid crystal polymer such as optically active polyester, polyamide, polycarbonate, polyester imide, or Examples thereof include side chain type liquid crystal polymers such as polyacrylate, polymethacrylate, and polysiloxane. Among them, polyester is preferable from the viewpoint of easiness of synthesis, orientation, glass transition point and the like. The polyester used is most preferably a polymer containing an ortho-substituted aromatic unit as a constituent, but an aromatic having a bulky substituent in place of the ortho-substituted aromatic unit, or an aromatic having a fluorine- or fluorine-containing substituent, etc. Polymers containing as a constituent can also be used. These optically active polyesters can be obtained by introducing the following optically active groups into the nematic liquid crystalline polyesters described so far using an optically active diol, dicarboxylic acid or oxycarboxylic acid. (In the formula, * indicates optically active carbon)

[Chemical 36]

[Chemical 37] Such.

The molecular weight of these polymers can be determined in various solvents such as phenol / tetrachloroethane (60/4
0) The logarithmic viscosity measured at 30 ° C. in the mixed solvent is 0.05.
To 3.0 are preferable, and more preferably 0.07 to 2.0. When the logarithmic viscosity is less than 0.05, the strength of the obtained polymer liquid crystal becomes weak, which is not preferable. On the other hand, when it is more than 3.0, the viscosity at the time of liquid crystal formation is too high, and problems such as a decrease in alignment and an increase in the time required for alignment occur. Polymerization of these polymers can be carried out by a melt polycondensation method or an acid chloride method.

As typical examples of the liquid crystalline polymer of the present invention described above, specifically,

[Chemical 38] Ch: cholesteryl group, polymer (m / n =
Usually 99.9 / 0.1-80 / 20, preferably 99.
5 / 0.5 to 90/10, more preferably 99/1 to
95/5)

[Chemical Formula 39] Polymer (m / n = normally 99.9 / 0.1)
80/20, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5)

[Chemical 40] Polymer (m / n = normally 99.9 / 0.1)
70/30, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5, p, q; 2
~ Integer of 20)

[Chemical 41] Polymer (m / n = normally 99.9 / 0.1)
70/30, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5, p, q; 2
~ Integer of 20)

[Chemical 42] Polymer (m / n = normally 99.9 / 0.1)
80/20, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5)

[Chemical 43] (M / n = 0.5 / 99.5-10)
/ 90, preferably 1/99 to 5/95)

[Chemical 44] (M / n = 0.5 / 99.5-10)
/ 90, preferably 1/99 to 5/95)

[Chemical formula 45] Polymer (K = 1 + m + n, K / n = 99.
5 / 0.5 to 90/10, preferably 99/1 to 95
/ 5, 1 / m = 5/95 to 95/55)

[Chemical formula 46] Polymer (K = 1 + m + n, K / n = 99.
5 / 0.5 to 90/10, preferably 99/1 to 95
/ 5, 1 / m = 5/95 to 95/55)

[Chemical 47] Polymer mixture represented by ((A) / (B) = normally 9
9.9 / 0.1-80 / 20 (weight ratio), preferably 9
9.5 / 0.5 to 85/5, more preferably 99/1
~ 95/5, K = 1 + m, 1 / m = 75 / 25-25 /
75, P = q + r, p / q = 80/20 to 20/80)

[Chemical 48] (B) Polymer mixture represented by cholesteryl benzoate ((A) / (B) = usually 99.9 / 0.1-70 /
30 (weight ratio), preferably 99.5 / 0.5 to 80 /
20, preferably 99/1 to 90/10, m = K + 1,
K / l = 80/20 to 20/80)

[Chemical 49] Polymer mixture represented by ((A) / (B) = normally 9
9.9 / 0.1 to 70/30 (weight ratio), preferably 9
9.5 / 0.5 to 80/20, preferably 99/1 to 9
0/10, K = 1 + m, 1 / m = 25/75 to 75/2
5, P = q + r, p / r = 20/80 to 80/20)
(Note that * indicates optically active carbon) and the like.

In any case, if a polyester polymer is adopted as the liquid crystal polymer, it is preferable since it has good adhesiveness to the acrylic resin used as the protective layer or the adhesive layer.

The liquid crystal polymer is formed into a long film by any method. For example, after dissolving in an appropriate solvent and applying,
A method of forming a film by drying, or a method of melt-extruding a liquid crystal polymer with a T die or the like can be used. From the viewpoint of quality such as film thickness, a method of applying a solution and drying is suitable. As described above, the meaning of a long film in the present invention means a continuous film having a constant length, and industrially means a continuous film that can be supplied in a rolled form. . Of course, the form of roll winding is not essential, and it may be a continuous film appropriately folded. The length of the long film may reach as long as 10,000 m in some cases.

That is, first, a liquid crystal polymer is dissolved in a solvent at a predetermined ratio to prepare a solution. The solvent used at this time varies depending on the type of polymer, but usually, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; halogenated carbonization such as chloroform, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, orthodichlorobenzene. Hydrogen; a mixed solvent thereof; a mixed solvent of these with phenol; an amide-based solvent such as dimethylformamide and dimethylacetamide; a solvent such as dimethyl sulfoxide; N-methylpyrrolidone can be used. The concentration of the solution varies depending on the viscosity of the polymer, but is usually in the range of 5 to 50% by weight, preferably 10 to 30% by weight.

Next, this solution is MD-treated at a predetermined angle.
Application is performed on a long alignment substrate obtained by rubbing in a direction oblique to the direction.

The coating method is not particularly limited, and for example, a die coating method, a slot die coating method, a roll coating method, a bar coating method, a curtain coating method, a dipping and pulling method and the like can be adopted. After coating, the solvent is removed by drying.

After a liquid crystal polymer layer is formed on a long alignment substrate formed by rubbing in a direction oblique to the MD direction at a predetermined angle, the liquid crystal is heated at a predetermined temperature for a predetermined time. Fix the orientation of molecules.

The fixing temperature is preferably such that the viscosity of the polymer at the time of fixing is low in order to assist the orientation by the interfacial effect. That is, the higher the heating temperature, the better. However,
If the temperature is too high, the cost is increased and the workability is deteriorated, which is not preferable. From this point of view, generally 50 to
300 ° C, preferably in the range of 100 to 250 ° C, 10
It is selected from the range of seconds to 60 minutes, preferably 30 seconds to 30 minutes. The heating means can be appropriately used, and examples thereof include hot air heating, infrared heating, dielectric heating, heating with an electric heater, and heating with a hot roll.

In any case, it is important to carry out heat treatment at a temperature not lower than the glass transition temperature and not higher than the transition temperature of the isotropic phase for a time sufficient to align the liquid crystal molecules.

After heating, the liquid crystal polymer is fixed by cooling it to a temperature below the glass transition temperature of the liquid crystal polymer. Since the glass phase appears after the liquid crystal phase, the alignment can be fixed by cooling without impairing the alignment state.

The cooling rate is not particularly limited and may be arbitrarily selected. For example, it is immobilized only by moving the heated liquid crystal polymer from the heating region into an atmosphere having a glass transition temperature or lower. For the purpose of improving production efficiency, air cooling or cooling with a refrigerant such as water can be adopted.

The thickness of the liquid crystal polymer film after fixation is
There is no particular limitation as long as the liquid crystal polymer film is in a range that functions based on the twisted nematic structure. Although it depends on the wavelength of light, it is 0.05 μm or more, preferably 1 μm or more, more preferably 2 μm or more in the field where visible light is important such as display applications.
If it is less than 0.05 μm, it is difficult to perform accurate adjustment, which is not preferable. The upper limit of the film thickness is not particularly limited, but if it is too thick, the regulation force as an optical element is weakened, which is not preferable. From this viewpoint, it is 100 μm or less, preferably 30 μm.
The following ranges are suitable.

In the present invention, since the lower alignment substrate is a long alignment substrate which is formed by rubbing in a direction oblique to the MD direction at a predetermined angle, a predetermined angle corresponding to this rubbing treatment is used. Accordingly, a long liquid crystal polymer film oriented obliquely with respect to the MD direction can be obtained.

The long alignment substrate itself, which is obtained by rubbing in a direction oblique to the MD direction at a predetermined angle,
When the substrate is a translucent substrate, the fixed laminate itself can be used as an optical element as it is or by appropriately combining it with a polarizing plate. Usually, it is transferred onto an appropriate transparent substrate as a support and finally used as an optical element.

The light-transmissive substrate is not particularly limited as long as it has transparency and optical isotropy and can support a liquid crystal polymer phase, but a plastic film is necessary because it needs to be long. Examples thereof include polymethyl methacrylate, polystyrene, polycarbonate, polyether sulfone, polyphenylene sulfide, polyarylate, polyethylene sulfide, amorphous polyolefin, and triacetyl cellulose. The thickness of these translucent substrates is not particularly limited, but is usually selected from the range of 1 to 500 μm.

The transfer to the transparent substrate can be performed by any method, for example, a transfer method. This method is a method in which an appropriate adhesive / adhesive layer is formed on the liquid crystal polymer layer side or the translucent substrate side, and one of them is adhesively / adhesively transferred. As this adhesive layer, any can be used as long as it is transparent and optically isotropic,
Acrylic, epoxy, ethylene-vinyl acetate, rubber, etc. can be used. An acrylic adhesive is preferable.

The long laminated film thus obtained is economical because its orientation is oblique to the MD direction.

To protect the surface of the liquid crystal polymer, a protective layer made of a curable acrylic resin may be provided, or a translucent film as a protective film may be attached via a tacky adhesive layer. .

If necessary, when used as a color compensating plate for a liquid crystal display device, it is further laminated with a polarizing plate. Even in such a case, since it is a long continuous film, it is possible to easily and continuously carry out a lamination operation with a continuous long polarizing plate. In addition, the lamination with such a polarizing plate needs to be laminated so that the transmission axis of the polarizing film and the optical axis of the liquid crystal polymer film have a constant relationship, but the liquid crystal polymer of the present invention is optional. Since the orientation angle can be set in the direction, continuous lamination can be easily performed.

A known polarizing film can be used as the polarizing plate. Since the polarizing film is usually commercially available as a laminated sheet having a three-layer structure of transparent substrate / polarizing film / transparent substrate, it can be used for bonding. here,
The type of transparent substrate is the same as that described above. The thickness is selected from the range of 1 to 500 μm, and the thickness of the polarizing film is the same.

The polarizing film is usually composed of a stretched polymer film, for example, a long uniaxially stretched film of a transparent polymer film such as polyester such as polyvinyl alcohol, polyvinyl butyral or PET in which iodine is absorbed or a two-color film. It is impregnated with a functional dye.

Also in the case of laminating the polarizing film and the liquid crystal polymer film, they can be laminated via a known translucent adhesive. In any case, the thickness of the adhesive layer for adhesive adhesion can be selected from the range of 1 to 100 μm.

The long film of the present invention is appropriately cut,
As an optical element, for example, it is appropriately attached to a liquid crystal display element panel.

[0081]

【The invention's effect】

1) Since a liquid crystal polymer film can be continuously produced and a long film can be obtained, productivity and economic efficiency are improved. 2) Since the orientation angle of the liquid crystal polymer film can be arbitrarily controlled, the liquid crystal polymer can be cut out without waste when assembling the optical element, which is excellent in economic efficiency and improves the yield. Furthermore, in the case of laminating and laminating with a polarizing film, a specific orientation angle can be set with respect to the optical axis of the polarizing film, so that both can be laminated continuously. 3) The orientation angle of the liquid crystal polymer film has a wider range than that in which the polymer is stretched and oriented. 4) Similarly, it has significantly fewer optical defects than those obtained by orienting a polymer by stretching.

[0082]

EXAMPLES The present invention will be described in detail below with reference to examples. The analytical methods used in the examples are as follows. (1) Measurement of twist angle and Δn · d The twist angle was determined by ellipsometry, and Δn · d was determined by analyzing the data measured by an ellipsometer. (2) Measurement of logarithmic viscosity It was measured at 30 ° C. in a phenol / tetrachloroethane (60/40 weight ratio) mixed solvent using a Ubbelohde viscometer.

(Preparation Example 1 of Liquid Crystal Polymer Solution) Mixed polymer represented by the formula (I) (logarithmic viscosity of base polymer = 0.
21, Tg = 60 ° C., logarithmic viscosity of optically active polymer =
A 20 wt% dimethylformamide solution containing 0.18) was prepared.

[Chemical 50]

(Preparation Example 2 of Liquid Crystal Polymer Solution) A phenol / tetrachloroethane (60/40 weight ratio) solution of 20 wt% of the mixed polymer represented by the formula (II) was prepared.

[Chemical 51] The optically active polymer represented by the formula (III) (logarithmic viscosity of 0.
An 18 wt% trichloroethane solution of 23) was prepared.

[Chemical 52]

Example 1 Using the apparatus shown in FIG. 1, a film made of PEEK as an alignment substrate and having a width of 20 cm and a thickness of 100 μm was 20 m / m 2.
Nylon cloth is wrapped around while conveying at a speed of 15 minutes
A rubbing roll of 0 mmφ was set at 45 ° with respect to the MD direction of the PEEK film, and the rubbing was continuously carried out by rotating at 1500 rpm while setting the indentation of the tip of the nylon cloth to 500 μm, and wound into a roll.

Liquid Crystal Polymer Solution The solution obtained in Preparation Example 1 was cast on a rubbing-treated long film using a roll coater and then dried, and 200 ° C. × 4
The alignment of the liquid crystal polymer was fixed by heat treatment for 0 minutes.
The twist angle of this compensation layer is −231 °, and Δn · d is 0.8.
It was 4 μm.

When this film was transferred to a transparent film and observed with a polarizing microscope, the dark field was 18 in rotation angle.
Since it appeared every 0 °, it was confirmed that the orientation was perfect. At that time, the direction perpendicular to the light transmission axis of the polarizer was 45 ° with respect to the MD direction of the PEEK film.

Example 2 A 20 μm thick copper foil was used instead of the PEEK film, and # 10 was used instead of nylon as a rubbing cloth.
Rubbing treatment, solution coating and drying, and orientation fixing were performed in the same manner as in Example 1 except that the rubbing roll was rotated at 150 rpm while slightly contacting the copper foil with the sandpaper of No. 00. It was

As a result, a liquid crystal polymer film substantially the same as that in Example 1 was obtained. That is, the twist angle of this compensation layer was −231 °, and Δn · d was 0.84 μm. Further, when this film was transferred to a transparent film and observed by a polarization microscope, a dark field appeared every 180 ° as a rotation angle, so that it was confirmed that the orientation was perfect. At that time, the direction perpendicular to the light transmission axis of the polarizer was 45 ° with respect to the MD direction of the copper foil.

Example 3 The immobilized liquid crystal polymer film obtained in Example 1 was transferred to a triacetyl cellulose (TAC) film by an ordinary method using an adhesive. Subsequently, a commercially available polarizing film (PVA film containing iodine), which is also long, was laminated with an adhesive. In this lamination, long films were laminated with a roll. That is, the structure of the obtained long laminate was polarizing film / adhesive layer / liquid crystal polymer layer / adhesive layer / TAC layer. In the obtained laminate, the orientation angle was 45 ° with respect to the optical axis of the polarizing film.

Example 4 Liquid Crystal Polymer Solution The same procedure as in Example 1 was carried out except that the solution obtained in Preparation Example 2 was used, followed by casting using a die coater, followed by drying and heat treatment at 200 ° C. for 40 minutes. Then, the orientation of the liquid crystal polymer was fixed. The twist angle of this compensation layer was −231 °, and Δn · d was 0.84 μm.

When this film was transferred to a transparent film and observed with a polarization microscope, the dark field was 18 in rotation angle.
Since it appeared every 0 °, it was confirmed that the orientation was perfect. At that time, the direction perpendicular to the light transmission axis of the polarizer was 45 ° with respect to the MD direction of the PEEK film.

[Brief description of drawings]

FIG. 1 is a plan view of an apparatus for rubbing a long film oriented substrate in a direction oblique to the MD direction thereof.

[Explanation of symbols]

 10 Rubbing Roll 11 Stage for Transporting Oriented Substrate 12 Long Film Oriented Substrate

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 20, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

[0012] As the polymer constituting the alignment substrate, the surface is physically or physicochemically treated is by rubbing
Are, also can be employed subsequently as a liquid crystal polymer in contact with the rubbing surface of one if like be oriented in correspondence to the rubbing treatment, either a thermosetting resin or a thermoplastic resin Good. For example, polyimide, epoxy resin, thermosetting resin such as phenol resin, polyamide such as nylon; polyether imide;
Polyether ketone; Polyether ether ketone (P
EEK); polyketone; polyether sulfone; polyphenylene sulfide; polyphenylene oxide;
Examples thereof include polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyacetals; polycarbonates; poly (meth) acrylates; cellulosic resins such as triacetyl cellulose; and thermoplastic resins such as polyvinyl alcohol.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

The method for forming an organic thin film as an orientation substrate on a base material on a continuous film is a cheap continuous method such as a die coater because the base material is a continuous film. it can. For example, a method of coating a thermosetting resin solution such as polyimide and then heat curing to obtain an organic thin film, or a method of coating a thermoplastic resin solution such as polyvinyl alcohol and then removing the solvent to obtain an organic thin film is adopted. be able to.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

The rubbing process can be performed by any method. For example, referring to FIG. 1 as one of the methods, a long continuous film (12) as an alignment substrate.
A long film (12) and a rubbing roll (10) are arranged obliquely at an arbitrary angle with respect to the MD direction on a stage (11) that conveys the long film (12). While rubbing the rubbing roll (10), the surface of the film (12) is rubbed. Carrying the rubbing roll (10) and the film (12)
The angle formed by the feeding direction is a mechanism that can be freely adjusted.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

Optical retardation plate, 1/2 wavelength plate and 1 /
When used as an optical element such as a four-wave plate , a liquid crystal polymer that exhibits a uniform and monodomain nematic phase in liquid crystal is preferable.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

The direction of twist of the liquid crystal polymer film
Is defined as follows. That is, the liquid crystal polymer fill
The plane of polarization of light incident perpendicularly to the vertical plane changes clockwise.
How to twist when passing through the film while turning
The direction is defined as right twist or minus. When used as an optical element such as a color compensator for eliminating coloring of the liquid crystal display element, an optical rotator for rotating the azimuth of linearly polarized light or the azimuth of elliptically polarized light,
A suitable liquid crystal polymer is a polymer having an optically active group itself and exhibiting twisted nematic liquid crystallinity, or a composition comprising a base polymer having no optically active group and exhibiting nematic liquid crystallinity and an optically active compound. There is a street.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043] As polymers used are polyesters not optically active, polyamides, polycarbonates, main chain type liquid crystal polymer such as polyester imides, or polyacrylates, polymethacrylates, polymalonates, and etc. side chain type liquid crystal polymers such as polysiloxane An example can be given. Among them, ease of synthesis, orientation,
Polyester is preferable because of its glass transition point and the like. The polyester used is most preferably a polymer containing an ortho-substituted aromatic unit as a constituent, but an aromatic having a bulky substituent in place of the ortho-substituted aromatic unit,
Alternatively, a polymer containing fluorine or an aromatic compound having a fluorine-containing substituent as a constituent can also be used. The ortho-substituted aromatic unit referred to in the present invention means a structural unit in which the bonds forming the main chain are ortho to each other. Examples of these are (X represents hydrogen, halogen such as Cl and Br, an alkyl group or an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and k is 0 to 2). Among these, the following can be exemplified as particularly preferable examples. (Me; methyl group, Et: ethyl group, Bu; butyl group)

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

Among these, the following aromatic and aliphatic diols can be mentioned as the diol component. (Y is hydrogen, halogen such as Cl and Br, and has 1 to 4 carbon atoms.
Represents an alkyl group, an alkoxy group, or a phenyl group. 1 is 0 to 2. ) (N represents an integer of 2 to 12) Above all Etc. are preferably used.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

Examples of the optically active compound used in the present invention include the following optically active polymer compounds. Any polymer compound having an optically active group in the molecule can be used, but a polymer compound having liquid crystallinity is preferable from the viewpoint of compatibility with the base polymer. Examples thereof include liquid crystalline polyacrylates, polymethacrylates, polymalonates, polysiloxanes, polyesters, polyamides, polyesteramides, polycarbonates having an optically active group, polypeptides, celluloses and the like. Among them, an optically active polyester mainly containing an aromatic compound is most preferable because of its compatibility with the nematic liquid crystal polymer as the base. The following polymers can be used as examples. A polymer composed of structural units of A polymer composed of structural units of A polymer composed of structural units of (n = 2-12), A polymer composed of structural units of A polymer composed of structural units of A polymer composed of structural units of A polymer composed of structural units of A polymer composed of structural units of A polymer composed of structural units of A polymer composed of structural units of A polymer composed of structural units of.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

The optical element of the present invention also uses a polymer liquid crystal which itself has a uniform and monodomain twisted nematic alignment without using other optically active compounds, and can easily fix the alignment state. Can also be manufactured. It is essential that these polymers have an optically active group in the main chain and are themselves optically active. Specifically, the main chain type liquid crystal polymer such as optically active polyester, polyamide, polycarbonate, polyester imide, or Examples thereof include side chain type liquid crystal polymers such as polyacrylate, polymethacrylate, and polysiloxane. Among them, polyester is preferable from the viewpoint of easiness of synthesis, orientation, glass transition point and the like. The polyester used is most preferably a polymer containing an ortho-substituted aromatic unit as a constituent, but an aromatic having a bulky substituent in place of the ortho-substituted aromatic unit, or an aromatic having a fluorine- or fluorine-containing substituent, etc. Polymers containing as a constituent can also be used. These optically active polyesters can be obtained by introducing the following optically active groups into the nematic liquid crystalline polyesters described so far using an optically active diol, dicarboxylic acid or oxycarboxylic acid. (In the formula, * indicates optically active carbon) Such.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

As typical examples of the liquid crystalline polymer of the present invention described above, specifically, Ch: cholesteryl group, polymer (m / n =
Usually 99.9 / 0.1-80 / 20, preferably 99.
5 / 0.5 to 90/10, more preferably 99/1 to
95/5) Polymer (m / n = normally 99.9 / 0.1)
80/20, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5) Polymer (m / n = normally 99.9 / 0.1)
70/30, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5, p, q; 2
~ Integer of 20) Polymer (m / n = normally 99.9 / 0.1)
70/30, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5, p, q; 2
~ Integer of 20) Polymer (m / n = normally 99.9 / 0.1)
80/20, preferably 99.5 / 0.5 to 90/1
0, more preferably 99/1 to 95/5) (M / n = 0.5 / 99.5-10)
/ 90, preferably 1/99 to 5/95) ( K = l + m + n, k / n = 99.
5 / 0.5 to 90/10, preferably 99/1 to 95
/ 5, 1 / m = 5/95 to 95/55) ( K = l + m + n, k / n = 99.
5 / 0.5 to 90/10, preferably 99/1 to 95
/ 5, 1 / m = 5/95 to 95/55) Polymer mixture represented by ((A) / (B) = normally 9
9.9 / 0.1-80 / 20 (weight ratio), preferably 9
9.5 / 0.5 to 85/5, more preferably 99/1
~ 95/5, k = 1 + m, 1 / m = 75 / 25-25 /
75, p = q + r, P / q = 80/20 to 20/80) (B) Polymer mixture represented by cholesteryl benzoate ((A) / (B) = usually 99.9 / 0.1-70 /
30 (weight ratio), preferably 99.5 / 0.5 to 80 /
20, preferably 99/1 to 90/10, m = k + 1,
k / l = 80/20 to 20/80)

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

Polymer mixture represented by ((A) /
(B) = normally 99.9 / 0.1 to 70/30 (weight
Ratio), preferably 99.5 / 0.5 to 80/20, preferably
Specifically, 99/1 to 90/10, k = 1 + m, 1 / m = 2
5/75 to 75/25, P = q + r, q / r = 20/8
0-80 / 20) (Note that * indicates optically active carbon)
And so on.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

The coating method is not particularly limited, and examples thereof include slide die coating method, slot die coating method,
A curtain coating method , a roll coating method, a bar coating method, a dipping and pulling method and the like can be adopted. After coating, the solvent is removed by drying.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

The orientation temperature is preferably such that the viscosity of the polymer at the time of melting is low in order to assist the orientation by the interfacial effect. That is, the higher the heating temperature, the better. However,
If the temperature is too high, the cost is increased and the workability is deteriorated, which is not preferable. From this point of view, generally 50 to
300 ° C, preferably in the range of 100 to 250 ° C, 10
It is selected from the range of seconds to 60 minutes, preferably 30 seconds to 30 minutes. The heating means can be appropriately used, and examples thereof include hot air heating, infrared heating, dielectric heating, heating with an electric heater, and heating with a hot roll.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

(Preparation Example 2 of Liquid Crystal Polymer Solution) A phenol / tetrachloroethane (60/40 weight ratio) solution containing 20 Wt% of the mixed polymer represented by the formula (II) was prepared . formula
(II)

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

The rubbing angle was 45 °. here,
The rubbing angle is the MD direction when the rubbing surface is viewed from above.
The angle is clockwise from. The solution obtained in Preparation Example 1 of a liquid crystal polymer solution on the elongated film was the rubbing treatment, and dried after coating using a roll coater, the liquid crystal polymer by the heat treatment 200 ° C. × 40 minutes The orientation of was fixed. The twist angle of this compensation layer is -230 °,
Δn · d was 0.84 μm.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0087

[Correction method] Change

[Correction content]

When this film was transferred to a transparent film and observed with a polarizing microscope, the dark field was 18 in rotation angle.
Since it appeared every 0 °, it was confirmed that the orientation was perfect. At that time, the direction perpendicular to the light transmission axis of the polarizer was 45 ° with respect to the MD direction of the PEEK film used as the alignment substrate .

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction content]

As a result, a liquid crystal polymer film substantially the same as that in Example 1 was obtained. That is, the twist angle of this compensation layer was −230 °, and Δn · d was 0.84 μm. Further, when this film was transferred to a transparent film and observed by a polarization microscope, a dark field appeared every 180 ° as a rotation angle, so that it was confirmed that the orientation was perfect. At that time, the direction perpendicular to the light transmission axis of the polarizer was 45 ° with respect to the MD direction of the copper foil.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

Example 3 The immobilized liquid crystal polymer film obtained in Example 1 was transferred to a triacetyl cellulose (TAC) film by an ordinary method using an adhesive. Next, a commercially available polarizing film (PVA film containing iodine), which is also long, is laminated on the liquid crystal polymer side with an adhesive. In this lamination, long films were laminated with a roll. That is, the structure of the obtained long laminate was polarizing film / adhesive layer / liquid crystal polymer layer / adhesive layer / TAC layer. In the obtained laminate, the polarizing film side of the liquid crystal polymer layer with respect to the transmission axis of the polarizing film
Had an orientation angle of 45 °.

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0091

[Correction method] Change

[Correction content]

Example 4 Preparation of Liquid Crystal Polymer Solution The same procedure as in Example 1 was carried out except that the solution obtained in Preparation Example 2 was used, followed by coating using a die coater and drying, and then 200 ° C. The liquid crystal polymer was fixed in orientation by heat treatment for 40 minutes. The twist angle of this compensation layer is -2
At 30 °, Δn · d was 0.84 μm.

Claims (2)

[Claims] 1. A long liquid crystal polymer film oriented obliquely with respect to the MD direction at a predetermined angle. 2. A long laminated sheet for an optical element, comprising a liquid crystal polymer film layer and a polarizing film layer which are oriented at an angle of at least a predetermined angle with respect to the MD direction.