JP3469272B2 - Liquid crystalline polymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystalline polymer composition that can be used in optical elements and the like.

[0002]

2. Description of the Related Art Polymeric liquid crystals exhibit various liquid crystal phases based on their unique alignment structure, and since these liquid crystal structures can be fixed, optical recording green, nonlinear optical materials, liquid crystal alignment films,
Active research is being conducted in various functional material fields such as optical fibers and optical elements for liquid crystal display elements. Since polymer liquid crystals exhibit various orientations, materials obtained by fixing these molecular orientations exhibit various optical properties such as refractive index and birefringence, such as the phase of light and the polarization state. Since it can be controlled, it can be applied in a wide range as an optical material.

A typical example of the orientation of the polymer liquid crystal is a nematic orientation or a twisted nematic orientation. When these are oriented on a substrate, in the nematic orientation liquid crystal, the orientation direction of liquid crystal molecules (hereinafter A homogeneous alignment in which the director is substantially parallel to the substrate or a homeotropic alignment in which it is substantially vertical to the substrate is obtained, and in a chiral nematic liquid crystal, an alignment having a helical structure is obtained while being homogeneously aligned. Furthermore, by controlling the structure of liquid crystal molecules, the refractive index distribution and the spiral structure can be easily controlled. Various optical properties can be expressed by controlling these structures.

As described above, the polymer liquid crystal has excellent characteristics not found in other polymers in the variety of structures and the flexibility of controlling the optical properties based on it, but even a polymer liquid crystal is not universal and its limit is limited. Exists. That is, in any orientation behavior, the director of liquid crystal orientation can only be oriented substantially parallel or substantially perpendicular to the substrate, and there is no example in which so-called tilt orientation in which liquid crystal molecules are tilted from the substrate plane is realized.

[0005]

If it is possible to realize a so-called tilted alignment in which the director is tilted from the plane of the substrate and fix them, new performances can be obtained more than optical materials obtained by conventional polymer liquid crystal technology. Therefore, it is possible to develop a completely new optical element.

An object of the present invention is to provide a liquid crystalline polymer composition which can be tilted on a substrate and whose tilt angle can be freely controlled.

[0007]

The present invention relates to a liquid crystalline polymer composition comprising at least a homeotropically aligned liquid crystalline polymer and a homogeneously aligned liquid crystalline polymer. The composition of the present invention is a novel liquid crystalline polymer composition capable of exhibiting an alignment behavior different from that of the homeotropic alignment polymer alone or the homogeneous alignment polymer alone.

The composition of the present invention has a nematic phase or a chiral nematic phase at a temperature above the liquid crystal transition point,
A preferred embodiment includes one which becomes a glass state at a temperature below the liquid crystal transition point. Secondly, the present invention provides the above liquid crystal property.
It consists of a polymer composition, and the composition is in a liquid crystal state.
It is characterized in that the formed alignment state is fixed.
Is an optical film for a liquid crystal display device. In this case, the liquid
Crystal director fixes alignment state tilted from the substrate plane
The optical film for a liquid crystal display device described above is preferable. The present invention
Thirdly, the above liquid crystalline polymer composition is placed on the alignment substrate.
The nematic phase at a temperature above the liquid crystal transition point of the composition.
After forming the film, cooling to a temperature below the liquid crystal transition point
Therefore, vitrification was performed and the nematic phase was fixed.
Is an optical film for a liquid crystal display device. this
In this case, the film formed on the alignment substrate is
Tilt along the bing direction to
Tilt angle (θ) and retardation when measuring
The relationship with the value is asymmetric when the tilt angle is 0 degree (θ = 0 degree)
Optical films for liquid crystal display devices, which have a good curve relationship, are preferred.
Good Also, refraction in the rubbing direction occurs on the interface side of the alignment substrate.
The index is greater than the index of refraction in the direction perpendicular to that direction
On the one interface side, the liquid with the same in-plane refractive index in all directions
An optical film for a crystal display element is more preferable. Further orientation
On the substrate interface side, liquid crystal molecules are arranged in a direction substantially parallel to the substrate.
On the other interface side, the liquid crystal molecules are
The optical film for liquid crystal display elements that is vertically aligned
More preferable. Fourthly, the present invention is for the above liquid crystal display device.
A liquid crystal comprising an optical film and a polarizing plate
It is an optical element for a display element. Fifth, the present invention provides the above liquid.
Crystal display having at least an optical film for a crystal display element
It is an element.

The present invention will be described in detail below.

The liquid crystalline polymer composition of the present invention is characterized in that it contains a homeotropically aligned liquid crystalline polymer and a homogeneously aligned liquid crystalline polymer as essential components.

Further, in order to fix the liquid crystal orientation, it is preferable to use a material that does not have a crystal phase and vitrifies at a temperature lower than that of the liquid crystal phase. The type of the liquid crystal phase of the composition includes a tilted nematic phase and a tilted chiral nematic phase obtained by introducing an optically active unit into the polymer or adding an optically active compound separately. Or the case of cholesteric phase) is preferable.

First, a homeotropic alignment liquid crystalline polymer (polymer) and a homogeneous alignment liquid crystalline polymer (polymer), which are important constituents of the polymer composition of the present invention.
The features of will be described. Homeotropic alignment refers to an alignment state in which the director is substantially vertical to the plane of the substrate, and homogeneous alignment refers to an alignment state in which the director is substantially horizontal to the plane of the director substrate.

The orientation of the polymer can be determined by determining the homeotropic orientation or the homogeneous orientation of the liquid crystalline polymer in the liquid crystal state when the liquid crystalline polymer layer is formed on the substrate. The substrate that can be used for this determination is not particularly limited, but examples include a glass substrate (such as soda glass, potash glass, borosilicate glass or crown glass, and optical glass such as flint glass), at the liquid crystal temperature of the liquid crystalline polymer. Heat-resistant plastic film or sheet such as polyethylene terephthalate, polyethylene naphthalate, polyphenylene oxide, polyimide, polyamide imide, polyether imide, polyamide, polyether ketone, polyether ether ketone, polyketone sulfide, polyether sulfone You can These substrates are used after cleaning their surfaces with acids, alcohols, detergents, etc., but they are used without surface treatment such as silicon treatment.
When a polymer film is formed on these appropriate substrates and heat-treated at a liquid crystal temperature, at least one of these exemplified substrates is homeotropically aligned on at least one of these substrates and is referred to as a homeotropic alignment polymer. Let's define it. On the other hand, a polymer having a homogeneous orientation with respect to any substrate, that is, a polymer determined not to have homeotropic orientation is defined as a homogeneous orientation polymer. However, since some polymers are specifically homeotropically aligned at a temperature near the liquid crystal phase-isotropic phase transition point, the heat treatment is usually performed at 15 ° C. or lower than the liquid crystal phase-isotropic phase transition temperature, preferably It is performed at a temperature of 20 ° C or lower.

Next, the structure of the polymer will be described. First, the features common to homeotropically oriented polymers and homogeneously oriented polymers will be described. The type of liquid crystal polymer used is not particularly limited, and examples thereof include main chain type liquid crystal polymers such as polyester, polyamide, polycarbonate, and polyesterimide, or side chain type liquid crystal polymers such as polyacrylate, polymethacrylate, polymalonate, and polysiloxane. can do.
Among them, polyester is preferable from the viewpoint of easiness of synthesis, orientation, glass transition point and the like. The constitutional unit of the polyester is not particularly limited, but a preferable example thereof is a unit derived from a dicarboxylic acid (a) (hereinafter,
Dicarboxylic acid unit), (b) a unit derived from a diol (hereinafter referred to as a diol unit), (c) a unit derived from an oxycarboxylic acid having both a carboxyl group and a hydroxyl group in one unit (hereinafter Oxycarboxylic acid unit) and the like. A unit derived from a compound having an asymmetric carbon can also be used as a structural unit,
Most of the polymers containing optically active units exhibit a chiral nematic phase (twisted nematic phase, cholesteric phase) as a liquid crystal phase. On the other hand, those containing no optically active unit show a nematic phase as a liquid crystal phase. The structure of polyester is (a) + (b) type, (a) +
There are (b) + (c) type and (c) single type.

Examples of the dicarboxylic acid unit (a) include, for example,

[0016]

[Chemical 1]

(X is hydrogen, halogen such as chlorine or bromine, an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, etc.)) Or an alkoxy group (for example,
Examples thereof include a methoxy group, an ethoxy group, a prepoxy group and a butoxy group) or a phenyl group. k is 0 to 2, the same applies hereinafter),

[0018]

[Chemical 2]

[0019]

[Chemical 3]

(* Indicates optically active carbon. The same applies hereinafter)

[0021]

[Chemical 4]

And the like.

Examples of the diol unit (b) include, for example,

[0024]

[Chemical 5]

[0025]

[Chemical 6]

And the like.

As the oxycarboxylic acid unit of (C),
For example

[0028]

[Chemical 7]

And the like.

Typical examples of homeotropically oriented polymers and homogeneously oriented polymers are shown below.

The homeotropically oriented polymer and the other homogeneously oriented polymers are distinguished by the above-mentioned judgment method. As the polymer having the homeotropic orientation, the above-mentioned polyester-based polymers are typically used. A polyester containing an aromatic unit having an alkyl group having 3 or more carbon atoms, preferably 3 to 12 carbon atoms as a substituent or a part of the substituent, as a part of the substituted structural unit or an additional structural unit of the structural unit, Examples of such constitutional units include polyesters containing an aromatic unit having a fluorine or a fluorine-containing substituent as a substituent or a part of the substituent.

Among such constitutional units, examples of the aromatic unit having a substituent or an alkyl group having 3 or more carbon atoms as a part of the substituent include, for example,

[0033]

[Chemical 8]

(R is an alkyl group having 3 to 12 carbon atoms , iP
Examples of r include isopropyl, and examples of tBu include tertiary butyl . Further, as the aromatic unit having a fluorine or fluorine-containing substituent,

[0035]

[Chemical 9]

And the like.

Further, in order to fix the alignment structure of the liquid crystalline polymer composition of the present invention, it is preferable to use one which does not crystallize at a temperature lower than the liquid crystal phase and takes a glass state. When the liquid crystal structure of the composition is fixed, the polymer molecules are once aligned at the liquid crystal temperature, and then cooling for fixing is performed.However, when a composition having a crystal phase is used, the alignment state once obtained is There is a risk of destruction. For example, in the case of the above-exemplified polyester-based polymer, an ortho-substituted aromatic unit is preferably used as a constituent unit that suppresses crystallization, and a polyester-based polymer containing such a unit is suitable. The ortho-substituted aromatic unit here means a structural unit in which the bonds forming the main chain are ortho to each other. In order for the composition to take the glass state without causing crystallization at a temperature lower than the liquid crystal phase, at least one of the homeotropically oriented polymer and the homogeneously oriented polymer forming the composition contains these structural units. Preferably. Specific examples of these ortho-substituted aromatic units include catechol units, salicylic acid units, phthalic acid units and those having a substituent on the benzene ring of these groups as shown below.

[0038]

[Chemical 10]

Etc. Among these, the following can be exemplified as particularly preferable examples.

[0040]

[Chemical 11]

[0041]

[Chemical 12]

With respect to the homeotropic alignment polymer and the homogeneous alignment polymer which compose the liquid crystal composition of the present invention, the following polymers can be specifically exemplified as suitable polyesters.

First, as the homeotropically oriented polymer,

[0044]

[Chemical 13]

A polymer composed of the structural unit of (wherein k, l, and m are merely composition ratios (mole), and k = 1 + m, 1 / m = 100/0 to 20/80, preferably Is 95/5 to 30/70)

[0046]

[Chemical 14]

A polymer composed of the structural unit of (wherein k, l, and m are merely compositional ratios (mole), and k = l + m, 1 / m = 98/2 to 20/80, preferably Is 95/5 to 30/70)

[0048]

[Chemical 15]

A polymer composed of the structural unit of (wherein k, l, m, and n are merely composition ratios (mole), and k = l + m + n, 1 / m = 98/2 to 20/8.
0, preferably 95/5 to 30/70, 1 / n = 98 /
2 to 20/80, preferably 95/5 to 30/70)

[0050]

[Chemical 16]

A polymer composed of the structural unit of (wherein k, l, and m are merely compositional ratios (mole), and k + 1 = m, k / l = 98/2 to 20/80, preferably Is 95/5 to 30/70)

[0052]

[Chemical 17]

A polymer composed of the structural unit (wherein k, l, and m are simply composition ratios (mole), and k / l = 98/2 to 20/80, preferably 95 / l.
5/30/70 and 1 / m = 98/2 to 20/8
0, preferably 95/5 to 30/70, and n is 2 to
It is an integer of 12)

[0054]

[Chemical 18]

A polymer composed of the structural unit of (wherein k, l, and m are merely compositional ratios (mole), and k = l + m, 1 / m = 98/2 to 20/80, preferably Is 95/5 to 30/70)

[0056]

[Chemical 19]

A polymer composed of the structural unit of (wherein k, l, m and n simply represent the composition ratio (mol), and k + l = m + n, k / l = 100/0 to 0/1.
00, preferably 95/5 to 5/95, m / n = 98 /
2 to 20/80, preferably 95/5 to 30/70)

[0058]

[Chemical 20]

A polymer constituted by the structural unit of (wherein k, l, and m are merely compositional ratios (mole), and k = 1 + m, 1 / m = 100/0 to 0/100, preferably Is 98/2 to 2/98, and n is an integer of 2 to 12)

And the like. Of course, in these formulas, the composition ratios of the respective structural units k, l, m, etc. merely indicate a molar ratio, not a block-like unit.

Examples of the homogeneously oriented polymer include, for example,

[0062]

[Chemical 21]

A polymer composed of the structural unit of (wherein k, l, and m are merely composition ratios (mole), and k = 1 + m, 1 / m = 80/20 to 20/80, preferably Is 75/25 to 25/75)

[0064]

[Chemical formula 22]

A polymer composed of the structural unit of (wherein k, l, and m are merely compositional ratios (mole), and k = l + m, 1 / m = 80/20 to 20/80, preferably Is 75/25 to 25/75)

[0066]

[Chemical formula 23]

A polymer composed of the structural unit (wherein k, l, and m are simply composition ratios (mole), and k = 1 + m, 1 / m = 80/20 to 20/80, preferably Is 75/25 to 25/75)

[0068]

[Chemical formula 24]

A polymer composed of the structural unit of (wherein k, l, m, and n are merely composition ratios (mole), and k = l + m + n, 1 / m = 80/20 to 20 /
80, preferably 75/25 to 25/75, 1 / n = 8
0/20 to 20/80, preferably 75/25 to 25 /
75)

[0070]

[Chemical 25]

A polymer composed of the structural unit of (wherein k, l, m and n simply represent the composition ratio (mol), and k + l = m + n, k / l = 80/20 to 20 /
80, preferably 75/25 to 25/75, m / n = 8
0/20 to 20/80, preferably 75/25 to 25 /
75)

[0072]

[Chemical formula 26]

A polymer constituted by the structural unit of (wherein k, l, and m are merely composition ratios (mole), and k = 1 + m, 1 / m = 80/20 to 20/80, preferably Is 75/25 to 25/75)

[0074]

[Chemical 27]

A polymer composed of the structural unit (wherein k, l, and m are merely composition ratios (mole), and k / l = 80/20 to 20/80, preferably 75.
/ 25 to 25/75, and 1 / m = 80/20 to 20
/ 80, preferably 75/25 to 25/75)

[0076]

[Chemical 28]

A polymer composed of the structural unit of (wherein k, l, m and n simply represent the composition ratio (mol), and k + l = m + n, k / l = 80/20 to 20 /
80, preferably 75/25 to 25/75, m / n = 8
0/20 to 20/80, preferably 75/25 to 25 /
75 and p is 2 to 12)

[0078]

[Chemical 29]

A polymer composed of the structural unit of (wherein k, l, and m are merely compositional ratios (mole), and k + 1 = m, k / l = 80/20 to 20/80, preferably Is 75/25 to 25/75, and p is 2 to 12
Is)

And the like.

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, and more preferably 0.07 to 2.0. Logarithmic viscosity is 0.0
If it is less than 5, 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 are 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.

As described above, the liquid crystalline polymer composition of the present invention is characterized in that it contains at least the above-mentioned homeotropically oriented polymer and homogeneously oriented polymer, but is twisted in the orientation structure of the composition. Further, an optically active substance can be added in order to imprint. In this case, as described above, the composition usually takes a chiral nematic phase as a liquid crystal phase also in the case where an optically active unit is contained in the skeleton of the homeotropically oriented polymer and / or the homogeneously oriented polymer.

As the optically active substance as such an additive, either a low molecular weight compound or a high molecular weight compound can be used as long as it is a compound having an optical activity, but it is an optically active substance from the viewpoint of compatibility with a liquid crystalline polymer as a base. A liquid crystal compound is preferable, and specific examples thereof include the following compounds.

[0085]

[Chemical 30]

[0086]

[Chemical 31]

Cholesterol derivatives, etc.

Further, as such an optically active compound, other optically active polymers can be mentioned. Any polymer having an optically active group in the molecule can be used, but a polymer exhibiting 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.

[0089]

[Chemical 32]

A polymer composed of structural units of

[0091]

[Chemical 33]

A polymer composed of structural units of

[0093]

[Chemical 34]

A polymer composed of structural units (n = 2 to 12),

[0095]

[Chemical 35]

A polymer composed of structural units of

[0097]

[Chemical 36]

A polymer composed of structural units of

[0099]

[Chemical 37]

A polymer composed of structural units of

[0101]

[Chemical 38]

A polymer composed of structural units of

[0103]

[Chemical Formula 39]

A polymer composed of structural units of

[0105]

[Chemical 40]

A polymer composed of structural units of

[0107]

[Chemical 41]

A polymer composed of structural units of

[0109]

[Chemical 42]

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 such that the logarithmic viscosity measured at 30 ° C. in phenol / tetrachloroethane is in the range of 0.05 to 5.0. If the logarithmic viscosity exceeds 5.0, the viscosity may be too high, resulting in a decrease in orientation, which is preferable in some cases.
If it is less than the above range, the composition may be difficult to control, which is not preferable.

The composition of the present invention comprises a homeotropic alignment polymer and a homogeneous alignment polymer which are essential components, or an optional component such as an optically active compound, which is a solid mixture, a solution mixture or a melt. It can be obtained by mixing. The conditions at this time are not particularly limited and are appropriately selected by a known method.

The mixing ratio of the homeotropic orienting polymer and the homogeneous orienting polymer varies depending on the polymer and the purpose, and cannot be generally referred to, but usually, the weight ratio is 99: 1 to 0.5: 99.5, More preferably 98:
2 to 1:99, and more preferably 95: 5 to 2:98. 0.5% by weight of homeotropic oriented polymer
When the amount is less than the above, the property of the composition is almost the same as when the homogeneously oriented polymer is used alone, and the desired novel oriented structure may not be obtained, and when the amount of the homogeneously oriented polymer is less than 1% by weight, the same is true. In some cases, the properties are almost the same as when the homeotropically oriented polymer is used alone.

When an optically active substance is added, its proportion in the composition is usually 50% by weight or less, preferably 40% by weight or less, more preferably 0.1 to 35%.
Weight percent is preferred.

The composition of the present invention does not contain an optically active substance, and when neither the homeotropically oriented polymer nor the homogeneously oriented polymer, which is an essential component, contains an optically active unit, a nematic phase is formed. Mochi,
When it exceeds 0% by weight, it has a twisted nematic phase (or cholesteric phase). However, when the amount of the optically active substance exceeds 50% by weight, phase separation tends to occur in the composition.

When the liquid crystalline polymer composition thus obtained is oriented on a substrate, it is possible to realize an intermediate tilted orientation, which is neither conventional homeotropic orientation nor homogeneous orientation. That is, the long axes of the polymer molecules constituting the composition can be oriented so that they are different from the substrate surface and the substrate normal direction. Furthermore, by introducing an optically active unit into the polymer or by allowing an optically active substance to coexist in the composition, a structure having a twisted structure (helical structure) while being tilted can be realized. Further, since the composition of the present invention has a glass phase at a temperature lower than the liquid crystal phase, it can be a transparent material in which the liquid crystal state is fixed to glass. The immobilization product having such a unique orientation structure has a novel optical performance because it has not been obtained in the past, and can be used for various optical applications, and is extremely industrially valuable.

[0118]

EXAMPLES Examples will be described below, but the present invention is not limited thereto. The analytical methods used in the examples are as follows.

(1) Determination of polymer composition The polymer was dissolved in deuterated chloroform or deuterated trifluoroacetic acid, and the solution was adjusted to 400 MHz. ^It was measured and determined by ¹ H- NMR (JNM-GX400 manufactured by JEOL Ltd.).

(2) Measurement of logarithmic viscosity Using an Ubbelohde viscometer, the viscosity was measured in a phenol / tetrachloroethane (60/40 weight ratio) mixed solvent at 30 ° C.

(3) Determination of liquid crystal phase sequence DSC (DuPont 990 Thermal An)
It was determined by the measurement of the alizer) and observation with an optical microscope (BH2 polarizing microscope manufactured by Olympus Optical Co., Ltd.).

(4) Measurement of Refractive Index The refractive index was measured with an Abbe refractometer (Type-4 manufactured by Atago Co., Ltd.).

Example 1 100 mmol of terephthalic acid, 50 mmol of hydroquinone diacetate, 50 mmol of tert-butylcatechol diacetate and 100 mg of sodium acetate were used to carry out polymerization at 300 ° C. for 1 hour under a nitrogen atmosphere.
Next, the obtained polymer is dissolved in tetrachloroethane and then reprecipitated with methanol to obtain a purified polymer 25.
0 g was obtained. This polymer had an inherent viscosity of 0.30, a nematic phase as a liquid crystal phase, an isotropic phase-liquid crystal phase transition temperature of 300 ° C. or higher, and a glass transition point of 130 ° C.

Using this polyester, a 10 wt% tetrachloroethane solution was prepared. This solution was applied onto a soda glass plate by a screen printing method, dried, heat treated at 220 ° C. for 30 minutes and then cooled to a film thickness of 50 μm.
A uniformly aligned liquid crystal film was obtained. Observation with a conoscope revealed that the polymer liquid crystal had a positive uniaxial structure and that this polymer had homeotropic alignment.

Example 2 A polymer of formula (1) was synthesized. Logarithmic viscosity is 0.35,
It had a nematic phase as a liquid crystal phase, an isotropic phase-liquid crystal phase transition temperature of 300 ° C. or higher, and a glass transition point of 105 ° C. Using this polyester, a 10 wt% tetrachloroethane solution was prepared, applied to various orientation test substrates by the screen printing method, and then dried, 250 ° C. × 30
Partial heat treatment was performed. As the substrate, soda glass, borosilicate glass, polyethylene terephthalate film, polyimide film, polyetherimide film, polyetheretherketone film, polyethersulfone film was used, but on any substrate schlieren structure by microscopic observation of the liquid crystal phase It was found that this polymer had a homogeneous orientation.

[0126]

[Chemical 43]

Example 3 5 g of the polymer of Example 1 and 5 g of the polymer of the formula (1) of Example 2 were mixed and dissolved in 90 g of tetrachloroethane. This solution was applied onto a glass substrate having a rubbing polyimide film by spin coating and dried. Treated in an oven at 220 ℃ for 30 minutes and then air-cooled to give a clear 6μm
A film of By constructing the optical measurement system as shown in Fig. 1 and Fig. 2,
The sample was tilted along the rubbing direction of the substrate to examine the apparent retardation value (product of birefringence Δn and film thickness d). The relationship between the sample tilt angle θ and the apparent retardation value is as shown by the solid line in FIG. It was found to have a structure tilted with respect to the substrate. Further, it was estimated by simulation that the apparent average tilt angle was about 20 degrees with respect to the substrate.

Comparative Example 1 Using only the polymer of the formula (2), a 10 wt% tetrachloroethane solution was prepared, coated on a glass substrate having a rubbing polyimide film, dried, heat-treated at 220 ° C. for 30 minutes and then air-cooled. A transparent film of about 6.5 μm was obtained. The same optical measurement as in Example 3 was performed to obtain the curve shown by the dotted line in FIG. In this case, it is symmetric with respect to θ = 0 degree,
It was found that the homogeneously oriented polymer of the formula (2) alone cannot provide a tilt structure.

Example 4 A homeotropically oriented polymer of the formula (2) and a homogeneously oriented polymer of the formula (3) were synthesized. The polymer of formula (2) had a logarithmic viscosity of 0.2 and had a crystal phase below the liquid crystal phase (liquid crystal phase-crystal phase transition temperature 180 ° C.).
The polymer of formula (3) had a logarithmic viscosity of 0.25 and a glass phase below the liquid crystal phase (Tg = 95 ° C.). Formula (2)
The polymer and the polymer of formula (3) are mixed in a weight ratio of 1: 2,
It was dissolved in chloroform to prepare a 5 wt% polymer solution. This solution was coated on a glass substrate with a polyimide film subjected to a rubbing treatment by a roll coater, dried, and then 200
It heat-processed at 30 degreeC for 30 minutes, and air-cooled. The obtained film on glass was transparent and no crystallization was observed. The apparent tilt angle was about 15 degrees.

[0130]

[Chemical 44]

[0131]

[Chemical formula 45]

Example 5 The chloroform solution used in Example 4 was used as a solvent.
The polymer composition obtained by evaporating chloroform was subjected to DSC measurement to obtain the chart in FIG. There was only a glass phase below the liquid crystal phase, and no crystal phase was found.

Example 6 Homeotropically oriented polymer of formula (4) and formula (5)
Of the homogeneously oriented polymer of Example 1 was synthesized by an acid chloride method, and these were mixed at a weight ratio of 1: 9 or 2: 8, and a mixed solvent of tetrachloroethane and phenol (4:
6 wt%) to prepare polymer solutions of 15 wt% each. A glass substrate with a polyvinyl alcohol film that had been subjected to a rubbing treatment was applied, dried and heat-treated to obtain a tilt-oriented polymer film having a thickness of about 4 μm. When formula (4): formula (5) is 9: 1, the apparent tilt angle is 1
The apparent tilt angle was 17 ° when 0 ° and the formula (4): formula (5) = 8: 2.

[0134]

[Chemical formula 46]

[0135]

[Chemical 47]

Example 7 A polymer of the formula (6) was synthesized and aligned on a flint glass to obtain homeotropic alignment. This sample was measured with a refractometer, ne = 1.74, no = 1.
54 was obtained. Therefore, it was estimated that the birefringence Δn = 0.20.

Further, the polymer of the formula (7) was a polymer having a homogeneous orientation behavior, but when the polymer was oriented on a flint glass having a rubbing polyimide film, a monodomain homogeneous orientation was obtained. It was ne = 1.76, no = 1.57, Δn = 0.
It was 19.

When a composition having a weight ratio of the formulas (6) and (7) of 1: 1 was oriented on a glass substrate having a rubbing polyimide film, a transparent film was obtained, and a thickness d = 5.2 μm.
The retardation Δnd was 0.53 μm.
From this, it was found that the apparent Δn was 0.10, which was significantly smaller than the birefringence values of the individual polymers of the formulas (6) and (7) forming this composition. From this, it was suggested that the composition represented by the formulas (6) and (7) had a tilt orientation.

[0139]

[Chemical 48]

[0140]

[Chemical 49]

Example 8 A composition prepared by melt-mixing a homeotropically oriented polymer of the formula (8) (2-methylbutanediol unit is a racemic body) and a homogeneously oriented polymer of the formula (9) in a weight ratio of 3: 2. Prepared. Then the composition is heated to 260 ° C.,
High refractive index glass (n =
1.84) in a molten state and then air-cooled for orientation fixing to obtain a transparent polymer film having a thickness of 10 μm.
When the refractive index near the interface of this sample was measured by a refractometer, the refractive index of the polymer near the interface between the polymer and the air was almost equal in all directions in the plane, n = 1.57, and in the thickness direction, n = 1.72. Met. On the other hand, at the interface between polyimide and polymer, n = 1.7 in the direction parallel to the rubbing direction.
2. n = 1.5 in the direction perpendicular to the in-plane rubbing direction
7, and n = 1.57 in the thickness direction. From this, it was estimated that the composition had the oriented structure shown in FIG.

[0142]

[Chemical 50]

[0143]

[Chemical 51]

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a method of measuring retardation used in Example 3.

FIG. 2 is a top view of the measurement system of FIG. 1, showing the axial orientation of each member.

FIG. 3 is a result of measuring the relationship between the apparent retardation value and the tilt angle of the sample in Example 3 (solid line).
And the dotted line are graphs showing the measurement results (dotted line) of the non-tilted sample of Comparative Example 1.

FIG. 4 is a DSC chart of the composition of Example 4.

5 is a conceptual diagram of an alignment structure of Example 8. FIG.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C09K 19/02 C09K 19/38 G02F 1/13

Claims (10)

(57) [Claims] 1. A liquid crystalline polymer composition comprising at least a homeotropic aligned liquid crystalline polymer and a homogeneous aligned liquid crystalline polymer. 2. The liquid crystalline polymer composition according to claim 1, which has a nematic phase or a chiral nematic phase at a temperature equal to or higher than the liquid crystal transition point and becomes a glass state at a temperature equal to or lower than the liquid crystal transition point. 3. The liquid crystalline polymer composition according to claim 1 or 2.
The composition formed in the liquid crystal state.
Liquid crystal table characterized by fixing the orientation state
Optical film for display element. 4. The liquid crystal director is tilted from the substrate plane
4. The alignment state is fixed, according to claim 3.
Optical film for liquid crystal display devices. 5. The liquid crystalline polymer composition according to claim 1 or 2.
The composition is placed on an alignment substrate and the liquid crystal transition temperature of the composition is not less than
After forming a nematic phase at a temperature, the temperature below the liquid crystal transition point
Vitrified by cooling to the nematic
An optical fiber for a liquid crystal display device characterized by fixing the phase
Film. 6. Orient the film formed on the substrate
Tilt along the rubbing direction of the substrate to
The tilt angle (θ) and retardation
Relationship with the orientation value is related to the tilt angle of 0 degree (θ = 0 degree).
Asymmetric curve relationship is obtained.
5. The optical film for a liquid crystal display device according to item 5. 7. Refraction in the rubbing direction on the interface side of the alignment substrate
The index is greater than the index of refraction in the direction perpendicular to that direction,
On one interface side, the in-plane refractive index is the same in all directions.
7. The light for a liquid crystal display element according to claim 5 or 6,
Science film. 8. On the interface side of the alignment substrate, liquid crystal molecules
And align in a substantially parallel direction, and the liquid crystal component on the other interface side.
Characteristic that the daughter is oriented substantially perpendicular to the substrate
The liquid crystal display element according to any one of claims 3 to 7.
Optical film for children. 9. The liquid according to any one of claims 3 to 6.
It consists of an optical film for crystal display element and a polarizing plate.
Optical element for liquid crystal display element. 10. The method according to any one of claims 3 to 6.
A liquid crystal table including at least an optical film for a liquid crystal display device
Display element.