JPH1048633A - Liquid crystal element and its production as well as apparatus for producing oriented film used for this production process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form oriented films having high anisotropy and to produce a liquid crystal element having excellent surface characteristics free from orientation defects by a clean process with good yield by developing and compressing a monomolecular film forming material on a liquid surface and laminating this material on a substrate, thereby forming the oriented films. SOLUTION: The monomolecular film forming material is developed and compressed on the liquid surface and is laminated on a pair of substrates 11a, 11b having electrodes on their respective opposite surface sides, by which the oriented films 14a, 14b are formed at the time of producing the liquid crystal element which is formed by holding a liquid crystal compsn. exhibiting a chiral smectic phase between these substrates and has the oriented films 14a, 14b on at least one of electrodes 12a, 12b. In such a case, the liquid crystal element is provided with shorting preventive films 13a, 13b at need between the oriented films 14a, 14b and the transparent electrodes 12a, 12b. The upper and lower substrates are stuck to each other by using a sealing material 15 via bead spacers 16, such as silica beads, by which a cell is constituted. The liquid crystals are injected into this cell by utilizing capillarity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal element used for a light valve used in a flat panel display, a projection display, a printer, and the like, and a method for manufacturing the same. The present invention relates to an apparatus for producing a monomolecular film constituting a certain orientation control film.

[0002]

2. Description of the Related Art Conventionally, widely used liquid crystal elements are described, for example, by M. Schadt and W. Helfrich.
Applied Physics Letters (Applied
Physics Letters, Vol. 18, No. 4 (published Feb. 15, 1971), pp. 127-128, Twisted Nematic (Twis)
A liquid crystal using a ted nematic liquid crystal is known. Further, a simple matrix type liquid crystal element is known as a typical liquid crystal element. This type is easy to fabricate the element and is significant in cost.
However, in the case of time-division driving using a matrix electrode structure with a high pixel density, there is a problem that crosstalk occurs, so that the number of pixels has been limited. Further, since the response speed is as slow as 10 msec or more, the use as a display is limited. In recent years, a TFT (Thin Fil) has been applied to such a simple matrix type element.
m Transistor) is being developed. In this type, a transistor is manufactured for each pixel, so that the problems of crosstalk and response speed are solved.However, the larger the area, the more difficult it is to manufacture a liquid crystal element without defective pixels. Greater costs are incurred for better retention.

In order to improve the disadvantages of the conventional liquid crystal device, a liquid crystal device having bistability is disclosed in Clark and Lagerwell.
(JP-A-56-107216, U.S. Pat. No. 4,367,924). In general, a ferroelectric liquid crystal having a chiral smectic C phase is used for a liquid crystal device having this bistability. Since this chiral smectic liquid crystal performs inversion switching by spontaneous polarization, it has a very fast response speed and can exhibit a bistable state with memory properties in a thin cell. Further, since it has excellent viewing angle characteristics, it is considered to be suitable as a high-speed, high-definition, large-area display element or light valve. Recently, a chiral smectic antiferroelectric liquid crystal device having three stable states has also been proposed by Chandani, Takezoe et al. (Japanese Journal of A).
Applied Physics, Vol. 27, 1988, L729).

In a chiral smectic liquid crystal element, for example, as described in “Structure and Physical Properties of Ferroelectric Liquid Crystal” (Atsuo Fukuda and Hideo Takezoe, 1990, published by Corona Co., Ltd.), zigzag alignment defects occur. As a result, there is a problem that the contrast is significantly reduced. This defect is attributable to the fact that the layered structure of the chiral smectic liquid crystal sandwiched between the upper and lower substrates forms two types of chevron structures. Recently, there has been a movement to eliminate the chevron structure having such a drawback and to realize a layered structure called a bookshelf or a structure similar thereto, thereby realizing a high-contrast good liquid crystal element (for example, "Next-generation liquid crystal display and Liquid crystal materials, edited by Atsuo Fukuda, 1
Published by CMC Co., Ltd. in 992).

A liquid crystal material having a perfluoroether side chain (US Pat. No. 5,262,082,
International Patent Application WO93 / 22396, 1993 Fourth International Conference on Ferroelectric Liquid Crystal P-46, Marc D. Radc
life et al.) are disclosed. This liquid crystal can exhibit a bookshelf or a structure with a small layer tilt angle close to the bookshelf without using an external field such as an electric field, and is suitable for high-speed, high-definition, large-area liquid crystal elements and display devices.

[0006]

Generally, to align a chiral smectic liquid crystal, a polyimide (P
I) A pair of substrates formed by forming a polymer film of horizontal orientation or inclined orientation such as polyvinyl alcohol (PVA) or polyamide (PA), and rubbing in substantially the same direction is used. The mechanism by which the rubbing treatment can achieve uniform alignment of the liquid crystal has not yet been clarified in many parts, but it is important that the molecular chains of the polymer film as the alignment film have anisotropy. Some have been confirmed in various ways (eg, MF Tonye et al., N.
ature. vol374.20, APRIL, p70
9, 1995). The rubbing method is very excellent in giving sufficient anisotropy to the polymer film, and is a simple method. However, this method has problems such as surface contamination of the film, alignment defects of the liquid crystal due to peeling of the film, and generation of dust in the production process of the liquid crystal element which should be a clean process.

On the other hand, the Langmuir-Blodgett method (hereinafter referred to as the LB method) has attracted attention in that it is a so-called rubbing-less process that can avoid contamination and peeling of a film. However, the orientation film formed by the LB method often cannot impart sufficient uniaxial orientation to the chiral smectic liquid crystal, and particularly has no cholesteric phase (Ch) and isotropic phase (Iso. ) → Smectic A phase (SmA) → Chiral smectic C phase (SmC ^* ) When using a liquid crystal, Iso. → At the time of SmA transition, since sufficient uniaxiality cannot be imparted to batone, alignment defects and the like are generated, and uniform alignment is often not obtained. This is considered to be mainly because the anisotropy of the alignment film formed by the LB method is smaller than that of the rubbing.

[0008] An object of the present invention is to solve the above-mentioned problem and to provide an LB
An object of the present invention is to produce a liquid crystal element having excellent display characteristics without alignment defects by forming an alignment film having higher anisotropy by using the method, with a very clean process and a good yield.

[0009]

According to a first aspect of the present invention, a liquid crystal composition exhibiting a chiral smectic phase is sandwiched between a pair of substrates each having an electrode on the opposite surface side, and an alignment is provided on at least one electrode. A method for manufacturing a liquid crystal element having a film, wherein a material for forming a monomolecular film is developed and compressed on a liquid surface,
A method for manufacturing a liquid crystal element, comprising a step of forming the alignment film by laminating on a substrate.

[0010] A second aspect of the present invention is an apparatus used in the above manufacturing method, wherein a developing region for developing the monomolecular film forming material on a liquid surface, and the monomolecular film forming material developed on the liquid surface are provided. A compression region that is a monomolecular film by compressing a monolayer, a lamination region for laminating the monomolecular film on a substrate, and a mechanism for constantly flowing a liquid from the development region to the lamination region via the compression region. And a surface pressure control loop for controlling the developing speed of the monomolecular film forming material to maintain the surface pressure of the developed monomolecular film forming material at a predetermined value, and flowing into the water tank. A water level control loop for maintaining the water level of the stacking region at a predetermined value by adjusting the amount of liquid to be applied, and a compression control for mechanically compressing the monomolecular film in the stacking region by a barrier on the water surface. And a loop That is an orientation film manufacturing equipment.

A third aspect of the present invention is a liquid crystal device manufactured by the above manufacturing method, wherein a liquid crystal composition exhibiting a chiral smectic phase is sandwiched between a pair of substrates each having an electrode on the opposite surface side. And a liquid crystal element having an alignment film made of a monomolecular film on at least one electrode.

Although the present invention is effective in obtaining a uniform alignment of a chiral smectic liquid crystal having no Ch, it can also improve the alignment uniformity of a chiral smectic liquid crystal having a Ch.

[0013]

FIG. 1 is a sectional view showing an example of the liquid crystal device of the present invention. In the figure, 10 is a liquid crystal layer, 11a and 11b.
Is a glass substrate, 12a and 12b are transparent electrodes, 14a and 1
Reference numeral 4b denotes an alignment film, and between the alignment films 14a and 14b and the transparent electrodes 12a and 12b, a short-circuit prevention film 13
a and 13b are provided as needed. The upper and lower substrates are sealed with a sealing material 15 through bead spacers 16 such as silica beads.
Are bonded together to form a cell, and a liquid crystal is injected by utilizing a capillary phenomenon or the like. The above transparent electrode 1
As 2a and 12b, In ₂ O ₃ , SnO ₂ or IT
A thin film such as O (Indium Tin Oxide) is used.

In the present invention, the liquid crystal composition to be used preferably has a terminal portion of a fluorocarbon and a terminal portion of a hydrocarbon, and both terminal portions are bound by a central nucleus and have a smectic intermediate phase or a potential smectic intermediate phase. Those containing a fluorine-containing liquid crystal compound are desirable.

In the fluorine-containing liquid crystal compound, the terminal portion of the fluorocarbon is a group represented by -D ¹ -C _xa F _2xa -X (provided that xa is 1 to 20;
It represents -H or -F, D ¹ is, -CO-O- (C
_{H 2) ra -, - O-} (CH 2) ra -, - (CH 2) ra -,
_{-O-SO 2 -, - SO} 2 -, - SO 2 - (CH 2) ra -,
_{-O- (CH 2) ra -O- (} CH 2) rb -, - (CH 2)
_{ra -N (C pa H 2pa +} 1) -SO 2 -, or - (CH _{2) ra
-N (C pa H 2pa + 1} ) represents the -CO-. ra and rb
Is independently 1 to 20, and pa is 0 to 4. ),
Alternatively, a group represented by -D ^2- (C _xb F _2xb -O) _za -C _ya F _{2ya + 1} (where xb is each of (C
_xb F _2xb -O) is independently 1 to 10, and ya is 1 to
10, za is 1 to 10, and D ² is -CO-
_{O-C rc H 2rc, -O} -C rc H 2rc -, - C rc H 2rc -,
_{-O- (C sa H 2sa -O)} ta -C rd H 2rd -, - O-SO
_{2 -, - SO 2 -,} - SO 2 -C rc H 2rc -, - C rc H 2rc
_{-N (C pb H 2pb + 1} ) -SO 2 -, - C rc H 2rc -N (C
_pb H _2pb + 1) -CO-, selected from a single bond, rc and r
d is independently 1 to 20, sa is independently 1 to 10 for each (C _sa H _2sa -O), and ta is 1
And pb is 0-4. ) Can be used.

Particularly preferably, a fluorine-containing liquid crystal compound represented by the following general formula (I) or (II) can be used.

[0017]

Embedded image Represents

Ga, ha and ia each independently represent an integer of 0 to 3 (provided that ga + ha + ia is at least 2).

Each of L ¹ and L ² is independently a single bond, -CO
-O-, -O-CO-, -COS-, -S-CO-,-
CO-Se-, -Se-CO-, -CO-Te-, -T
_{e-CO -, - CH 2} CH 2 -, - CH = CH -, - C≡
C -, - CH = N - , - N = CH -, - CH 2 -O-,
-O-CH ₂ -, - CO- or represent -O-.

Each of X ¹ , Y ¹ and Z ¹ is a substituent of A ¹ , A ² and A ³ and independently represents —H, —Cl, —F, —Br,
_{I, -OH, -OCH 3, -CH} 3, -CN, or -NO
₂ and each of ja, ma and na independently represents an integer of 0-4.

J ¹ is —CO—O— (CH ₂ ) _ra —, —O
_{- (CH 2) ra -,} - (CH 2) ra -, - O-SO 2 -,
_{-SO 2 -, - SO 2 -} (CH 2) ra -, - O- (CH 2)
_{ra -O- (CH 2) rb -} , - (CH 2) ra -N (C pa H
_2pa + 1) -SO ₂ -, or _{- (CH 2) ra -N (} C pa H
_{2pa + 1} ) represents -CO-. ra and rb are independently 1
-20 and pa is 0-4.

R ¹ is _{-OC qa} H _{2qa -OC qb} H
_{2qb + 1, -C qa H 2qa} -O-C qb H 2qb + 1, -C qa H 2qa -
_{^{R 3, -O-C qa H}} 2qa -R 3, -CO-O-C qa H 2qa -
R ³ or —O—CO—C _qa H _2qa —R ³ , which may be linear or branched (where R ³ _{is-
O-CO-C qb H 2qb} + 1, -CO-O-C qb H 2qb + 1, -
_{H, -Cl, -F, -CF 3} , -NO 2, represents a -CN, qa and qb are 20 independently).

R ² represents C _xa F _2xa -X (X represents -H or -F, and xa is an integer of 1 to 20).

[0024]

Embedded image Represents

Gb, hb and ib are each independently 0 to 3
(Where gb + hb + ib is at least 2).

Each of L ³ and L ⁴ is independently a single bond, -CO
-O-, -O-CO-, -CO-S-, -S-CO-,
-CO-Se-, -Se-CO-, -CO-Te-,-
Te-CO -, - (CH 2 CH 2) ka - (ka is 1
4), -CH = CH-, -C≡C-, -CH = N-,-
_{N = CH -, - CH 2} -O -, - O-CH 2 -, - CO-
Or -O-.

Each of X ² , Y ² , and Z ² is a substituent of A ⁴ , A ⁵ , and A ⁶ and independently represents —H, —Cl, —F, —Br, —
_{I, -OH, -OCH 3, -CH} 3, -CF 3, -O-C
F ₃ , —CN, or —NO ₂ , and each jb, m
b and nb each independently represent an integer of 0 to 4;

J ² is —CO—O—C _rc H _2rc —, —O—
_{C rc H 2rc -, - C} rc H 2rc -, - O- (C sa H 2sa -
O) _ta -C _rd H _2rd- , _-O -SO _2- , -SO ₂ -,-
_{SO 2 -C rc H 2rc -,} - C rc H 2rc -N (C pb H 2pb + 1)
_{-SO 2 -, - C rc H} 2rc -N (C pb H 2pb + 1) -CO-
_Where rc and rd are independently 1-20, sa is independently 1-10 for each (C _sa H _2sa -O), ta is 1-6, pb is 0-4. is there.

[0029] R ⁴ _{is, -O- (C qc H 2qc -O} ) wa -C qd
_{H 2qd + 1, - (C} qc H 2qc -O) wa -C qd H 2qd + 1, -C
_qc H _2qc -R ⁶ , _{-OC qc} H _2qc -R ⁶ , -CO- _OC
qc H _2qc -R ^6, or represents _{-O-CO-C qc H 2qc} -R 6, linear, may be either branched (Here, R
⁶ is _{-O-CO-C qd H 2qd} + 1, -CO-O-C qd H
_{2qd + 1, -Cl, -F,} -CF 3, -NO 2, represents -CN, or -H, qc and qd are independently an integer of 1 to 20, the wa is an integer of 1 to 10).

R ⁵ is (C _xb F _2xb -O) _za -C _ya F
_{2ya + 1} is represented by (wherein, the formula xb is 1 to 10 independently of each _{(C xb F 2xb -O),} ya is 1
And za is 1-10).

The compound represented by the above general formula (I) is
JP-A-2-142755, U.S. Pat.
2,587.
Specific examples of such compounds are listed below.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The compound represented by the above general formula (II) is described in WO 93/22396, JP-T-Hei 7-506.
368 can be obtained.
Specific examples of such compounds are listed below.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

Embedded image Further, specific examples of so-called hydrocarbon type liquid crystal compounds having no perfluorocarbon chain as other components include those having the following structures, but the present invention is not limited thereto.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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Further, specific examples of the chiral compound include those having the following structures, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

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[0069]

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In the present invention, the chiral smectic liquid crystal composition may contain other compounds, for example, additives such as dyes, pigments, antioxidants, and ultraviolet absorbers.

In the present invention, the chiral smectic liquid crystal composition containing the compounds represented by the above general formulas (I) and (II) generally shows SmA and SmC as liquid crystal phases, but does not have Ch. Therefore, in order to obtain uniform uniaxial alignment, it is preferable to adopt an asymmetric alignment film configuration.

Next, the production method of the present invention and an apparatus for producing an alignment film according to the production method will be described.

FIG. 2 is a schematic sectional view of a monomolecular film accumulating apparatus which is an apparatus for producing an alignment film according to the present invention. Water tank 2 of this device
Reference numeral 4 denotes roughly three areas, that is, an expansion area S, a compression area C,
And pure water flows continuously from the region S in the directions of C and D, and the pure water 25 circulates so that the water level is kept constant. Or have been excluded.

First, in the region S, a solution containing a material for finally forming a film from the nozzle 21 is dropped and dispersed on the surface of pure water flowing, and the film material is spread on the water tank.

Subsequently, as the solvent in the membrane material solution evaporates (or dissolves in pure water), the developed membrane material molecules move to the region C continuously along the water flow. In this region, the film material is compressed, and when reaching the region D, a monomolecular film is formed on the water surface. The area C is configured to have a slight downward gradient along the water flow. In the region D, the substrate 22 connected to the moving mechanism in the direction perpendicular to the water surface is repeatedly moved up and down as indicated by the arrow, and a monomolecular film is continuously deposited on the surface of the substrate to obtain an LB film.

In the above apparatus, when the amphiphilic polymer 23 is developed in the region S, the polymer chain is gradually compressed in the region C. At that time, the polymer chains tend to be parallel to the ends of the already compressed monomolecular film, and a uniaxial LB film as shown in FIG.

The present inventors have confirmed that the LB film obtained by the above operation has uniaxiality in a direction substantially perpendicular to the substrate pulling direction. This is because the flow velocity of the water flow is faster than the vertical movement speed of the substrate, so that the polymer chains move under the force of flowing water and move, and anisotropy is developed in the direction perpendicular to the vertical direction of the substrate. Probable cause.

In view of this result, the present inventors anticipated a synergistic effect of the anisotropy of the monomolecular film on the water surface and the anisotropy developed when the substrate was raised and lowered, and the present inventors made the following contrivances. In addition, an apparatus for producing a monomolecular film according to the present invention was configured. That is, as shown in the schematic plan view of FIG. 4, together with the control loop of the surface pressure and the water level of the monomolecular film, the control of mechanically compressing the monomolecular film in the laminated region D on the water surface by the barriers 31 to 33. It is provided with a loop.

In the present apparatus, a monomolecular film is formed in the region D in a state where the barriers 31 and 32 are provided, as described above. In this state, after the barrier 33 is gently landed on the water surface in the area D by the vertical moving mechanism, the water flow is stopped. In this state, there is a monomolecular film in a region surrounded by the barriers 31 to 33, and its uniaxiality is maintained. Furthermore, the water flow is stopped, and the monomolecular film does not receive the force from the flowing water. In other words, the control completely shifts from the surface pressure control loop by the water flow to the mechanical compression control loop by the barriers 31 to 33.

The substrate is repeatedly moved up and down while maintaining a predetermined surface pressure by moving only the barriers 31 and 32 in the directions indicated by the arrows in the region surrounded by the barriers 31 to 33. At this time, the monomolecular film on the water surface is accumulated on the substrate in a state of being oriented in parallel with the pulling direction of the substrate without losing its uniaxiality, so that a monomolecular cumulative film having a very high anisotropy is obtained. By using the monomolecular accumulation film as the alignment film, uniform alignment of the liquid crystal can be obtained.

[0081]

【Example】

[Example] A pair of glass substrates on which amorphous ITO having a thickness of 70 nm was formed as a transparent electrode by a sputtering method was prepared. The average surface roughness of this amorphous ITO is about 2 nm, and it is very flat. LB on this substrate
One layer of ODA (octadecylamine) was formed by an LB method as a hydrophobic treatment for improving the adsorptivity of the film.

Next, a polyamic acid LP64 (manufactured by Toray Industries, Inc.) as a polyimide precursor was dissolved in NMP (N-methylpyrrolidone) to a concentration of 1 mM. Further, dimethylhexadecylamine was dissolved in NMP to a concentration of 2 mM and mixed with the LP64 solution in an equivalent amount to obtain an amphiphilic polyimide precursor. This precursor is shown in FIGS.
And the water flow was adjusted so that the accumulated surface pressure became 30 mN / m.
While the barrier 33 was gently installed, the water flow was stopped and the barriers 31 and 32 were appropriately moved to maintain the surface pressure of the monolayer, and the substrate was raised and lowered to accumulate the monolayer.

The substrate on which the monomolecular film was accumulated was heat-treated in an oven at 350 ° C. for 60 minutes to thermally imidize the polyamic acid to obtain a polyimide horizontal alignment film. A silica bead having an average particle size of 2.0 μm
An IPA (isopropyl alcohol) solution dispersed at 1% by weight was spin-coated at 1500 rpm for 10 seconds, and dispersed at a dispersion density of 100 / mm ² .

On the other transparent electrode, a solution obtained by diluting a silane coupling agent ODSE (manufactured by Chisso) with ethanol to 0.5% by weight was spin-coated at 2000 rpm for 20 seconds, and temporarily baked at 90 ° C. for 5 minutes. After drying, it was dried at 180 ° C. for 1 hour. Thereafter, a thermosetting liquid adhesive was applied by a printing method.

The two substrates thus obtained were bonded to face each other, and the adhesive was thermally cured in an oven at 150 ° C. for 90 minutes to form a liquid crystal cell.

The liquid crystal composition used in this example is shown below.

[0087]

Embedded image

The above liquid crystal composition was prepared using Iso. Temperature (90
C.) into the liquid crystal cell, and a Mettler FP80
Place on the FP82 hot stage controlled by the HT temperature controller, From SmC to SmC ^* via SmA to cause a phase transition to obtain a liquid crystal element.
The orientation of the liquid crystal element was very uniform, and sufficiently satisfied the requirements as a display element.

Next, as an evaluation of the anisotropy of the alignment film obtained in this example, the dichroic ratio was measured by polarized light FT-IR. At this time, regarding the stretching vibration of the C ＝ O bond at 1720 cm ^−1, the dichroic ratio (A⊥ / A‖) is obtained from the absorbance A‖ for the polarized light parallel to the vertical direction of the substrate and the absorbance A⊥ for the polarized light in the vertical direction. I asked. As a result, the dichroic ratio was 2.
A value of 7 was obtained, indicating that the substrate had high anisotropy along the vertical direction of the substrate. It is considered that this high anisotropy resulted in uniform alignment of the liquid crystal element of this example.

Comparative Example A monomolecular film was formed using a monomolecular film accumulator as shown in FIG. This device is the most commonly used type, in which a film material is spread on a still water surface, and then the film is compressed using barriers 51 and 52. In the figure, 53 is a monomolecular film, 54 is a surface pressure monitor,
55 is a substrate, 56 is pure water, and 57 is a water tank. In this apparatus, the film on the water surface is completely isotropic, and anisotropy is expressed only by raising and lowering the substrate. Using this apparatus, an alignment film similar to that of Example 1 was formed, and the dichroic ratio was measured. The value was 1.6. Further, the same liquid crystal cell as that of Example 1 was formed, and the alignment of the liquid crystal was examined. As a result, alignment defects were observed, and uniform alignment could not be obtained.

[0091]

As described above, according to the present invention,
An alignment film having good uniaxiality can be formed without generating dust, and a liquid crystal element in which liquid crystal is uniformly aligned can be provided with high yield.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of one example of a liquid crystal element of the present invention.

FIG. 2 is a schematic cross-sectional view of one example of an alignment film manufacturing apparatus of the present invention.

FIG. 3 is a plan view showing a state in which polymers of a monomolecular film forming material are arranged by a water flow.

FIG. 4 is a schematic plan view of the alignment film manufacturing apparatus of the present invention shown in FIG.

FIG. 5 is a schematic sectional view of a general monomolecular film accumulating apparatus.

[Explanation of symbols]

 11a, 11b Substrate 12a, 12b Transparent electrode 13a, 13b Short prevention film 14a, 14b Alignment film 15 Seal material 16 Bead spacer 21 Nozzle 22 Substrate 23 Amphiphilic polymer 24 Water tank 25 Pure water 31-33, 51, 52 Barrier 53 Monomolecular film 54 Surface pressure monitor 55 Substrate 56 Pure water 57 Water tank

Claims (8)

[Claims] 1. A method for producing a liquid crystal element comprising a liquid crystal composition exhibiting a chiral smectic phase sandwiched between a pair of substrates each having an electrode on the opposite surface side, and having an alignment film on at least one of the electrodes. A method of developing a monomolecular film forming material on a liquid surface, compressing the material, and laminating the material on a substrate to form the alignment film. 2. An apparatus used in the manufacturing method according to claim 1, wherein a developing region for developing the material for forming a monomolecular film on a liquid surface and a material for compressing the material for forming a monomolecular film developed on the liquid surface are compressed. A compression region to be a monomolecular film, a lamination region for laminating the monomolecular film on the substrate, a mechanism for constantly flowing a liquid from the development region to the lamination region via the compression region, A water tank having a surface pressure control loop for controlling the developing speed of the monomolecular film forming material to maintain the surface pressure of the developed monomolecular film forming material at a predetermined value, and a liquid flowing into the water tank. By adjusting the amount of, a water level control loop that keeps the water level of the stacking region at a predetermined value, and a compression control loop for mechanically compressing a monomolecular film in the stacking region by a barrier on the water surface Alignment film characterized by having Manufacturing equipment. 3. A liquid crystal device manufactured by the manufacturing method according to claim 1, wherein a liquid crystal composition exhibiting a chiral smectic phase is sandwiched between a pair of substrates each having an electrode on an opposite surface side, and A liquid crystal element having an alignment film made of a monomolecular film on one electrode. 4. A fluorine-containing liquid crystal compound having a fluorocarbon terminal portion and a hydrocarbon terminal portion, wherein both terminal portions are bound by a central nucleus and having a smectic intermediate phase or a potential smectic intermediate phase. The liquid crystal device according to claim 3, further comprising: 5. The liquid crystal device according to claim 4, wherein the terminal portion of the fluorocarbon in the fluorine-containing liquid crystal compound is a group represented by -D ¹ -C _xa F _2xa -X. (However, the formula xa is 1 to 20, X represents -H or -F, D ¹ _{is, -CO-O- (CH 2)} ra -, - O- (CH
_{2) ra -, - (CH} 2) ra -, - O-SO 2 -, - SO
_{2 -, - SO 2 - (} CH 2) ra -, - O- (CH 2) ra -O
_{- (CH 2) rb -,} - (CH 2) ra -N (C pa H 2pa + 1)
-SO _{2- or-} (CH ₂ ) _ra -N (C _pa H _{2pa + 1} )-
Represents CO-. ra and rb are independently 1-20, and pa is 0-4. ) 6. The fluorocarbon terminal in the fluorine-containing liquid crystal compound is -D ^2- (C _xb F _2xb -O) _za
-C _ya F _{2ya + 1} liquid crystal device according to claim 4, wherein a group represented by. (However, in the above formula, xb is the respective (C _xb F
_2xb- O) independently represents 1 to 10, and ya represents 1 to 10
And za is 1 to 10, and D ² is -CO-O-
_{C rc H 2rc -, - O} -C rc H 2rc -, - C rc H 2rc -, -
_{O- (C sa H 2sa -O)} ta -C rd H 2rd -, - O-SO 2
_{-, - SO 2 -, -} SO 2 -C rc H 2rc -, - C rc H 2rc -
_{N (C pb H 2pb + 1} ) -SO 2 -, - C rc H 2rc -N (C pb
_{H2pb + 1} ) -CO-, a single bond, rc and rd
Is independently 1 to 20, sa is independently 1 to 10 for each (C _sa H _2sa -O), and ta is 1
And pb is 0-4. ) 7. The liquid crystal device according to claim 4, wherein the fluorine-containing liquid crystal compound is represented by the following general formula (I). Embedded image Represents ga, ha, and ia each independently represent an integer of 0 to 3 (provided that ga + ha + ia is at least 2). Each L ¹ and L ² is independently a single bond, —CO—O—,
-O-CO-, -COS-, -S-CO-, -CO-S
e-, -Se-CO-, -CO-Te-, -Te-CO
_{-, - CH 2 CH 2 -} , - CH = CH -, - C≡C -, -
CH = N -, - N = CH -, - CH 2 -O -, - O-C
Represents H ₂ —, —CO— or —O—. Each X ¹ ,
Y ¹ and Z ¹ are substituents of A ¹ , A ² and A ³ , and independently
H, -Cl, -F, -Br, -I, -OH, -OC
Represents H ₃ , —CH ₃ , —CN, or —NO ₂ , and each of ja, ma, and na independently represents an integer of 0 to 4. J ¹
_{Is, -CO-O- (CH 2)} ra -, - O- (CH 2)
_{ra -, - (CH 2)} ra -, - O-SO 2 -, - SO 2 -,
_{-SO 2 - (CH 2) ra} -, - O- (CH 2) ra -O-
(CH ₂ ) _rb -,-(CH ₂ ) _ra -N (C _pa H _{2pa + 1} )-
SO ₂ — or — (CH ₂ ) _ra —N (C _pa H _{2pa + 1} ) —C
Represents O-. ra and rb are independently 1-20, and pa is 0-4. R ¹ is _{-OC qa} H _2qa -O
-C _qb H _{2qb + 1} , -C _qa H _{2qa -OC qb} H _{2qb + 1} , -C
_qa H _2qa -R ³ , _{-OC qa} H _2qa -R ³ , -CO- _OC
qa H _2qa -R ^3, or represents _{-O-CO-C qa H 2qa} -R 3, linear, may be either branched (Here, R
_{^3, -O-CO-C qb H} 2qb + 1, -CO-O-C qb H
_{2qb + 1, -H, -Cl,} -F, -CF 3, -NO 2, -C
N, and qa and qb are independently 1-20).
R ² represents a C _xa F _2xa -X (X represents -H or -F, xa is an integer of 1 to 20). ] 8. The liquid crystal device according to claim 4, wherein the fluorine-containing liquid crystal compound is represented by the following general formula (II). Embedded image Represents gb, hb, and ib are each independently an integer of 0 to 3 (however, gb + hb + ib is at least 2)
Represents L ³ and L ⁴ are each independently a single bond, -CO-
O-, -O-CO-, -CO-S-, -S-CO-,-
CO-Se-, -Se-CO-, -CO-Te-, -T
e-CO -, - (CH 2 CH 2) ka - (ka is 1 to 4),
-CH = CH-, -C≡C-, -CH = N-, -N = C
_{H -, - CH 2 -O -} , - O-CH 2 -, - CO- or -
Represents O-. Each of X ² , Y ² , and Z ² is a substituent of A ⁴ , A ⁵ , and A ⁶ and independently represents —H, —Cl, —F, —Br, —
_{I, -OH, -OCH 3, -CH} 3, -CF 3, -OC
F ₃ , —CN, or —NO ₂ , and each jb, m
b and nb each independently represent an integer of 0 to 4; J ² is, -C
_{O-O-C rc H 2rc} -, - O-C rc H 2rc -, - C rc H
_{2rc -, - O- (C sa} H 2sa -O) ta -C rd H 2rd -, -
_{O-SO 2 -, - SO} 2 -, - SO 2 -C rc H 2rc -, - C
_rc H _2rc -N (C _pb H _{2pb + 1} ) -SO _2- , -C _rc H _2rc-
N (C _pb H _{2pb + 1} ) —CO—, rc and rd are independently 1 to 20, and sa is the respective (C _sa H _2sa −).
O) independently from 1 to 10, ta from 1 to 6, p
b is 0-4. R ⁴ _{is, -O- (C qc H 2qc -O} ) wa
_{-C qd H 2qd + 1, -} (C qc H 2qc -O) wa -C
_qd H _{2qd + 1} , -C _qc H _2qc -R ⁶ , _{-OC qc} H _2qc-
R ⁶ , -CO- _{OC qc} H _2qc -R ⁶ , or -O-CO-
_{C qc} H 2qc -R ⁶ represents a linear, it may be either branched (wherein, R ⁶ is _{-O-CO-C qd H 2qd} + 1, -
_{CO-O-C qd H 2qd} + 1, -Cl, -F, -CF 3, -N
Represents O ₂ , —CN, or —H, qc and qd are each independently an integer of 1 to 20, and wa is an integer of 1 to 10). R
^5, (C _xb F _2xb -O) represented by _za -C _ya F _{2ya + 1} (where the above formula xb is each (C _xb F _2xb -O)
Is independently 1 to 10, ya is 1 to 10, za
Is 1 to 10.) ]