JP3477000B2 - Reflective liquid crystal display - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a reflection type liquid crystal display element.
About the child. [0002] 2. Description of the Related Art In general, a liquid crystal display device is separated by a certain distance.
A pair of electrode substrates arranged opposite to each other, and an opposite electrode base;
An alignment film covering the surface of the plate, and an alignment film between the substrates
It is composed of a sandwiched liquid crystal material. To liquid crystal material
Is applied to the transparent area formed in the pixel area on the electrode substrate.
Or through a non-transparent electrode. Especially in recent years, acte
As a liquid crystal display element used for the active matrix method,
Thin Film Transistor (TFT)
Which driving element is mounted on one electrode substrate of the pixel section
A structure with a different structure has been developed and put into practical use. In a liquid crystal display device, the orientation / alignment of the liquid crystal material is
Deformed by electric / magnetic fields applied from outside
It works by changing its optical properties. General
In addition, the light component transmitted through the polarizing plate is controlled by the liquid crystal alignment.
Light state and dark state are realized, twisted nematic
(TN) element, super twisted nematic (STN)
Device, surface stabilized ferroelectric liquid crystal (SSFLC) device, anti-static
Ferroelectric liquid crystal (AFLC) devices and the like have been developed.
However, the use efficiency of the light is up to 5 due to the use of the polarizing plate.
It is as low as about 0%. Incidentally, in recent years, notebook personal computers,
PCs, mobile phones, PHS, PDAs, etc.
Mobile information devices are attracting great attention and are becoming popular,
Low power consumption is indispensable for portability. That
Low power consumption for display devices mounted on portable information devices
Is required. But need traditional backlight
The transmissive liquid crystal display element satisfies this requirement.
Extremely difficult, no backlight required and low power consumption
There is a strong demand for a reflective liquid crystal display device. [0005] As a reflection type liquid crystal display element, TN, ST
The backlight of a transmissive liquid crystal display device such as N
Although the one replaced by is already in practical use,
As described above, since the polarizing plate is used, the light
The performance is not enough. For these reasons,
Several reflective liquid crystal display devices that do not use a light plate have been proposed.
Some of them are being put to practical use. As one of them, a liquid crystal material is contained in a polymer material.
Disperse and use the birefringence of the liquid crystal to change the scattering and transmission states
Electrically controlled, relatively good without using polarizing plate
(Polymer Dispersed Li) with excellent viewing angle characteristics
quid Crystal type liquid crystal display device
No.-501631, No.61-502128, Special table
No. 63-501512) has been proposed. But
Low scattering, requires relatively high driving voltage
There is a problem. For the former, see, for example,
In -273527, a half mirror is placed behind the display element.
By installing, as described in JP-A-4-250418
In Japanese Unexamined Patent Publication No. Hei 4-318518, an uneven portion is connected to a liquid crystal layer.
In addition, Japanese Patent Application Laid-Open No. 5-88153,
In Kaihei 6-11712, the average refractive index of the liquid crystal material is
A diffraction grating made of a material with a high refractive index into the liquid crystal layer
Attempts to improve scattering by installing in contact
It is difficult to obtain good contrast and sufficient brightness
It was difficult. Further, the scattering state and the transmission state are electrically controlled.
Using cholesteric liquid crystal material
 G.H.Heilmeier, J.E. Goldmacher et al. (RCA La
b. (Eg, Appl.Phys.Le)
tt., 13, 132 (1968)). This liquid crystal display element has a helical axis
A planar (Pl) in which the electrode substrate surface is oriented almost vertically
Anar) structure or helical structure is eliminated and liquid crystal molecules are
Homeotropic oriented vertically to the substrate
Transparent state in the structure and spiral axis is random but electrode
Focal conic relatively parallel to the substrate
 The display is performed using the scattering state in the structure.
Planar structure and focal conic when no voltage is applied
Focus structure between locking structures or when holding voltage is applied
Bistability between luconic and homeotropic structures
Although the display method used has been proposed, the PDLC method
As with liquid crystal display devices of the formula,
There are problems of emissivity and low contrast. On the other hand, anti-reflection films using cholesteric liquid crystal materials
Selective reflection different from scattering / transmission mode as projection display
The mode called mode is J.E.Aams, W.E.Hass, J.J.
(Xerox Co.)
(Eg, Phys. Rev. Lett., 24, 577 (1970)). Selective reflection
Is the spiral periodic structure pin in the planar structure.
Wavelength defined by the product of the switch length and the average refractive index of the liquid crystal material.
Select the circularly polarized light component in the same rotational direction as the helix as the reflection maximum.
This is a phenomenon of selective reflection. In selective reflection mode, visible
Adjust the helical pitch to reflect the light,
Reflection state and focal conic structure
The display is performed using the scattering state in the display. But selective reflection mode
The mode has a high reflectance and contrast, but a viewing angle
Narrow or narrow wavelength range of reflected light, making whitening difficult
There is such a problem. On the other hand, D.K.Yang, L.-C.Chein, J.W.
Doane (Kent State Univ.) Et al.
Re-domaining allows viewing angle and selective reflection wavelength range
Wide area, planar structure and focal conic structure
Trying to improve the bistability of In addition, this bistability improvement
Matrix drive utilizing the storage effect
Prototype panels have also been prototyped (for example, SID 95 DIGIST p.
706 (1995)). It should be noted that the planar structure is polydomain
Is that the helical axis is almost normal to the substrate in almost the entire area of the liquid crystal layer.
Consists of approximately single regions or monodomains aligned
Check that the spiral axis is slightly inclined from the substrate normal
In addition, there are many areas where the projection directions of the helical axis onto the substrate are different.
In other words, change to a planar structure consisting of poly domains.
I say. As a method for forming a polydomain, a liquid crystal material
Dispersion of a small amount of polymer material in
7505, Appl.Phys. Lett., 64, 1905 (1994), SID 94
 DIGEST p.841 (1994)) and non-orientation treatment of the electrode substrate surface
(For example, J. Appl. Phys., 761, 1331 (1994), SID 95 DIG
EST p.172 (1995)). However, PSCT (Polymer Stabil)
high in liquid crystal material called ized Cholesteric Texture)
In the method of dispersing the molecular material, as the selective reflection area decreases,
Reflectance and scattering in homeotropic structures
Besides the fact that relatively high voltage is required for driving
There is a title. Also, do not intentionally perform the alignment treatment on the substrate surface.
Is a problem caused by the introduction of polymer materials in PSCT
Does not occur, but the selective reflection light by the planar structure
Some are not reflected to the observer side, so brightness and contrast
There is a problem with trust. In addition to the various display methods described above, scattering and selection
Attempts to use both selective reflections include scattering / transmission layers and selective
Display element composed of selective reflection layer and light reflection plate proposed
(JP-A-59-116613). This is scattering
Selectively reflects part of the light transmitted through the scattering / transmission layer in the state
Reflecting light from the layer enhances light use efficiency and improves brightness.
What is going to be whitened by the scattering layer while improving
It is. However, the selective reflection layer switches its state
Because it is fixed to the selective reflection state
The contrast is completely inadequate and the viewing angle dependence is large.
There is a problem such as crispness. As described above, in the prior art, the reflection
Broadening of the wavelength range of light is insufficient, and whitening
It is virtually impossible. Furthermore, regarding the reflectance,
Maximum reflectance because only one of the circularly polarized components can be selectively reflected
The essential problem with the selective reflection mode of 50% is
I can't solve it. [0013] SUMMARY OF THE INVENTION The present invention provides a bright and
Reflective liquid crystal display device with good trust and wide viewing angle
The purpose is to provide. [0014] A reflection type liquid crystal according to the present invention.
At least one of the display elements facing each other has transparency.
HaveFirst and secondElectrode substrateAnd the electrode substrateSky between
BetweenRetainedPresents cholesteric phaseILight in the visible range
Liquid crystal material with a helical pitch effective for reflectionAnd
And a surface of the first electrode substrate in contact with the liquid crystal material.
Subjecting the first electrode substrate to horizontal alignment treatmentMonodome
A liquid crystal material region having an in-plane structure is formed,Previous
SecondA poly-domain planar structure on the electrode substrate side
Liquid crystal material regions are formed,SaidLiquid crystal material area
ButThe first and second electrodesPerpendicular to the substrate surface
ArrangeWith the electrode substrate in contact with each other
MakeIt is characterized by the following. [0015] DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a reflection type liquid crystal display element of the present invention will be described.
The child will be described in detail. This reflective liquid crystal display element is
Electrodes, at least one of which opposes the transparent electrode
A cholesteric liquid crystal material is stored in the space between the substrates.
The liquid crystal material is effective to reflect light in the visible region.
A liquid crystal display device having a helical pitch, the structure and
Liquid crystal materials having at least one of different electro-optical characteristics
Between the two electrode substrates with respect to the substrate surface
It has a configuration formed continuously in the vertical direction. In the reflection type liquid crystal display device according to the present invention,
Specifically, the following form is allowed. (1) Liquid crystal material region with mono-domain planar structure
And a liquid crystal material region with a polydomain planar structure,
Reflection of the form continuously formed in the vertical direction of the electrode substrate
Liquid crystal display device. (2) In the liquid crystal display device having the structure of (1),
Here, of the two electrode substrates, one of the electrode substrates
A horizontal alignment process is performed on a surface in contact with the liquid crystal material. (3) Liquid crystal material region showing selective reflection state and scattering state
Liquid crystal material region continuously in the vertical direction of the electrode substrate.
A reflective liquid crystal display element in a form to be formed. (4) In the liquid crystal display device having the structure of (3),
In addition, at least one of the two electrode substrates
Perform vertical alignment treatment on the surface of the electrode substrate in contact with the liquid crystal material.
You. (5) Of different spiral orientations and different pitch lengths
A liquid crystal material region in a selective reflection state that takes at least one of
Reflection of the form continuously formed in the vertical direction of the electrode substrate
Liquid crystal display device. (6) In the liquid crystal display device having the structure of (5),
In addition, at least one of the two electrode substrates
Optically active substance is supported on the surface of the electrode substrate in contact with the liquid crystal substance
Let it. (7) In the liquid crystal display device having the structure of (5),
Between the two electrode substrates together with the liquid crystal material.
Of the physical material and its physical and chemical properties
At least one property is different in the vertical direction of the electrode substrate.
To hold it. (8) In the liquid crystal display device having the structure of (5),
Between the two electrode substrates together with the liquid crystal material.
Retains polymeric material with active sites. (9) In the liquid crystal display device having the configuration of (5),
Two electrode substrates with different surface energies and
Prepare a plurality of liquid crystal materials with different surface energies,
Holding a plurality of liquid crystal substances between the electrode substrates;
Phase separation spontaneously in the opposite direction. In the present invention, the liquid crystal substance is provided between the electrode substrates.
Cholesteric phase in the retained state and visible
With a helical pitch effective to reflect light in the
There is no particular limitation as long as there is a single liquid crystal material
Not limited to this, two or more types of liquid crystal substances and substances other than liquid crystal substances
Mixtures may be used. Nematic liquid crystal as liquid crystal material
Besides, cholesteric liquid crystal, nematic liquid crystal and cholesteric
Teric liquid crystals or optically active substances, and even optically active
It is possible to use a mixture with a nematic liquid crystal having
Wear. The optically active substance is the product of the helical pitch length and the weight concentration.
Helical Twisting P defined by the reciprocal of
ower) and the desired selective reflection wavelength,
What is necessary is just to set the amount. From the viewpoint of keeping the drive voltage low
Is the torsional elastic constant for the dielectric anisotropy of the liquid crystal material.
Refractive anisotropy in terms of small ratio and improvement of reflectance
It is preferable that the property (birefringence) is large. Where visible
Is a light having a wavelength of 400 to 800 nm.
As expected. In the present invention, the purpose of adjusting the color tone of selective reflection
May be mixed with a dichroic dye. However, in that case
Ideally, a material that exhibits absorption characteristics outside the selective reflection wavelength range
The fee is suitable. In the present invention, a voltage is applied to the liquid crystal material.
The electrode formed on the electrode substrate for
Both are limited as long as the observer's electrode has transparency
It is not done. As a transparent electrode, for example, IT
Using a thin film of O (indium tin oxide)
Can be. The other electrode that does not require transparency
Luminium, nickel, copper, silver, gold, platinum, etc.
Polar materials can be used. The electrode formation on the substrate
For example, evaporation, sputtering, photolithography, etc.
Normal methods are employed. In the present invention, the substrate on which the electrodes are formed
Has sufficient strength and insulating properties, and
Is particularly limited as long as the substrate has transparency.
Not, for example, glass, plastic, ceramic, etc.
Can be used. In the present invention, the distance between two electrode substrates
Is a member provided between the electrode substrates, that is, a spacer
Is kept constant by The spacers are usually
Are used, but the
Less risk of spacers getting close to each other during alignment
A columnar body that can be uniformly dispersed is preferable. this
Such pillars can be formed at regular intervals on the substrate.
More desirable. In addition, the table for one spacer
Different orientation treatment or different optically active substance supported on the surface
In this case, it is more preferable that the spacer is a columnar body.
Are suitable. The material of the spacer may be an insulating material.
Without reacting or dissolving with the liquid crystal molecules used
If it is stably dispersed, the material is particularly limited.
No, for example, divinylbenzene, polystyrene, etc.
Polymers or inorganic oxides such as alumina and silica
Which can be used. The particle size distribution of the spacer,
Desirably narrow. Columns are placed on the electrode substrate at regular intervals.
As a method of forming, it is used in photolithography.
It is possible in the usual way. The material is liquid crystal
Electrically insulating without reactivity or solubility for materials
Use of positive or negative photosensitive resin
it can. For example, polyimide, polyamide, polyvinyl
Alcohol, polyacrylamide, cyclized rubber, novola
Resin, polyester, polyurethane, acrylic resin,
Bisphenol resin or gelatin made photosensitive resin
Can be mentioned, but in general, negative type photosensitive
Polyimide is preferred. The distance between the electrode substrates is not particularly limited.
It is not reflected, but selective reflection from the point of low voltage drive
As small as possible within the range where the reflectance in the state does not decrease.
Is preferred. In the present invention, the liquid crystal material is transferred between the electrode substrates.
The method of encapsulation is not particularly limited and may be a known method.
Just do it. Horizontal orientation to electrode substrate surface in the present invention
Processing involves aligning the liquid crystal material in a direction substantially parallel to the substrate surface.
This refers to the processing to be performed. The processing target is in contact with the liquid crystal layer.
Is not limited to the electrode surface,
Of course, a thin film covering the electrode is also included. processing
Although the method is not particularly limited, for example,
Electrode or thin film such as polyimide covering the electrode
Rubbing treatment in which the surface is rubbed in one direction with a cloth etc., on the water surface
Transfer the monomolecular film formed on the
Langmuir-Blodgett method for forming thin films, electrodes
Photopolymerize the polymerizable monomer coated on the substrate by polarized light
Known method, or oblique evaporation method of silicon oxide
This is possible. As a material for thin films covering electrodes
Is not particularly limited, and is usually a horizontal alignment film.
Use materials suitable for each forming method
be able to. The thickness of the thin film depends on the voltage applied to the liquid crystal layer.
There is no particular limitation as long as the addition is sufficient.
No. In the present invention, the vertical alignment treatment on the electrode substrate
Refers to the process of orienting the liquid crystal substance in a direction substantially perpendicular to the substrate surface.
It means things. The object to be processed is the surface in contact with the liquid crystal layer.
Therefore, the electrode is not limited to the surface of the electrode.
Of course, the covering thin film is also included. The processing method
Although not particularly limited, long-chain alkyl
Or silane coupling agents containing perfluoro groups, etc.
And quaternary ammonium salts, lecithin and long-chain carboxylic acids
Using chromium complex, fluororesin, etc. as the alignment film material,
Known methods such as coating the electrode surface with these thin films
Is possible. The thickness of the thin film should be sufficient to apply voltage to the liquid crystal layer.
There is no particular limitation as long as it can be performed in minutes. In the present invention, an electrode not subjected to an orientation treatment
For thin films that cover the substrate or electrodes and are in contact with the liquid crystal layer
Process is performed when the liquid crystal material has a planar structure.
Anything that realizes the redomain state is limited
Not something. For example, by spinner coating
Polyimide thin film and silicon oxide formed by vertical evaporation
The thin film can be used as it is. Also, T
In recent years, research has been actively conducted to increase the viewing angle of N elements.
Processing using a polydomain method may be performed. In the present invention, a shape is formed at an interface in contact with a liquid crystal material.
The formed uneven structure is made of photosensitive polyimide, photosensitive resist
Organic materials formed using optical lithography technology
Stamping technology using thin film or photo-curing or thermosetting resin
Organic thin film or metal oxide formed by surgery
Inorganic thin film etc. formed by the etching technology of
However, in general, a fine uneven structure can be formed
Can be used as long as it is an insulating thin film that can transmit light in the optical wavelength range
Noh. As the physical uneven structure, the height of the convex and concave portions
The height where the difference is low is 0.3 to 1.5 μm.
The distance between the individual protrusions or depressions is 1.5 to 30 μm
It is preferable that the fine structure is In the present invention, the spacer subjected to the orientation treatment
The following method is employed to prepare Spherical ball
In the case of a pacer, the hemisphere is aligned using a mask.
You. In the case of a columnar spacer, two different compositions are used.
Laminate the photosensitive resin sequentially or use the same photosensitive resin
Are laminated in two stages, and different surface treatments are performed in each stage. Table of members in contact with the liquid crystal material in the present invention
As the optically active substance carried on the surface, an optically active site
In particular, as long as it has and can be fixed to the member surface
Is not specified, and two or more
Use optically active substances or mixtures with optically inactive substances.
Can be used. Examples of optically active substances include the following
Can be used. Polyamino acids, cellulose
Like collagen, collagen, DNA (deoxyribonucleic acid)
Biopolymers and their derivatives, or amino acids,
Small biomolecules such as sterols and cholic acid and their induction
Conductor or cholesteryl-ω- (4-methacryluro
Yloxyphenyl alkanoate) with methylene chain char
Monomers, homopolymers and copolymers having a prime number of 2 to 12
Body, 1-phenylmethylbenzylideneaminobenzoate
Methacrylic acid monomer having a side chain of
And a copolymer with another methacrylic acid ester, S-2-
Methyl butyl methacrylate monomer, homopolymer and
With other methacrylates and their induction
Synthetic low- and high-molecular materials such as conductors, or commercially available chira
CB15, C15, CE2, CE8, S811,
R811, S1011, R1011, CN (above, ME
RK), CM, CM19, CM20, CM21, CM
22 (above, Chisso) and its derivatives
Is a molecule. In addition, the density of optically active sites
Optically active substances include optically active monomers and optically inactive
Copolymers composed of reactive monomers, such as methoxybi
Phenylbenzoate and 1-phenylethylbenzylide
Esters with aminobenzoate as side chains
Copolymers of the same can be used. In the present invention, a portion supporting an optically active substance
Materials include the above-mentioned electrode substrate and spacer
Can be. The optically active substance is silica, alumina or the like.
High content of inorganic oxide fine particles or novolak resin
An electrode that is supported by fine particles of a particle and is in contact with the liquid crystal layer
It may be fixed on the substrate surface. Also carries an optically active substance
Optical resolution column commercially available as fine particles
The filler can be used as it is. In the present invention, the optically active substance is changed to a liquid crystal substance.
As a method of supporting on the surface of the member in contact,
Normal methods such as coating, spin coating, spray coating, etc.
Can be used as appropriate. In addition, the optically active substance
Chemical coupling on the member surface
Can be supported together. Furthermore, polyamino
For acid derivatives, etc., see Langmuir, 11, 4838 (1995).
As shown, supported via silane coupling agent
Is also effective. The thickness of the optically active substance depends on the voltage
Limited as long as sufficient voltage can be applied to crystalline material
It is not done. Note that the optically active substance is
It can also be used by adding to a film or a spacer. In the present invention, an electrode substrate is used together with a liquid crystal material.
As the polymer material held between them, it reacts with the liquid crystal substance.
There is no particular limitation as long as it does not dissolve.
However, it is desirable that it be transparent to visible light. example
For example, polyimide, polyamide, polyvinyl alcohol,
Polyacrylamide, cyclized rubber, novolak resin, poly
Ester, polyurethane, acrylic resin, bisphenol
Resin or the like can be used. In the present invention, an object is placed in a direction perpendicular to the electrode substrate.
Polymers with different physical and / or chemical properties
As the polymerizable monomer used to form the material,
Any of thermoplastic, thermosetting, and photocurable
Forms a transparent polymer having a three-dimensional network structure
Is desirable. For example, styrene and its derivatives
Body: acrylic acid, acrylic ester, acrylic acid
And its derivatives; N-vinylpyrrolidone, N-vinyl
Vinyls such as luimidazole and vinyl acetate. Ma
Dibasic diacrylic acid and its derivatives, dimeta
Divalent monomers such as crylic acid and its derivatives, 3
Valent or tetravalent acrylic acids and methacrylic acids
Can be mentioned. Further, the α-position of the vinyl group and / or
Or hydrogen at the β-position is a phenyl group, an alkyl group, a halogen
Or a group such as a cyano group. Even better
Also, siloxanes can be used. Reactivity and viscosity
Oligomers derived from monomers in terms of degree of choice
Can be used alone or with monomers
it can. Among the aforementioned materials, heavy
Acrylic monomers and oligomers that cure are preferred
, 2-ethylhexyl acrylate, 2-hydroxy
Ethyl acrylate, 4,4'-bisacryloyl bif
Phenyl, as a commercially available and readily available oligomer,
Kayarad Manda, Kayarad HX-220, Kaya
Rad HX-620, Kayarad R-551, Kayara
R-712, Kayarad R-604, Kayarad R-
167 (Nippon Kayaku Co., Ltd.) can be used. What
Incidentally, the monomer is not limited to one kind, but two or more kinds.
To form copolymer macromolecules using various monomers
You can also. Furthermore, the amount added to the liquid crystal material
Reduces both scattering by the polymer and rise in driving voltage.
Physical properties and / or the vertical direction of the electrode substrate
Alternatively, the formation of polymer materials with different chemical properties
To the extent that different fields can be given to the crystalline material,
It is preferable that it is as small as possible.
0.1 to 10% by weight based on the total weight of the material
Good. In addition, polymerizable monomers or oligomers are required.
Cross-linking agent, surfactant, polymerization accelerator, chain transfer as required
And a modifier such as a photosensitizer. In the present invention, polymerization having an optically active site
The reactive monomer is not particularly limited,
Tylene and its derivatives; acrylic acid, acrylic acid ester
Ter, acrylamide and derivatives thereof; N-vinyl
Pyrrolidone, N-vinylimidazole, vinyl acetate, etc.
Optically active sites such as vinyls or siloxanes
Anything should do. In controlling the alignment of liquid crystal, liquid
Those containing mesogens that interact with crystalline material are preferred,
For example, cholesteryl acrylate, 4'-acryloyl
4- [2- (s) -methylbutyl] biphenyl, 4
'-Acryloyl-4- [2- (s) -methylheptyl
Oxy] biphenyl, 4 '-(6-acryloylhexyl
Loxy) -4- [2- (s) -methylbutyl] biffe
Nil, 2-methyl-4- (4-biphenyl) butylac
Relates can be used. In the present invention, in order to carry out polymerization promptly,
A polymerization initiator may be used. As the polymerization initiator,
If it is suitable for the selected monomers and oligomers
For example, as commercially available and easily available,
Darocure 1173 (Merk), Darocure 111
6 (Merk), Irgacure 184 (Ciba Geigy)
Irgacure 651 (Ciba Geigy), Irgah
Cure 907 (Ciba Geigy), Kaya Cure DETX
(Nippon Kayaku), Kaya Cure EPA (Nippon Kayaku), etc.
Can be mentioned. The amount of polymerization initiator added is
From the viewpoint of maintaining a high retention
5% by weight or less based on the
You. In the present invention, the polymer material is placed near the electrode substrate.
The method of dispersing in the liquid crystal material region of
For example, a polymerizable polymer having a net charge
Nomer dispersed in liquid crystal material and held in space between electrode substrates
In this state, the polymerizable monomer is applied by applying a voltage.
It is unevenly distributed near the electrode substrate of the opposite polarity.
A method of irradiating and polymerizing is employed. In the present invention, physical properties and / or
Is a polymer material whose chemical properties differ in the vertical direction of the electrode substrate
As a method of forming the polymer, a polymerizable monomer or
Keep the ligoma in a uniform state between the electrode substrate and the liquid crystal material.
After heating, heat or heat from at least one electrode substrate side.
Can employ a method of performing light irradiation. This place
Distribution of heating temperature and light irradiation intensity in the vertical direction of the electrode substrate
Is formed, which results in high polymer density, degree of polymerization and copolymer
Induces distribution in the composition of the polymer, and finally the network structure of the polymer
Different environments and fields for liquid crystal materials held in
Will be. In addition, monomer or oligomer
The same effect can be obtained by polymerizing in a state where it is unevenly distributed in the substance.
It is possible to get fruit. In the present invention, polymerization having an optically active site
The reactive monomer or oligomer is charged together with the liquid crystal material.
It is held between the polar substrates and has a planar structure of selective reflection.
In this state, polymerization is performed by light irradiation or the like. At this time,
Heating or light irradiation from at least one electrode substrate
Techniques, such as polymer density, degree of polymerization, and copolymer composition
Induced distribution in the vertical direction of the electrode substrate and formed by polymerization
Of helical pitch length of optically active polymer
You. In the present invention, the polymerizable site on the electrode substrate
Reacts with polymerizable monomers or oligomers
It is not particularly limited as long as it has a double bond at the terminal.
Silane coupling agents such as vinyl trichloro
Silane, vinyltriethoxysilane, vinyltrimethoxy
Sisilane, vinyl tris (β-methoxyethoxy) sila
Γ-methacryloxypropyltrimethoxysilane
Can be used. In the present invention, liquids having different surface energies
The liquid material held between the electrodes
It is not limited as long as the crystalline substance is phase-separated.
But not the presence or size of the boundary area from one phase to another
The size is not limited. Preferred material systems include
Hydrocarbon liquid crystal material and electrode coating material and perfluorinated
Liquid crystal material, electrode coating material and perfluoro liquid crystal
Substances, and electrode coating substances. Charring
As a hydrogen-based or perfluoro-based liquid crystal material,
Although not limited to, perfluoro-based liquid crystal material
As the material, for example, the structural formulas listed in Chemical Formulas 1 and 2 shown below
Can be used. In addition, hydrocarbon-based electrodes
The coating material is a hydrocarbon-based material such as polyimide or polyamide.
Polymers and other materials are used for perfluoro-based electrode coating materials.
Perfluoro resin, polyimide or polyamide side chain
Use of perfluoropolymers, etc.
Can be. [0044] Embedded image[0045] Embedded imageThe reflection type liquid crystal display according to the present invention described above.
The display of the indicator element is based on the species (I) to (VII) described below.
This is done in various ways. (I) Liquid crystal material region having a mono-domain planar structure
Liquid crystal material domain with planar and polydomain planar structure
Are formed separately from each other in the vertical direction of the electrode substrate
Display: FIG. 1 is used for a display method of such a configuration.
And will be described briefly. In this case, the electrode 3 of the electrode substrate 1 ′
Only the horizontal alignment processing is performed. Electrode substrate 1, 1 '
And the liquid crystal layer injected into the space surrounded by the spacer 4
The power supply 6 is used to apply the voltage of
This is done. In the case where the voltage is turned off, no particular alignment treatment is performed.
The liquid crystal layer on the electrode 2 side of the electrode substrate 1 is formed by liquid crystal molecules.
The axis of the spiral structure is slightly tilted from the substrate normal and the
Many domains with different projection directions on the polar substrates 1 and 1 '
Formed a polydomain planar structure composed of
Have been. On the other hand, the liquid crystal layer on the side of the electrode 3 which has been subjected to horizontal alignment processing
Is that the axis of the helical structure formed by the liquid crystal molecules is perpendicular to the substrate
A uniform mono-domain planar structure is formed
You. As described above, the substrate which is not subjected to the alignment process and the horizontal alignment process are performed.
By holding the liquid crystal layer between the treated substrates,
Liquid crystal structures that are clearly different without separating the liquid crystal layer
A structure can be formed between a pair of electrodes. this
Therefore, two liquid crystal layers each sandwiched between a pair of electrodes are used.
The effect of improving display characteristics with a simpler cell structure
Can be realized. Regarding the display when the voltage is off, the present invention
When both liquid crystal display elements are viewed from the electrode 2 side,
The details are described below in comparison with the conventional case with the same orientation treatment.
I do. The electrodes 2 and 3 were both horizontally aligned.
In the case of the conventional system, the liquid crystal layer is mono-domain over the entire area.
The spectral width of the reflected light is
Not only narrow, but also the brightness and brightness of the display depending on the viewing angle
There is a problem in viewing angle characteristics such as a large change in color.
In contrast, in the case of the liquid crystal display device of the present invention, the polymer
Inner planar structure 7 is mono-domain planar structure
Formed in front of structure 8, that is, on the observer side.
The viewing angle characteristics of the mono-domain planar structure 8 are improved.
In addition to being improved, the spectral width of reflected
Display color slightly white due to scattering contribution at main boundary
It can be like. Both electrodes 2 and 3 were vertically aligned.
In the case of the conventional method, a portion sufficiently separated from the electrode substrates 1 and 1 '
Except for the liquid crystal layer has a focal conic structure,
The reflected light is white due to scattering and has good viewing angle characteristics.
The low backscattering ability of
And it is not enough. In contrast, the liquid crystal table of the present invention
In the case of the indicator element, the coloring of the reflected light and the slight
Despite the drop, the planar structure takes selective reflection
7 and 8 are formed to greatly improve the reflectance.
Can be When both electrodes 2 and 3 are not aligned,
In the conventional method, the liquid crystal layer has a polydomain
Mono-domain planar for a planar structure
Significant improvement in viewing angle dependence, which was a problem with the structure
Is recognized. However, the helical axis is tilted with respect to the substrate normal.
Part of the reflected light is reflected to the observer side
There is room for improvement in brightness and contrast. This
In contrast, in the case of the liquid crystal display device of the present invention, the polymer
Mono-domain planar behind the planar structure
By the arrangement of the structure, the selection
The reflected light can be reflected back to the observer,
While maintaining the advantages of the poly domain such as viewing angle,
It is possible to improve the brightness. It should be noted that the liquid crystal display device of the present invention is
When viewed from the side not as good as when viewed from the electrode 2 side
The advantages of both poly and mono domains
Can be displayed. Next, when the voltage is turned on, the cholesteric
Applying a voltage sufficient to induce a nematic transition
The crystalline layer is homeotropic in the optically
The lock structure 9 is taken. In the case of the present invention, when no voltage is applied,
The liquid crystal layer, which had two separate structures, was
Since the entire area can be in a transmission state,
It is possible to obtain contrast. This point is
By installing a scattering plate on the user side, sufficient contrast is ensured
This is in contrast to becoming difficult. Further, in the reflection type liquid crystal display device of the present invention,
Can also take advantage of the storage effects described above.
This will be briefly described with reference to FIGS. What
2, 11 and 11 'in FIG. 2 are electrode substrates, and 12 and 13 are front.
The electrodes formed on the electrode substrates 11 and 11 'and 14 are
15 is a switch, and 16 is a power supply. Homeotropic when voltage is applied as shown in FIG.
As shown in FIG. 2, the voltage is rapidly turned off from the structure 9.
The poly-domain planar structure 17 and the mono-domain
A liquid crystal layer composed of two structures of the planar structure 18 is formed.
This state is maintained thereafter. On the other hand,
1 is a homeotropic structure shown in FIG.
Lowering the applied voltage relatively slowly from the lock structure 9
Can be formed over the entire liquid crystal layer in this state.
Is maintained even after the voltage is turned off. Therefore,
Realizing two optically different states even when the voltage is off
Control compared to when voltage is applied.
Although the last is slightly inferior, it is possible to obtain sufficient display performance.
Wear. (II) The liquid crystal material region in the selective reflection state
The regions of the liquid crystal material in the scattering state are alternated in the vertical direction of the electrode substrate.
Indication of a structure formed separately: Such a structure
The display method will be briefly described with reference to FIG. electrode
Electrodes 22 and 23 formed on substrates 21, 21 '
Are subjected to vertical and horizontal alignment treatment, respectively.
I have. The electrode substrates 21, 21 'and the spacer 24
The voltage from the power supply 26 to the liquid crystal layer injected into the enclosed space
The application is controlled by the switch 25. In the case where the voltage is turned off, a vertically aligned electrode
The liquid crystal layer on the 22 side is the axis of the helical structure formed by the liquid crystal molecules.
Is relatively horizontal to the substrate 21 but in a random direction
To form a focal conic structure 27,
State. On the other hand, the side of the electrode 23 subjected to the horizontal alignment process
In the liquid crystal layer, the axis of the helical structure formed by the liquid crystal molecules is
To form a planar structure 28 aligned in the vertical direction,
It is in a reflection state. Thus, the horizontal alignment process is performed.
Liquid crystal layer between the substrate with vertical alignment and the substrate with vertical alignment.
Clarity without physically separating the liquid crystal layer
Different liquid crystal structures between a pair of electrodes
It becomes possible. For this reason, each is sandwiched between a pair of electrodes.
The effect of improving display characteristics using the two liquid crystal layers
It can be realized with a pure cell structure. Regarding the display when the voltage is off, both electrodes
Below compared to the conventional case where the same orientation treatment was applied.
It will be described in detail. The electrodes 22 and 23 were both horizontally aligned.
In the case of the conventional system, the liquid crystal layer is mono-domain over the entire area.
Brightness depending on the viewing angle
Not only changes significantly but also changes color, and is dependent on viewing angle.
Is large. In contrast, the liquid of the present invention
Consider the case where the crystal display element is viewed from the electrode 22 side. this
In the case where both electrodes 22 and 23 are horizontally aligned,
Focal conic structure that takes a scattering state compared to
27 is formed on the observer side to form a planar structure
In addition to improving the viewing angle characteristics of
The spectrum width of the reflected light is expanded by the
Una whiteness can be added. On the other hand, the liquid crystal display of the present invention
When the indicator element is viewed from the side of the electrode 23, both electrodes 22, 23
Compared to the case where both are horizontally aligned.
-Focal conic structure formed behind structure 28
27 improves viewing angle dependency and plays
Part of the light transmitted through the corner structure 28 is reflected to improve the reflectance.
It is possible to raise. Both electrodes 22 and 23 are vertically aligned.
In the conventional method, the liquid crystal layer is focused over the entire area.
Is the reflected light white due to scattering due to the ruconic structure?
The viewing angle characteristics are good, but the backscattering power is low.
Bright display cannot be performed. In contrast, the present invention
When the liquid crystal display element of FIG.
Compared to the case where both 2 and 23 were vertically aligned,
The planar structure 28 in the selective reflection state
To be formed behind the nick 27
In the selected wavelength region of the light transmitted through the
Reflects a circularly polarized light component in the same direction as the helix,
Can be improved. On the other hand, the liquid crystal display element of the present invention
When viewed from the side of the electrode 23, both electrodes 22, 23 are both
Whiteness is inferior to the case where
Formed on the observer side of the focal conic structure 27
Reflectivity is improved by the selective reflection state of the planar structure 28
It is possible to do. Next, when the voltage is on, cholesteric-
Applying a voltage sufficient to induce a nematic transition
Crystal layer is optically transmissive homeotropic throughout
Structure 39 is taken. In the case of the present invention, a scattering layer separately from the liquid crystal layer
Alternatively, unlike when a selective reflection layer is installed,
The whole area can be made to be in a transmission state by
High contrast can be obtained. Also, the drive power
Although it is desirable that the pressure be low in terms of power consumption, the present invention
In this case, since one of the electrodes is vertically aligned,
Homeotropic when two electrodes are horizontally aligned.
Voltage required for the transition to the lock structure 29, that is, the drive voltage
Can also be reduced. Further, in the reflection type liquid crystal display device of the present invention,
Can also take advantage of the storage effects described above.
This will be briefly described with reference to FIGS. What
4, 31 and 31 'in FIG. 4 are electrode substrates, and 32 and 33 are front.
The electrodes formed on the electrode substrates 31 and 31 ',
A switch 35; and 36, a power supply. Homeotropic when voltage is applied as shown in FIG.
FIG. 4 shows that the voltage is rapidly turned off from the structure 29.
The focal conic structure 37 and the planar structure 3
8, a liquid crystal layer having two structures is formed.
It is kept after that. Meanwhile, Focal Conic 3
7 is comparatively different from the homeotropic structure 29 shown in FIG.
Formed over the entire liquid crystal layer by slowly lowering the applied voltage
This condition then turns off the voltage
Even it is kept. Therefore, even when the voltage is off
Two optically different states can be realized
The contrast is slightly lower than when a voltage is applied
However, sufficient display performance can be obtained. Liquid Crystal Material Region in Selective Reflection State and Scattering
Liquid crystal material regions separated from each other in the vertical direction of the electrode substrate.
As a method of forming the electrodes at a distance,
We have described the case of performing horizontal and horizontal alignment processing.
Gives a physical uneven structure to the surface of the electrode substrate
Or disperse the polymer near the substrate surface
Can obtain the same effect. In that case, physical concave
On the side with a convex structure or on the side where the polymer is dispersed
A liquid crystal layer in a scattering state is formed. The method using the physical concavo-convex structure is a liquid crystal material.
Type, irregularity forming substance type, spacing, height, etc.
The dispersion method of the polymer material near the electrode substrate is the polymer material
Liquid crystal by setting conditions such as type of material, degree of polymerization, dispersion density, etc.
Large angle θ between the spiral axis formed by the substance and the electrode substrate
The size can be controlled. The liquid crystal layer has a θ of 90 °
If close, select polydomain by planar structure
Reflection state, and focal θ when θ is small.
It takes a scattering state due to the rock structure. For example, a scattering state is formed by an uneven structure.
If the height difference between the convex portion and the concave portion is 0.3 to 0.3
1.5 μm, the interval between individual convex portions or concave portions is 1.5 to
It is preferable to have a fine structure of 30 μm. The irregular structure
If the structure is too low, the angle θ between the spiral axis and the electrode substrate will be large.
This may cause formation of a selective reflection layer. Meanwhile, before
If the uneven structure is too high, the thickness of the liquid crystal layer will increase,
There is a risk that the applied voltage will increase. Also, adjust the interval between
When the thickness is less than 1.5 μm, helix formation of the liquid crystal material is inhibited.
Light at a preset reflection wavelength
May not be reflected. On the other hand, when the interval between
If it exceeds 0 μm, one pixel when performing matrix drive
Scattered light brightness
May drop. The vertical alignment substrate and the horizontal alignment substrate
When cholesteric liquid crystal is sealed in a liquid crystal cell consisting of a plate
The description concerning the combination is disclosed in JP-A-55-73023 and JP-A-55-73023.
It is in the sho 56-138721. However, the former is dichroic
PCGH (Phase) with dye added to cholesteric liquid crystal
Change Guest Host) method, the latter is dichroic color
Not limited to element addition, but limited to scattering / transmission mode
There is no description about the selective reflection mode.
The effect is completely different from the present invention. (III) different helical orientations and / or
The liquid crystal material region in the selective reflection state that takes the pitch length is used as the electrode substrate
Different spirals when formed continuously in the vertical direction
Electrode carrying an optically active substance that guides the orientation to the liquid crystal material
When a substrate is used and the liquid crystal material has at least one type of optical
Of the composition containing the toxic substance: For the indication method of such a composition
This will be briefly described with reference to FIG. For example, liquid crystal
The quality considers the case of a left-helical periodic structure by itself.
Electrodes 44, 4 formed on electrode substrates 41, 42, respectively
Optically active layers 46 and 47 covering
Composed of optically active substances that induce liquid crystals in different directions
And the former optically active layer 46 induces a right helix.
Active substance layer, the latter optically active layer 47 induces left helix
Consider the case of an optically active material layer that occurs. Electrode substrate 4
Injected into the space surrounded by 1, 42 and the spacer 45
A voltage is applied to the liquid crystal material 48 by the switch 51.
It is controlled and performed using a power supply 52. The electrode substrate 4
Either one of the transparent substrates 1 and 42 is transparent, and the transparent substrate
Observe the display element from the side. When the voltage is turned off, the optics that induces the right helix
The liquid crystal layer in contact with the active layer 46 has a liquid crystal material
Pitch structure longer than that of the periodic structure
A formed cholesteric phase is formed. on the other hand,
In the liquid crystal layer in contact with the optically active layer 47 that induces a left helix
Has a shorter pitch length than the helical periodic structure inherent to liquid crystal materials.
Cholesteric phase with planar structure of left helix
Is formed. Thus, a helical structure is induced in the liquid crystal layer.
By using an optically active layer to raise the
Different pitch lengths in the vertical direction of the substrate without separation
Cholesteric phase can be formed in a single cell
It works. Select as pitch width distribution width increases
The wavelength range expands. This makes the display color closer to white
Also, if the liquid crystal material layer is thick enough,
You can get an indication. Here the thickness of the liquid crystal layer is thick enough
Means that one circularly polarized component at the central wavelength of selective reflection is
It means that the thickness is more than necessary to reflect everything.
In the case of the present invention, the difference in pitch length can be obtained in a single cell without a separation layer.
Pitch length because a spiral structure can be constructed
No parallax compared to stacking multiple cells with different
High display quality can be obtained and the display element
Cost reduction is possible by weight reduction and simplified manufacturing process
Becomes Next, when the voltage is turned on, the cholesteric
Applying a voltage sufficient to induce a nematic transition
Crystal layer is optically transmissive homeotropic throughout
Structure 50 is taken. In the case of the present invention, when no voltage is applied
The liquid crystal layer having a different pitch length is
Since the entire area can be in a transmission state,
It is possible to obtain contrast. Further, in the reflection type liquid crystal display device of the present invention,
Can use the storage effect described above.
That is, from the homeotropic structure 50 when a voltage is applied,
By turning off the voltage sharply, the planar structure and
By slowly lowering the applied voltage, the focal
A liquid crystal structure can be formed over the entire liquid crystal layer.
These states are maintained as they are when the voltage is turned off. That is,
Realizing two optically different states even when the voltage is off
Control compared to when voltage is applied.
Although the last is slightly inferior, it is possible to obtain sufficient display performance.
Wear. Light that induces different helical orientations into the liquid crystal material
Using an electrode substrate carrying a biologically active substance and the liquid crystal substance
Describes the case that contains at least one optically active substance
Solid, other than this, optically active substance immobilized on the substrate
Helical Twisting Pow
er), immobilized area density,
Composition ratio when using several, and the liquid crystal substance is an optically active substance
The characteristic of the selectively reflected light, that is, the selective reflection
It is possible to control the emission wavelength range and the reflection intensity. For example, the same optically active substance is immobilized equally.
When used at the area density, the distance from the two electrode substrate surfaces
In the central part of the liquid crystal material, the liquid crystal material is in a nematic liquid crystal state
Cholesteric liquid crystal state on both sides
You. At this time, the refractive index anisotropy of the liquid crystal material, nematic liquid crystal
The thickness of the state region is sufficient to form a half-wave plate
If the conditions are met, the cholesteric liquid crystal pitch length and liquid
Wave defined by the average refractive index of crystalline material and refractive index anisotropy
All the circularly polarized light components in the long region are reflected, and a bright display can be obtained.
Can be. This will be described with reference to FIG. For example,
Space surrounded by electrode substrates 61 and 62 and spacer 63
Nematic liquid crystal is injected as a liquid crystal material into the electrode 64.
That the optically active layer 65 covering the layer induces a left helix
I do. In the area near the optically active layer 65, cholesteric
While a liquid crystal planar structure 66 is formed,
In a region sufficiently distant from the conductive layer 65, a homogeneous structure
A nematic liquid crystal layer 67 is formed. Nematic liquid crystal layer
The thickness of 67 is d and the optical anisotropy of the nematic liquid crystal material is Δ
When n is set, d × Δn × 2 is the wavelength region of visible light.
Adjust the distance between the electrodes as described above. Now, from the electrode substrate 61
Cholesteric on the electrode substrate 61 side
The layer 66 reflects only the left circularly polarized light component of the selective reflection area
However, the right circularly polarized light component is transmitted even in the selective reflection area.
The right circularly polarized light component is converted into a left circularly polarized light by the nematic liquid crystal layer 67.
Cholesteric on the electrode substrate 62 side
The light is reflected by the liquid crystal layer 68. This light is a nematic liquid crystal
At 67, the light is again converted into a right-handed circularly polarized light component.
The light can pass through the cholesteric liquid crystal layer 66 on one side. This liquid
When viewed as a whole crystal display element, all circles in the selective reflection wavelength region
It is possible to reflect the polarization component, and only one
The reflectivity doubles as compared with the conventional type that reflects a light component. This
Thereby, a bright display can be performed. Of the present invention
In the case of liquid crystal display elements, when no voltage is applied
The entire area of the liquid crystal layer can be made more transparent.
Therefore, good contrast can be obtained. This place
In this case, the storage effect can be used. Further, an optically active substance fixed to a substrate
When a substance has many optically active sites in one molecule,
Liquid crystal material corresponding to the spatial distribution of active sites between electrode substrates
Helical orientation and helical pitch length distribution
To control the properties of the selectively reflected light.
It works. (IV) different helical orientations and / or
The liquid crystal material region in the selective reflection state that takes the pitch length is used as the electrode substrate
When two electrodes are formed continuously in the vertical direction
Spacers and electrodes, which are members that keep the distance between plates constant
A configuration in which the optically active substance is immobilized on both of the substrates
Display: A display method of such a configuration will be described with reference to FIG.
It will be explained briefly. For example, optically active substances as liquid crystal substances
Light that induces a left helix on the electrode substrate 81 side
Active layer 85 bears on electrode substrate 81 and spacer 83.
Optical activity to guide the right helix on the electrode substrate 82 side.
Layer 86 is supported on electrode substrate 82 and spacer 84
ing. This structure uses a photosensitive resin or the like,
By adopting the method of forming the pacer on the electrode substrate,
Can be prepared relatively easily. When no voltage is applied, the liquid crystal material 8
Reference numeral 8 denotes a left spiral planar structure on the electrode substrate 81 side.
On the other hand, a planar structure of a right spiral is formed on the electrode substrate 82 side.
Take. When the helical forces of the optically active layers 85 and 86 are equal,
If the pitch lengths are equal and their orientations are reversed,
A structure is formed between the electrode substrates 81,. Accordingly
All the light components in the selective reflection wavelength range are reflected,
Brighter than when only one of the circularly polarized components is reflected
It is possible to obtain a bright display twice as high. Voltage
When applied, the entire liquid crystal layer is optically transparent
Obtain good contrast with tropic structure
Can be. Also in this case, the storage effect can be used. Note that an optically active resin is used as the alignment film.
The invention was published as Japanese Patent Application Laid-Open No. 58-10721,
After the patent is registered. Langmuir, 11, 4838 (19
95) also when using an optically active layer as an alignment film
Although both have been reported,
There is no description, and the effect is completely different from the present invention.
Are different. (V) different helical orientations and / or
The liquid crystal material region in the selective reflection state that takes the pitch length is used as the electrode substrate
Of the cases where two electrodes were continuously formed in the vertical direction,
A polymer material is held between the polar substrates together with the liquid crystal material.
Physical properties and / or chemicals
Displaying different configurations in the vertical direction: a display method for such a configuration
Will be briefly described with reference to FIG. In this example
In the case of polymer, submicron-order fine particles of polymer
An eye structure 105 is employed. Electrode substrates 101, 102 and
And less injected into the space surrounded by the spacer 103
The liquid crystal material 106 containing one kind of optically active substance
It exists in the gap of the child network structure. Each electrode 104
Vertically in relation to the electrode substrates 101 and 102
Under symmetric polymerization conditions, monomers or oligomers overlap
By combining, the occupation of the polymer material between the liquid crystal substances
The volume is from the electrode substrate 101 to the electrode substrate 102
A reduced state has been realized. In this case, the liquid crystal material
Of the optically active substances contained,
When a certain amount is taken into the polymer material,
The optical activity in the liquid crystal material in the gaps of the polymer network
The content of the substance is changed from the electrode substrate 101 to the electrode substrate 102.
To increase. Incorporated into polymer material
Light that cannot interact with other liquid crystal materials
Bioactive substance does not contribute to helix formation and / or does not
The helical pitch length of the liquid crystal material is
From 01 to the electrode substrate 102,
The selective reflection wavelength shifts to a shorter wavelength. As a whole element
By expanding the selective reflection wavelength range, white light of reflected light,
Has an effect of increasing brightness. Above is the voltage
This is the case when no voltage is applied.
Takes homeotropic structure 107 and responds to selective reflection
Thus, a sufficient contrast can be obtained. in this case
Even the storage effect can be used. Using a copolymer as a polymer material,
Under asymmetric polymerization conditions perpendicular to the plate, the monomer or
Oligomerization of the polymer material that contacts the liquid crystal substance by polymerizing the oligomer
Change the surface component in the direction perpendicular to the electrode substrate, or
Table asymmetrically perpendicular to the electrode substrate for a uniform polymer
Even if a method such as surface modification is applied,
Of the optically active substance and / or helix forming power
Controllable and gradient distribution of polymer material
The same effect as in the above-described example can be obtained. Said co-heavy
Combination of hydrophilic monomer and hydrophobic monomer
Or a hydrocarbon monomer and a perfluoro
Nomer combinations can be mentioned as preferred examples.
Wear. (VI) Different spiral orientations and / or
The liquid crystal material region in the selective reflection state that takes the pitch length is used as the electrode substrate
Optically active site when formed continuously in the vertical direction
A polymerizable monomer and / or oligomer having
After once holding it between the electrode substrates with other liquid crystal substances
Indication of superimposed structure: How to display such a structure
This will be briefly described with reference to FIG. In this case, no voltage
In addition, the liquid crystal layer has a planar structure before polymerization, and
Spiral pitch length changed in the direction perpendicular to the electrode substrate
The polymerization is carried out in the state. In this state, each of the electrodes 114 has
Heat that is asymmetrical in the direction perpendicular to the electrode substrates 111 and 112
It can be realized by processing. After the polymerization, the electrode substrates 111, 11
The optically active portion is in a space surrounded by
Of the spiral formed by the polymeric material 116 having
The length is fixed with a gradient. The liquid crystal material
Orientation along the polymer helix, wide pitch length distribution
A planar structure 115 is formed, resulting in a selective reflected wave.
The long range is widened, and whitening and high luminance of the display are realized.
Under a voltage applied state, the polymer material 116 changes its structure.
Although not available, the liquid crystal material has a homeotropic structure 117.
Optical transmission. In the case of this method,
Storage effect on display because it does not go through nick structure
Cannot be used, but from the planar structure
Low drive voltage for direct transition to homeotropic structures
Display device driving effects such as
You. In addition, a small amount of non-polymerizable optically active substance
By including it, the focal voltage can be
It is also possible to use the storage effect using a nick structure.
You. Further, the planar portion shown in the left part of FIG.
The following method is used as a method for realizing the structure. light
Polymerizable monomer having a biologically active site and / or
The ligomer is used together with other liquid crystal materials for the electrode substrates 111, 11
After holding once between the two, unpaired in the vertical direction of the electrode substrate
The electrode substrates 111 and 11 are polymerized under nominal conditions.
2 was graded in the degree of polymerization in the vertical direction.
Increasing the helical force of the sexual site. (VII) Two electrodes having different surface energies
By using the substrate and multiple liquid crystal materials, the electrode substrate direction
Of a configuration in which a structure that is spontaneously phase-separated is taken:
A display method having such a configuration will be briefly described with reference to FIG.
Will be described. Electrode substrate 13 each having electrode 134
1, 132 are electrode substrate coating layers 135 and 136, respectively.
Coated with different layers of surface energy,
Surrounded by the electrode substrates 131 and 132 and the spacer 133
The space is filled with two components with different surface energies
Liquid crystal material is injected. Now, the surface energy
Assuming that the smaller one is the electrode coating layer 135,
Liquid crystal material with low surface energy
137, while electrode coating with high surface energy
A liquid crystal material having a large surface energy is
A laner structure 138 is formed. At this time, the liquid crystal material
Depending on the choice of charge, the planar structures 137, 138
When the pitch length is the same and the helical direction is different,
The case where the pitch length is different regardless of the direction can be selected.
Reflects all light components in the selective reflection wavelength range
Brightness in the latter case.
Whitening and high luminance can be realized by widening the area. Share
In order to further stabilize the separation state, keep the distance between the electrode substrates constant.
A similar covering layer may be provided on a member to be carried. Voltage application
Is performed, the entire liquid crystal layer becomes homeotropic structure 139, 1
40, which is optically transparent,
And a sufficient contrast can be obtained. This place
You can also use the storage effect. [0081] DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail.
I do. (Example 1) On the electrode surfaces of two glass substrates with ITO electrodes
Polyimide (AL-1051: Nippon Gosei
With a spinner to a thickness of 70 nm.
To the surface of the alignment film for only one substrate.
The rubbing treatment was performed by the method described above. Then, use standard methods
Epoxy adhesive for bonding to the other electrode surface
And the other electrode surface is made of a resin having a diameter of 9 μm.
Spacer balls were sprayed. After that, the electrode surfaces face each other
We stuck together and sealed. The liquid crystal material is nematic
Liquid crystal material E48 (trade name, manufactured by MERCK) 60wt
% And optically active substance CB15 (trade name of MERCK) 4
0% by weight of a mixture is injected in a conventional manner in an isotropic state,
The above-described liquid crystal display element shown in FIG. 1 was manufactured. The display state of the element is as follows: voltage on (square wave, V
(p = 55 V, 60 Hz). Turn off the voltage
Then, it becomes a selective reflection state, and the display is a little white green (reflection pole
Large wavelength 560 nm), the reflectance is 80% or more,
The contrast with the in-state was as good as 40 or more. Electric
When the applied voltage is gradually lowered from the pressure
The color is pale white and this state is maintained even after the voltage is turned off.
Was. Both the selective reflection state and the scattering state shown in FIG.
Pressure is off and stable for more than one month for sufficient storage effect
confirmed. Display of the liquid crystal display device manufactured as described above
The characteristics are shown in Table 1 below. The liquid crystal display device of the present invention
In order to obtain better display characteristics, the display observation direction is
It is from the side of the substrate that is not subjected to horizontal alignment processing. this
The observation direction is common to the following Examples 2 to 28. 2
Example 1 in which no horizontal alignment treatment is performed on a glass substrate
However, the observation direction is not limited. The display characteristics are
White light is incident on the glass substrate from the direction of 10-20 °
To measure the luminance (Y value) of reflected light in the vertical direction of the substrate.
More evaluated. This evaluation method is described in Examples 2 to 28 below.
But it is common. Table 1 shows the results of horizontal alignment treatment.
Two electrode substrates (Comparative Example 1), both with vertical alignment
Two electrode substrates (Comparative Example 2) and
Display composed of two electrode substrates (Comparative Example 3)
The characteristics of the element are also described. [0084] [Table 1](Embodiment 2) The electrode base was formed in the same manner as in Embodiment 1.
The process up to the sealing of the plate was performed. Next, nematic is used as a liquid crystal material.
Liquid crystal material E48 (product name, manufactured by MERCK) 67wt
% And optically active substance CB15 (trade name of MERCK) 3
A 3 wt% mixture is injected in the isotropic state by a conventional method and
A crystal display element was produced. The display state of the element is as follows: voltage on (square wave, V
(p = 55 V, 60 Hz). Turn off the voltage
Then, it becomes a selective reflection state, and the display is slightly white red (reflection
The reflectance is 70% or more at the maximum wavelength of 660 nm, and the voltage is
The contrast with the ON state was as good as 35 or more.
If the applied voltage is gradually lowered from the voltage on, scattering state will occur.
The color is pale white, and this state is maintained even after the voltage is turned off.
Was done. Both the selective reflection state and the scattering state
After confirming that it is stable for more than one month and has a sufficient storage effect
Was. (Embodiment 3) An electrode base was formed in the same manner as in Embodiment 1.
The process up to the sealing of the plate was performed. Next, nematic is used as a liquid crystal material.
Liquid crystal material E48 (trade name of MERCK) 53wt
% And optically active substance CB15 (trade name of MERCK) 4
A 7 wt% mixture is injected in the form of an isotropic phase by a conventional method and
A crystal display element was produced. The display state of the element is as follows: voltage on (square wave, V
(p = 55 V, 60 Hz). Turn off the voltage
Then, it is in the selective reflection state, and the display is slightly white blue (reflection
Maximum wavelength 480nm), its reflectance is 70% or more, voltage
The contrast with the ON state was as good as 35 or more.
If the applied voltage is gradually lowered from the voltage on, scattering state will occur.
The color is pale white, and this state is maintained even after the voltage is turned off.
Was done. Both the selective reflection state and the scattering state
After confirming that it is stable for more than one month and has a sufficient storage effect
Was. (Embodiment 4) The electrode base was formed in the same manner as in Embodiment 1.
The process up to the sealing of the plate was performed. Next, nematic liquid crystal material
Liquid crystal material ZLI4900-000 (MERCK, Inc.)
(Product name) 60 wt% and optically active substance CB15 (MERC
K company product name) 40 wt% mixture is always in isotropic phase
The liquid crystal display device was manufactured by injection by a method. The display state of the element is as follows: voltage on (square wave, V
(p = 55 V, 60 Hz). Turn off the voltage
Then, it is in the selective reflection state, and the display is a little
Emission wavelength of 520 nm), its reflectance is 80% or more,
The contrast with the pressure-on state is as good as 40 or more.
Was. When the applied voltage is gradually lowered from the voltage on, the scattering state
The color is pale white, and this state remains after the voltage is turned off.
Held. Both the selective reflection state and the scattering state
Is stable for more than a month and has sufficient storage effect
did. (Embodiment 5) The electrode base was formed in the same manner as in Embodiment 1.
The process up to the sealing of the plate was performed. Next, nematic is used as a liquid crystal material.
Liquid crystal material E48 (trade name of MERCK) 72wt
% And optically active substance S811 (trade name, manufactured by MERCK) 2
8 wt% of the mixture is injected in the isotropic state by a conventional method
A crystal display element was produced. The display state of the element is as follows: voltage on (square wave, V
(p = 55 V, 60 Hz). Turn off the voltage
Then, it is in the selective reflection state, and the display is slightly orange (reflection
A maximum wavelength of 620 nm), the reflectance is 70% or more, and the voltage is
The contrast with the ON state was as good as 35 or more.
If the applied voltage is gradually lowered from the voltage on, scattering state will occur.
The color is pale white, and this state is maintained even after the voltage is turned off.
Was done. Both the selective reflection state and the scattering state
After confirming that it is stable for more than one month and has a sufficient storage effect
Was. (Example 6) Two glass substrates with ITO electrodes
Polyimide (AL-105) as an alignment film on the electrode surface of the plate
1: Nippon Synthetic Rubber Co., Ltd.) to a thickness of 70 nm
Caster and distribute it to only one substrate.
Rubbing treatment was performed on the surface of the facing film by a usual method. Next
Then, use an ordinary method to attach an electrode to one electrode surface.
Apply a xy adhesive in place and apply a diameter to the other electrode surface.
3 μm resin spacer balls were sprayed. afterwards,
The electrodes were bonded so that the electrode surfaces faced each other and sealed. liquid
The crystal material is a nematic liquid crystal material E48 (MERCK)
(Product name) 60 wt% and optically active substance CB15 (MERC
K company product name) 40 wt% mixture is always in isotropic phase
The liquid crystal display device shown in FIG.
Made. The display state of the element is as follows: voltage on (square wave, V
(p = 20 V, 60 Hz). Turn off the voltage
Then, it becomes a selective reflection state, and the display is a little white green (reflection pole
Large wavelength 560 nm), the reflectance is 70% or more,
The contrast with the in-state was as good as 35 or more. Electric
When the applied voltage is gradually lowered from the pressure
The color is pale white and this state is maintained even after the voltage is turned off.
Was. Both the selective reflection state and the scattering state shown in FIG.
Pressure is off and stable for more than one month for sufficient storage effect
confirmed. (Example 7) Glass substrate with one ITO electrode
Polyimide (AL-105) as an alignment film on the electrode surface of the plate
1: Nippon Synthetic Rubber Co., Ltd.) to a thickness of 70 nm
And the alignment film surface Rabin by the usual method
Treatment. The other electrode of the glass substrate with ITO electrode
The surface is oxidized from 80 degrees to the substrate normal.
Oblique deposition of Recon (OCD: trade name of Tokyo Ohka Kogyo Co., Ltd.)
To form a thin film having a thickness of 50 nm.
Polyvinyl alcohol on the surface (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
Was cast by a spinner. The two electrode substrates
And a liquid crystal display element was fabricated in the same manner as in Example 6.
Was. As a result, display characteristics almost similar to those of the sixth embodiment, and
Confirmed the storage effect. (Embodiment 8) Glass base with one ITO electrode
Polyimide (AL-105) as an alignment film on the electrode surface of the plate
1: Spinner made by Japan Synthetic Rubber Co., Ltd. to a thickness of 70 nm
Cast by. Of the other glass substrate with ITO electrode
The electrode surface is accumulated by the Langmuir-Blodgett method.
With a surface pressure of 25 mN / m and a cumulative speed of 20 mm / min,
Water surface of dimethyl hexadecyl ammonium riamate
Ten upper monolayers were accumulated. Next, the two electrodes
Using a substrate, a liquid crystal display element was fabricated in the same manner as in Example 6.
Made. As a result, the display characteristics and the display characteristics were almost the same as those in Example 6.
And the storage effect was confirmed. (Example 9) Glass substrate with one ITO electrode
Polyimide (AL-105) as an alignment film on the electrode surface of the plate
1: Nippon Synthetic Rubber Co., Ltd.) to a thickness of 70 nm
Cast by Gnar. Glass base with the other ITO electrode
Polyvinyl cinnamate with a thickness of 100
It was cast with a spinner to a thickness of nm. Then,
Helium-neon laser linearly polarized on a thin film of aluminum
-(325 nm, 5 mW / cm^Two ) Irradiate for 1 hour,
A photoduplexing reaction was performed. Using the two electrode substrates,
A liquid crystal display device was manufactured in the same manner as in Example 6. That
As a result, the display characteristics and the storage characteristics were almost the same as those in Example 6.
The effect was confirmed. Example 10 Glass with One ITO Electrode
Polyimide (AL-105) is used as an alignment film on the electrode surface of the substrate.
1: Nippon Synthetic Rubber Co., Ltd.) to a thickness of 70 nm
Cast by Gnar. Glass base with the other ITO electrode
For the electrode surface of the plate, the direction is 60 degrees with respect to the substrate normal.
Silicon oxide (OCD: trade name of Tokyo Ohka Kogyo Co., Ltd.)
Oblique deposition was performed. Example using the two electrode substrates
A liquid crystal display device was manufactured in the same manner as in No. 6. as a result,
Display characteristics and storage effect almost the same as those of the sixth embodiment.
It was confirmed. (Example 11) Glass with one ITO electrode
On the electrode surface of the substrate, a polyimide for horizontal alignment (A
L-3046: trade name, manufactured by Nippon Synthetic Rubber Co.)
Cast by spinner to the thickness and align the film in the usual way
The surface was rubbed. Glass with the other ITO electrode
Polyimide for vertical alignment as an alignment film on the electrode surface of a substrate
(SE-7511: trade name, manufactured by Nissan Chemical Industries, Ltd.)
m was cast by a spinner. Then, the usual method
Epoxy bonding to one electrode surface for bonding
The adhesive is applied to a predetermined position, and the other electrode surface has a diameter of 3 μm.
Was sprayed. Then, the electrode surface
They were stuck together and sealed. Liquid crystal material
Is a nematic liquid crystal material E48 (product of MERCK)
Name) 60wt% and optically active substance CB15 (MERCK company)
Product name) 40wt% mixture in isotropic phase in a conventional manner
The liquid crystal display element shown in FIG.
A child was made. The display state of the element is as follows: voltage on (square wave, V
(p = 18 V, 60 Hz). Turn off the voltage
Then, it became a scattering + reflection state and the color of the reflected light was greenish
White (reflection maximum wavelength 560 nm) with a reflectance of 40%
As described above, the contrast with the voltage-on state is as good as 20 or more.
Met. When the applied voltage is gradually reduced from the voltage on,
Disturbance occurs and the color is pale white.
After being retained. The scattering + reflection state and the scattering state are both
It was stable for more than one month with the voltage off. The liquid crystal table of Example 11 manufactured as described above was used.
Table 2 below shows the display characteristics of the display elements. In Table 2,
Two electrode substrates both subjected to vertical alignment processing (Comparative Example 4)
And two electrode substrates with horizontal alignment
The characteristics of the display element configured in Example 5) are also described. [0102] [Table 2] (Example 12) Glass with one ITO electrode
On the electrode surface of the substrate, a polyimide for horizontal alignment (A
L-3046: trade name, manufactured by Nippon Synthetic Rubber Co.)
Cast by spinner to the thickness and align the film in the usual way
The surface was rubbed. Glass with the other ITO electrode
Octadecyl triethoxy as an alignment film on the electrode surface of the substrate
Sisilane (manufactured by Wako Pure Chemical Industries, Ltd.) is formed to a monolayer thickness.
Was. Next, a bonding method is applied to one of the electrode surfaces by a conventional method.
Epoxy adhesive in place and apply the other
Spray 10μm diameter resin spacer balls on the extreme surfaces
Was. After that, the electrodes are stuck so that the electrode faces face each other.
Sealed. The liquid crystal material is a nematic liquid crystal material E48 (M
ERCK brand name) 60wt% and optically active substance CB1
5 (Merck product name) 40wt% mixture isotropically
A liquid crystal display element was produced by injecting in a conventional manner in the state of the phase. The display state of the element is as follows: voltage on (square wave, V
(p = 55 V, 60 Hz). Turn off the voltage
Then, it became a scattering + reflection state and the color of the reflected light was greenish
White (reflection maximum wavelength 560 nm) with a reflectance of 40%
As described above, the contrast with the voltage-on state is as good as 20 or more.
Met. When the applied voltage is gradually reduced from the voltage on,
Disturbance occurs and the color is pale white.
After being retained. The scattering + reflection state and the scattering state are both
It was stable for more than one month with the voltage off. (Example 13) Glass with one ITO electrode
On the electrode surface of the substrate, a polyimide for horizontal alignment (A
L-1051: trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.)
Cast by spinner to the thickness and align the film in the usual way
The surface was rubbed. Glass with the other ITO electrode
Fluorine resin (CTX-8) as an alignment film on the electrode surface of the substrate
07: Spinner made by Asahi Glass Co., Ltd.) with a thickness of 80 nm
Cast by. Then, one of the electrode surfaces
The epoxy adhesive for bonding in place
5 μm diameter resin spacer on the other electrode surface
The ball was sprayed. After that, the electrode surfaces will face each other
We stuck together and sealed. Liquid crystal material is nematic liquid
Material E48 (trade name of MERCK) 60 wt% and light
Chemically active substance CB15 (trade name of MERCK) 40wt
% Of the mixture in the state of an isotropic phase by a conventional method.
An indicator element was manufactured. The display state of the element is as follows: voltage on (square wave, V
(p = 28 V, 60 Hz). Turn off the voltage
Then, it became a scattering + reflection state and the color of the reflected light was greenish
White (reflection maximum wavelength 560 nm), its reflectance is 40%
As described above, the contrast with the voltage-on state is as good as 20 or more.
Met. When the applied voltage is gradually reduced from the voltage on,
Disturbance occurs and the color is pale white.
After being retained. The scattering + reflection state and the scattering state are both
It was stable for more than one month with the voltage off. (Embodiment 14) In the same manner as in Embodiment 11,
The process up to the sealing of the polar substrate was performed. Next, as a liquid crystal material,
Matic liquid crystal material E48 (trade name, manufactured by MERCK) 67
wt% and optically active substance CB15 (product of MERCK)
Name) Inject 33% by weight of the mixture by a conventional method
A child was made. The display state of the element is as follows: voltage on (square wave, V
(p = 18 V, 60 Hz). Turn off the voltage
Then, it becomes a scattering + reflection state and the color is reddish white
(Reflection maximum wavelength 660 nm), the reflectance of which is 30% or less
Above, the contrast with the voltage on state is as good as 10 or more
there were. Scattering when the applied voltage is gradually reduced from voltage on
It became a state and the color was pale white, and in this state the voltage was turned off
Later retained. Both the scattering + reflection state and the scattering state
It was stable for more than one month when the voltage was turned off. (Embodiment 15) In the same manner as in Embodiment 11,
The process up to the sealing of the polar substrate was performed. Next, as a liquid crystal material,
Matic liquid crystal material E48 (trade name, manufactured by MERCK) 53
wt% and optically active substance CB15 (product of MERCK)
Name) Injection of 47wt% mixture in isotropic phase by standard method
Then, a liquid crystal display device was manufactured. The display state of the element is as follows: voltage on (square wave, V
(p = 18 V, 60 Hz). Turn off the voltage
Then, it becomes a scattering + reflection state and its color is blueish white
(The maximum wavelength of reflection is 480 nm), and the reflectance is 30% or less.
Above, the contrast with the voltage on state is as good as 10 or more
there were. Scattering when the applied voltage is gradually reduced from voltage on
It became a state and the color was pale white, and in this state the voltage was turned off
Later retained. Both the scattering + reflection state and the scattering state
It was stable for more than one month when the voltage was turned off. (Embodiment 16)
The process up to the sealing of the polar substrate was performed. Next, as a liquid crystal material,
Matic liquid crystal material ZI4900-000 (MERCK company)
60% by weight of optically active substance CB15 (MER
CK company trade name) 40wt% mixture in isotropic phase
Injection was performed by a conventional method to produce a liquid crystal display device. The display state of the element is as follows: voltage on (square wave, V
(p = 18 V, 60 Hz). Turn off the voltage
Then, it becomes a scattering + reflection state and its color is blueish white
(The maximum reflection wavelength is 520 nm) and the reflectance is 30% or less.
In addition, the contrast with the voltage-on state is as good as 20 or more.
there were. Scattering when the applied voltage is gradually reduced from voltage on
It became a state and the color was pale white, and in this state the voltage was turned off
Later retained. Both the scattering + reflection state and the scattering state
It was stable for more than one month when the voltage was turned off. (Embodiment 17)
The process up to the sealing of the polar substrate was performed. Next, as a liquid crystal material,
Matic liquid crystal material E48 (trade name, manufactured by MERCK) 72
wt% and optically active substance S811 (product of MERCK)
Name) Inject 28% by weight of mixture in isotropic phase according to standard method
Then, a liquid crystal display device was manufactured. The display state of the element is as follows: voltage on (square wave, V
(p = 55 V, 60 Hz). Turn off the voltage
Then, it becomes a scattering + reflection state and the color is orange-white
(The maximum reflection wavelength is 620 nm), and the reflectance is 30% or less.
In addition, the contrast with the voltage-on state is as good as 20 or more.
there were. Scattering when the applied voltage is gradually reduced from voltage on
It became a state and the color was pale white, and in this state the voltage was turned off
Later retained. Both the scattering + reflection state and the scattering state
It was stable for more than one month when the voltage was turned off. (Embodiment 18) Glass substrate with ITO electrode
Photosensitive polyimide (Provimide 4) is used as an alignment film on the electrode surface.
12: Fuji Hunt's product name)
I did. An optical mask with a predetermined pattern
Using a parallel exposure machine (PLA105: product made by Nikon Corporation)
Exposure of the polyimide film formed on the substrate
Was. After forming uneven structure by development and rinsing process
Polyimide film (AL3) for the purpose of assisting the adsorption of liquid crystal molecules
045: Nippon Synthetic Rubber Co., Ltd.)
It was formed at 0 nm. Then, on one electrode surface by the usual method
Attaches the epoxy adhesive for bonding in place.
And a resin spacer having a diameter of 3 μm on the other electrode surface.
Sprayed. Then, make sure that the electrode surfaces face each other.
Laminated and sealed. The liquid crystal material is a nematic liquid crystal material
E63 (trade name of MERCK) 63wt% optical activity
Mixture of substance CB15 (trade name of MERCK) 37wt%
The compound is injected in a conventional manner in the isotropic state to
Produced. The display state of the element is as follows: voltage on (square wave, V
(p = 15 V, 60 Hz). Turn off the voltage
Then, it became a scattering + reflection state and the color of the reflected light was greenish
White (reflection maximum wavelength 590 nm), the reflectance is 60%
As described above, the contrast with the voltage on state is as good as 10 or more.
Met. When the applied voltage is gradually reduced from the voltage on,
Disturbance occurs and the color is pale white.
After being retained. The scattering + reflection state and the scattering state are both
It was stable for more than one month with the voltage off. (Example 19) Glass with one ITO electrode
Polybenzyl-L-gluta as an alignment film on the electrode surface of the substrate
Mate (P-5386: Sigma)
In addition, an alignment film is provided on the electrode surface of the other glass substrate with an ITO electrode.
To give polybenzyl-D-glutamate (P-3388:
Sigma Co., Ltd.)
(TSL8345: trade name of Toshiba Silicone Co., Ltd.)
Fixed. Then, it is attached to one electrode surface by a usual method.
Apply epoxy adhesive for alignment in place,
A 4.5 μm diameter resin spacer board is mounted on the other electrode surface.
Sprayed. Then, stretch so that the electrode surfaces face each other.
We joined and sealed. The liquid crystal material is a nematic liquid crystal material
E48 (MERCK company name) 60wt% and chiral
Mixing of 40wt% of agent CB15 (trade name, manufactured by MERCK)
The material is injected in a conventional manner in an isotropic state, and FIG.
The liquid crystal display device shown was produced. The display state of the element is as follows: voltage on (square wave, V
(p = 30 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state, and the display is slightly greenish green
Color (maximum reflection wavelength: 560 nm), its reflectance is 70% or less
Above, the contrast with the voltage-on state is as good as 40 or more
there were. Scattering when the applied voltage is gradually reduced from voltage on
It became a state and the color was pale white, and in this state the voltage was turned off
Later retained. Both the selective reflection state and the scattering state
Pressure is off and stable for more than one month for sufficient storage effect
confirmed. The liquid crystal table of Example 19 prepared as described above
Table 3 below shows the display characteristics of the display elements. In Table 3,
Both electrode substrates are coated with polyimide as alignment film
And a nematic liquid crystal material E48 (ME
RCK product name) 60wt% and chiral agent CB15
(Merck product name) 40 wt% mixture was injected
Of the conventional type liquid crystal display device as Comparative Example 6.
You. [0120] [Table 3] (Example 20) Glass with one ITO electrode
4-carboxy-4'- as an alignment film on the electrode surface of the substrate
[2- (S) -methylbutyl] -biphenyl is replaced with the other
On the electrode surface of the glass substrate with ITO electrodes, 4-
Carboxy-4 '-[2- (R) -methylbutyl] -bi
Each phenyl is bonded to a silane coupling agent (TSL834).
5: trade name, manufactured by Toshiba Silicone Co., Ltd.).
Then, for bonding to one electrode surface by a conventional method,
Apply epoxy adhesive in place and apply to the other electrode surface
A resin spacer ball having a diameter of 4.5 μm was sprayed.
After that, they are bonded together so that the electrode surfaces face each other, and sealed.
did. The liquid crystal material is a nematic liquid crystal material E48 (MER
CK (trade name) 60 wt% and chiral agent CB15 (M
ERCK product name) 40wt% mixture in isotropic phase
The liquid crystal display element shown in FIG.
A child was made. The display state of the element is as follows: voltage on (square wave, V
(p = 30 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state, and the display is slightly greenish green
Color (maximum reflection wavelength: 560 nm), its reflectance is 60% or less
Above, the contrast with the voltage-on state is as good as 30 or more.
there were. Scattering when the applied voltage is gradually reduced from voltage on
State and the display is pale white.
Held. Both the selective reflection state and the scattering state
Is stable for more than a month and has sufficient storage effect
did. Example 21 One Glass with ITO Electrode
Polybenzyl-L-gluta as an alignment film on the electrode surface of the substrate
Mate (P-5386: trade name, manufactured by Sigma), and others
On the electrode surface of the glass substrate with ITO electrode
Polybenzyl-L-glutamate (P-5386: Si
gma product name) and polybenzyl-D-glutamate
(P-3388: trade name, manufactured by Sigma)
(A quantitative ratio of 6: 4) with a silane coupling agent (TSL83).
45: Toshiba Silicone Co., Ltd.)
Was. Then, one of the electrode surfaces was laminated by a conventional method.
Epoxy adhesive in place and apply the other electrode
Spray 4.5μm diameter resin spacer balls on the surface
Was. After that, the electrodes are stuck so that the electrode faces face each other.
Sealed. The liquid crystal material is a nematic liquid crystal material E48 (M
ERCK brand name) 60wt% and chiral agent CB15
(Merck product name) 40wt% mixture isotropic phase
In the state described above, injection was carried out by a conventional method to produce a liquid crystal display device. The display state of the element is as follows: voltage on (square wave, V
(p = 30 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state, and the display is slightly greenish green
Color (maximum reflection wavelength: 560 nm), its reflectance is 60% or less
Above, the contrast with the voltage-on state is as good as 30 or more.
there were. As a result of the reflection spectrum measurement,
Compared to conventional display devices using imide,
Confirm that the wavelength range is expanded about 1.3 times
Was. Note that if the applied voltage is gradually reduced after the voltage is turned on,
The display is light white and the display is in a disturbed state.
Was also retained. Both the selective reflection state and the scattering state
Off and stable for more than one month to ensure a sufficient storage effect
I accepted. Example 22 Polybenzyl-L-gluta
Fixing mate (P-5386: Sigma product name)
In order to make electrode substrates with different densities,
Polybenzyl- as an alignment film on the electrode surface of a glass substrate with electrodes
L-Glutamate (P-5386: Sigma product)
Amino-terminated silane coupling that reacts with name
(TSL8340: trade name, manufactured by Toshiba Silicone Co., Ltd.)
Reaction of methyl group end type silane coupling agent (T
SL8241: Toshiba Silicone's product name)
(1: 3 by weight) and then treated with polybenzyl-L-G
Rutamate (P-5386: Sigma)
Immobilized. The other glass substrate with ITO electrode is made of silane
Coupling agent (TSL8340: manufactured by Toshiba Silicone Co., Ltd.)
Polybenzyl-L-gluta)
Mate (P-5386: Sigma)
It has become. Then, it is stuck to one electrode surface by a usual method.
Apply epoxy adhesive for the predetermined position and the other
4.5μm diameter resin spacer balls are scattered on the electrode surface.
Clothed. After that, the electrodes are stuck so that the electrode faces face each other.
And sealed. The liquid crystal material is a nematic liquid crystal material E48
(Merck product name) 60wt% and chiral agent CB
15 (trade name of MERCK) 40 wt% mixture etc.
The liquid crystal display element is manufactured by injecting the liquid crystal in the state of
Was. The display state of the element is as follows: voltage on (square wave, V
(p = 30 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state and the display is slightly white green
(The maximum reflection wavelength is 545 nm), and the reflectance is 50% or less.
Above, the contrast with the voltage-on state is as good as 25 or more.
there were. As a result of the reflection spectrum measurement,
Compared to conventional display devices using imide,
Confirm that the wavelength range is expanded about 1.2 times
Was. Note that if the applied voltage is gradually reduced after the voltage is turned on,
The display is light white and the display is in a disturbed state.
Was also retained. Both the selective reflection state and the scattering state
Off and stable for more than one month to ensure a sufficient storage effect
I accepted. (Example 23) Glass with both ITO electrodes
Polybenzyl-L-gluta as an alignment film on the electrode surface of the substrate
Mate (P-5011: Sigma)
Coupling agent (TSL8345: Toshiba Silicone Co., Ltd.)
(Product name). Then, use standard methods
Epoxy adhesive for bonding to the other electrode surface
And the other electrode surface is made of resin with a diameter of 10 μm.
Spacer balls were sprayed. Then, the electrode faces
They were stuck together and sealed. The liquid crystal material is Nema
Tic liquid crystal material E48 (MERCK company name) isotropic
The liquid crystal shown in FIG.
A display element was manufactured. The display state of the element is as follows: voltage on (square wave, V
(p = 30 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state and the display is slightly white green
(Reflection maximum wavelength 560 nm), the reflectance of which is 140% or less
In addition, the contrast with the voltage-on state is as good as 70 or more.
there were. As a result of the reflection spectrum measurement,
Compared to conventional display devices using imide,
While the wavelength regions are almost equal, the reflectance at the reflection maximum is doubled
I confirmed that. Note that the applied voltage gradually increases after the voltage is turned on.
When the pressure is reduced, the display becomes scattered and the display is pale white.
The state was maintained even after the voltage was turned off. Selective reflection state and scattering state
The state is stable for more than one month with both the voltage turned off and sufficient
The storage effect was confirmed. (Example 24) Alkali to which an acidic hydroxyl group is bonded
Photosensitive polyimide alignment film with a kill chain on the side chain
Used as material for pacer. Gala with one ITO electrode
Spin the photosensitive polyimide onto the substrate at 1500 rpm.
I did. This is usually at 110 ° C for 15 minutes.
The polyimide film was prebaked under the conditions. Spacer
Polyimide film via photomask with turns formed
Was exposed. Place this substrate on a hot plate at 170 ° C
By heating for 10 minutes, the photosensitive resin on the substrate side polymerizes
Of the light-irradiated part and the part polymerized by heat treatment
Slow solubility in liquid. This photosensitive resin is
Developer (QZ3301: Ciba-Geigy)
Spray and develop with developer and rinse solution
(QZ3311: Ciba-Geigy)
And spray the rinse solution (QZ3312: Ciba Geigy)
Rinse) and spin dry using nitrogen gas.
did. The substrate is cured at 250 ° C. for 1 hour and the height is 5 μm.
m, cylindrical spacer with a diameter of 15 μm and a thickness of 12
An alignment film having a thickness of 0 nm was formed. This spacer and orientation
A silane coupling agent (TSL8345: Toshiba Silicon)
Polybenzyl-L-gluta
Mate (P-5386: Sigma)
Of the chiral agent and the spacer
The polar substrate was formed at the same time. Then, again, the same photosensitivity
Spin coat polyimide under the same conditions as above,
And exposure. This time on the hot plate we did last time
Development without heating by heating
A new columnar spacer is laminated on top with a height of 5 μm.
Was. Next, silane caps are added to the newly formed spacers.
Pulling agent (TSL8345: product made by Toshiba Silicone Co., Ltd.)
Polybenzyl-D-glutamate
(P-3386: Sigma product name)
Was. The other glass substrate with an ITO electrode was also treated with silane.
Coupling agent (TSL8345: manufactured by Toshiba Silicone Co., Ltd.)
Polybenzyl-D-glutamate (P)
-3386: Sigma). Next, one electrode surface is adhered by a conventional method.
Apply epoxy adhesive to the predetermined position for alignment,
Laminate and seal so that the two electrode surfaces face each other
Was. The liquid crystal material is a nematic liquid crystal material E48 (MERC
60 wt% of chiral agent CB15 (ME
RCK product name) 40wt% mixture in isotropic phase
The liquid crystal display element shown in FIG.
Was prepared. The display state of the element is as follows: voltage on (square wave, V
(p = 60 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state and the display is slightly white green
(Reflection maximum wavelength 560 nm), the reflectance of which is 140% or less
In addition, the contrast with the voltage-on state is as good as 70 or more.
there were. As a result of the reflection spectrum measurement,
Compared to conventional display devices using imide,
While the wavelength regions are almost equal, the reflectance at the reflection maximum is doubled
I confirmed that. Note that the applied voltage gradually increases after the voltage is turned on.
When the pressure is reduced, the display becomes scattered and the display is pale white.
The state was maintained even after the voltage was turned off. Selective reflection state and scattering state
The state is stable for more than one month with both the voltage turned off and sufficient
The storage effect was confirmed. (Example 25) Process up to sealing of an electrode substrate
Performed in the same manner as in Example 1. Next, as a liquid crystal material,
Tic liquid crystal material E48 (MERCK company name) 60w
t% and optically active substance CB15 (trade name by MERCK)
40wt% mixture, and as UV curable monomer
Of 4,4'-bisacryloylbiphenyl as liquid crystal material
2% by weight, Darocure 117 as a polymerization initiator
3 (manufactured by Merk) as UV curable monomer
0.5% by weight of each
The solution was injected in a conventional manner in an isotropic phase. Then,
To make the light irradiation intensity gradient in the direction perpendicular to the electrode substrate
UV in the wavelength range close to the absorption maximum wavelength of the UV-curable monomer
External line is 3 mW / cm from one electrode substrate^Two Irradiate in front
The above-described reflective liquid crystal display element shown in FIG. 8 was produced. The display state of the element is as follows: voltage on (square wave, V
(p = 65 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state and the display is slightly white green
(The maximum reflection wavelength is 560 nm), and the reflectance is 60% or less.
In addition, the contrast with the voltage-on state is as good as 20 or more.
there were. As a result of the reflection spectrum measurement,
Compared to conventional display devices using imide,
Confirm that the wavelength range is expanded about 1.2 times
Was. Note that if the applied voltage is gradually reduced after the voltage is turned on,
The display is light white and the display is in a disturbed state.
Was also retained. Both the selective reflection state and the scattering state
Off and stable for more than one month to ensure a sufficient storage effect
I accepted. (Example 26) Steps up to sealing of an electrode substrate are performed.
Performed in the same manner as in Example 1. Then, as a liquid crystal material,
Matic liquid crystal material E48 (trade name of MERCK) 60
wt% as UV curable monomer with optical activity
Resteryl acrylate 40wt%, as polymerization initiator
UV of Darocure 1173 (Merk)
0.5 wt% is added to the cured monomer,
One mixed solution was injected by an ordinary method in an isotropic phase. Pre
In the state where the toner structure is formed,
The polymer was polymerized to produce a reflective display element shown in FIG.
During polymerization, the light irradiation intensity is degraded in the direction perpendicular to the electrode substrate.
The maximum wavelength of the UV-curable monomer so that
3mW / c from one electrode substrate
m^Two Irradiation. The display state of the element is as follows: voltage on (square wave, V
(p = 40 V, 60 Hz). Steep voltage
When it is turned off, it is in the selective reflection state and the display is white green (reflection
The maximum wavelength is 560 nm), the reflectance is 70% or more, and the voltage is
The contrast with the ON state was as good as 20 or more.
As a result of the reflection spectrum measurement, polyimide was used as the alignment film.
Compared to the conventional display device used, the reflection wavelength range
Has been expanded about 1.3 times. Real truth
In the case of the twenty-sixth embodiment, polyimide is used as the alignment film.
Without the storage effect of conventional display devices
It was confirmed that the driving voltage could be reduced. (Example 27) Sealing of electrode substrate and liquid
Crystalline material, optically active UV curable monomer, polymerization initiator
The same procedure as in Example 26 was performed up to the injection of the initiator. Next
The heating element on one electrode substrate surface and the other electrode substrate surface
Install and operate the cooling element in the direction perpendicular to the electrode substrate.
Irradiation of UV rays with a spiral pitch length of 20
mW / cm²And polymerize the UV-curable monomer.
The pitch length gradient was fixed. The display state of the element is as follows: voltage on (square wave, V
(p = 40 V, 60 Hz). Steep voltage
When turned off, it is in the selective reflection state and the display is slightly white green
(Reflection maximum wavelength 560 nm), the reflectance is 70% or more,
The contrast with the pressure-on state is as good as 20 or more.
Was. As a result of reflection spectrum measurement, polyimide
Wavelength compared to conventional display elements that use
It was confirmed that the area was expanded about 1.3 times.
In the case of Example 27, polyimide was used as the alignment film.
The storage effect of a conventional display device using
Although not available, it was confirmed that the driving voltage could be reduced. (Example 28) Glass with one ITO electrode
Polyimide (AL-105) is used as an alignment film on the electrode surface of the substrate.
1: Nippon Synthetic Rubber Co., Ltd.) to a thickness of 70 nm
Cast by Gnar. Glass base with the other ITO electrode
Fluororesin (CTX-80) as an alignment film on the electrode surface of the plate
7: Asahi Glass Co., Ltd.) as spinner to 80nm thickness
More cast. Then, on one electrode surface by the usual method
Attaches the epoxy adhesive for bonding in place.
And a 5 μm diameter resin spacer board on the other electrode surface.
Sprayed. Then, make sure that the electrode surfaces face each other.
Laminated and sealed. The liquid crystal material has the structure shown in the following chemical formula 3.
Perfluoro-based nematic liquid crystal material 35 represented by formula
wt% and perful represented by the following structural formula.
Oro-based optically active substance 15 wt%, and hydrocarbon-based nema
35w of tic liquid crystal material E48 (trade name, manufactured by MERK)
t% and hydrocarbon-based optically active substance S811 (MERK)
(Trade name) was used. this
FIG. 10 described above by injecting in an isotropic phase by a conventional method.
Was manufactured. [0140] Embedded image [0141] Embedded image The display state of the element is as follows: voltage on (square wave, V
(p = 28 V, 60 Hz). Turn off the voltage
Then, it was in a scattering + reflection state and the color of the reflected light was white
Orange (reflection maximum wavelength 600 nm) with a reflectance of 90%
As described above, the contrast with the voltage-on state is as good as 20 or more.
Met. When the applied voltage is gradually reduced from the voltage on,
The state was disturbed, the color was pale white, and this state was turned off
Later retained. In the scattering + reflection state, the voltage is off
It was stable for over a month. [0143] As described in detail above, according to the present invention,
Liquid crystal materials having different structures and / or electro-optical properties
Forming regions continuously in the vertical direction of the electrode substrate
Bright, good contrast and wide viewing angle
A reflective liquid crystal display device can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. FIG. 2 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. FIG. 3 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. FIG. 4 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. FIG. 5 is a conceptual diagram illustrating an example of a liquid crystal display element of the present invention. FIG. 6 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. FIG. 7 is a conceptual diagram illustrating an example of a liquid crystal display element of the present invention. FIG. 8 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. FIG. 9 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. FIG. 10 is a conceptual diagram illustrating an example of a liquid crystal display device of the present invention. [Description of Signs] 1, 1 ', 11, 11', 21, 21 ', 31, 31
', 41, 42, 101, 102, 111, 112, 1
31, 132 ... electrode substrate, 2, 3, 12, 13, 22, 23, 32, 33, 44,
45, 64, 87, 104, 114, 134 ... electrodes, 4, 14, 24, 34, 43, 63, 83, 84, 10
3, 113, 133 ... spacers 7, 8, 9, 17, 18, 20, 27, 28, 29, 3
7, 38, 48, 50, 66, 67, 68, 69, 8
8, 89, 90, 106, 107, 115, 117, 1
37, 138, 139, 140: liquid crystal material, 6, 16, 26, 36, 52, 71, 92, 109, 1
19, 142 ... power supply circuit, 5, 15, 25, 35, 51, 70, 91, 108, 1
18, 141 ... switch, 46, 47, 65, 85, 86 ... optically active material layer.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takaki Takato 33, Shinisogo-cho, Isogo-ku, Yokohama-shi, Kanagawa Prefecture Inside Toshiba Production Technology Research Institute Co., Ltd. JP-A-7-287214 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02F 1/13-1/141

Claims (1)

(57) Claims 1. A first and second electrode substrate , at least one of which opposes each other, is transparent, and is held in a space between the electrode substrates , and a cholesteric phase is formed. > coloration and a liquid crystal material having an effective helical pitch to reflect light in the visible region, horizontal surface in contact with the liquid crystal material of said first electrode substrate
An alignment process is performed to form a liquid crystal material region having a monodomain planar structure on the first electrode substrate side, and a liquid crystal material region having a polydomain planar structure on the second electrode substrate side. wherein together with the liquid crystal material regions are arranged in a direction perpendicular to the first and second electrode groups <br/> plate surface, said electrodes
A reflective liquid crystal display element formed between substrates in contact with each other .