JP3532295B2 - Manufacturing method of liquid crystal optical element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device and a liquid crystal display device.
Optoelectronics as storage elements, liquid crystal acoustic elements, light control glass, etc.
Suitable for use in the field of clitronicsLiquidCrystal optics
The present invention relates to a method for manufacturing an element. [0002] 2. Description of the Related Art Liquid crystal optical elements are thin and lightweight.
In the field of optoelectronics
Applications and improvements are being actively studied. Current state of liquid crystal optical elements
Currently, glass substrates are used as substrates for forming liquid crystal cells.
Although a plate is used, the manufacturing method is
Complex methods such as vacuum injection of liquid crystal after standing
Has been taken. Also, the completed liquid crystal panel is shocked
Weak, broken glass substrate, even if not broken
For example, when pressed with a finger, the liquid crystal easily flows and the display is disturbed.
There is a strength problem such as. On the other hand, recently, as a substrate, it is difficult to break and
Liquid crystal optical element using plastic substrate that is easy to fabricate
Is being developed, but also in this case, display by pressing etc.
Has not been resolved. Solving these strength problems
Various proposals have been made as a decision method. example
For example, Japanese Patent Application Laid-Open No. 5-27246 discloses that
Liquid crystal connected by columns of UV curable resin with uniform distribution
It describes how to improve the mechanical strength of the panel.
You. In this method, a UV curable resin monomer is added to the liquid crystal.
After dissolving and injecting it into the cell,
The column is formed by curing the external curable resin monomer.
However, in this method, the columns are grown to a cell thickness or more.
However, sufficient mechanical strength cannot be obtained. JP-A-1-250930 discloses a non-liquid
A solution prepared by dissolving a crystalline polymer and liquid crystal in a solvent
Apply to a plate, dry at room temperature and then dry at 60 ° C
Then, the opposing substrates are laminated to form a scattering type liquid crystal display device.
A method for making is described. In this method, non-liquid crystal
Liquid crystalline polymer and liquid crystal, non-liquid crystalline polymer: weight of liquid crystal
Used at a ratio of 100: 100 to 100: 300.
You. When the amount of non-liquid crystalline polymer is large, birefringence
Non-liquid crystalline polymer is directly
Low light transmittance due to visible light and unnecessary light scattering
Not applicable. Japanese Patent Application Laid-Open No. 5-61051 discloses a liquid crystal layer.
A column-shaped thermosetting port in contact between the spacer and the upper and lower substrates
A liquid crystal display device in which a rim is arranged is described. I
However, there is no description of the distribution of the columnar thermosetting polymer.
In addition, the mechanical strength is sufficiently improved and good
It is unclear whether the display characteristics can be maintained. Also,
The thermosetting polymer pillars consist of liquid crystal, spacers, and spaces.
Consists of thermosetting polymer spheres larger in diameter than sir
After applying the mixture to one of the substrates, place the counter substrate and
It is formed by pressing and heating. Therefore,
It requires a process of spheroidizing the thermosetting polymer,
The problem that it is necessary to select a material that can be spheroidized
There is. [0006] Japanese Patent Application Laid-Open No. 6-59246 discloses that 0.6
Liquid crystal droplet of 0.1 to 0.5 μm holding the liquid crystal droplet
The liquid crystal layer is composed of a polymer material with a partition wall thickness of μm.
Light modulator that has a light modulation function of scattering and transmitting light.
A tuning element is described. In this case, the liquid crystal is independent
Since it is a layer, the orientation cannot be controlled, and scattering and non-scattering are displayed.
It cannot be used, and even if a polarizing plate is placed outside the device, a practical display
I can't show it. In Comparative Example 1, the liquid crystal and the polymer material were used.
When the composition is isotropic, i.e., they are compatible with each other,
UV-cured to obtain a relatively transparent element, but phase separation
Only progresses due to the curing of the polymer material,
The molecular material cannot grow to a sufficient size and the mechanical strength is
Does not improve in minutes. In addition, this method uses a high
It is necessary to select a child material. Japanese Patent Application Laid-Open No. 60-153025 discloses a basic
Using a plastic film substrate as the plate,
The mechanical strength has been improved by fixing the adhesive to the orientation control film.
A liquid crystal display element is described. However, the orientation control
Fix the gap material without damaging the orientation of the control film
Is difficult, and it is difficult to fix the spherical gap material.
So its adhesive area is small and strong against strong pressing
Is inadequate. Japanese Patent Application Laid-Open No. 7-56145 discloses that 0.1
By adding 10 to 10% by weight of a polymer material to the liquid crystal layer,
Non-scattering type liquid crystal table with steep display voltage threshold characteristics
Illustrated elements are described. However, the resulting liquid crystal display element
No mention is made of improving the mechanical strength of the child,
Also, there is no description about the distribution of the polymer material.
No. In addition, as described in the detailed description section of the publication,
A curable resin is simply added, and ultraviolet light is applied after injection between the substrates.
Just by shooting, the resin will not be large enough,
Strength does not improve. [0009] SUMMARY OF THE INVENTION The present invention relates to the above prior art.
To solve the problems of operation, for example, used as a liquid crystal display device
Display characteristics such as contrast,
Double bending with excellent mechanical strength that does not disturb the display due to pressure, etc.
Foldable liquid crystal display elementOf childThis method is suitable for manufacturing
Manufacturing such a liquid crystal optical element by an easy process.
Providing a method of manufacturing a liquid crystal optical element that enablesToEye
Target. [0010] The present inventors have solved the above-mentioned problems.
As a result of studying to solve the problem, the continuous liquid crystal phase and its
Spacers and upper and lower groups distributed separately from the liquid crystal phase
With a columnar non-liquid crystalline polymer that comes into surface contact with the board in a specific area
Distribution of pillars of non-liquid crystalline polymer material forming liquid crystal layer
By setting the state and amount within a specific range, the display characteristics and
Liquid crystal optical element with excellent mechanical strength and mechanical strength.
And found that the present invention was completed based on this finding.
Was. [0011] [0012]That isThe present invention,oneSmall number of substrates with pairs of electrodes
At least the liquid crystal material and the liquid crystal
Common to materials and non-liquid crystalline polymeric substances that are practically incompatible
The solution dissolved in the solvent and the coating liquid consisting of the spacer
After coating, the solvent is evaporated to form a liquid crystal layer material layer.
The two substrates are electrically connected to each other through the liquid crystal layer material layer through the electrode surface.
And heat the obtained laminate.
By doing so, phase separation with the liquid crystal material occurs in the liquid crystal layer material layer.
The islands of the non-liquid crystalline polymer material are separated from each other by the two substrates.
Surface contact with an average diameter of 2 to 50 μm and uniformly distributed
A columnar growth process, and then the non-liquid crystalline polymer
A method for manufacturing a liquid crystal optical element including a step of curing the quality.
To offer. Hereinafter, the liquid crystal optical element and the liquid crystal optical element of the present invention will be described.
The method for manufacturing the device will be described in detail. [Liquid Crystal Optical Element] FIG. 1 shows one embodiment of the liquid crystal optical element of the present invention.
FIG. The liquid crystal optical element of the embodiment of FIG.
A pair of substrates 1 with electrodes 2, sandwiched between these substrates 1
Liquid crystal layer 3 and a pair of polarizers arranged outside the two substrates 1.
It consists of a light plate 7. The liquid crystal layer 3 includes a continuous liquid crystal material 4,
Spacer 5 separated from liquid crystal material 4 and columnar non-liquid crystal
It consists of islands 6 of a cured product of a conductive polymer substance. Spacer 5
Are fixed to the upper and lower substrates 1 by surface contact and uniformly distributed.
By the island 6 of the cured product of the columnar non-liquid crystalline polymer substance
Reinforced, cell gap changes by pressing
Nothing. In the present invention, in addition to the spacer, a liquid crystal
The shape of the cured product of the phase-separated non-liquid crystalline polymer substance is columnar
Contact the upper and lower substrates to achieve the mechanical strength of the device.
Has been significantly improved. Compared to this, with a normal element
Has only a spacer, so for example,
In the case of a pointer for a pacer, for a fibrous spacer
Line contact, and the contact area with the substrate is extremely small.
Please. Further, in the present invention, the average diameter of this columnar island is
By specifying it to be 2 to 50 μm or less, polarizing plates are arranged on both sides.
Good display is obtained with the birefringent type. Surface contact on this island
If the diameter of is less than 2 μm, it approaches the wavelength of visible light
Light is strongly scattered and the display as a birefringent type is markedly dark.
It will get worse. Conversely, if it exceeds 50 μm, the island-like structure
Structure can be visually recognized, degrading the display quality.
is there. The island of the cured product of the non-liquid crystalline polymer liquid crystal is large.
In the case of high intensity, the fixing force of the upper and lower substrates on each island is large, so
The distribution density in the child plane can be reduced. Also, conversely
If the size of the island is relatively small, increase the distribution density
It is necessary to secure sufficient strength. Therefore, the liquid crystal optical element
Ensuring sufficient mechanical strength while maintaining the display quality of
As a condition for maintaining the island, the average diameter of the island is Lμm.
1 mm area in the liquid crystal optical element^TwoThe number of islands per
2.5 × 10^Four≤NL^Two≦ 2.5 × 10
^FiveNeed to be NL^TwoIs 2.5 × 10^FourLess than
Mechanical strength may be insufficient, and conversely 2.5 × 1
0^FiveIf it exceeds, the display of the liquid crystal optical element may be dark.
You. The liquid crystal optical element of the present invention is a birefringent liquid crystal.
It is an optical element, the selection of the liquid crystal material of the liquid crystal layer,
Depending on the selection of the alignment method, various types of liquid crystal optical elements can be used.
Can be used. Suitable for the liquid crystal optical element of the present invention
For example, as a liquid crystal material, a ferroelectric liquid crystal is used.
Non-memory system, memory system, nematic
Twisted nematic system composed of
Random domain twisted nematic, random domain
And a uniaxial orientation method. An embodiment of an element configuration suitable for these systems is as follows.
This is described below. A. Liquid crystal material: ferroelectric liquid crystal (1) Element configuration A-1 (non-memory type) In this non-memory system, the thickness of the liquid crystal layer is
Constructed wider than the helical pitch of the liquid crystal to provide a smectic layer
An orientation process is performed so as to stand almost perpendicular to the substrate surface. Orientation treatment
As a parallel orientation on the electrode surface of at least one substrate
Method of providing control layer, shearing while applying electric field to liquid crystal
A known method such as a method of applying can be used. As the orientation control layer, a well-known Rabin
Film and an obliquely evaporated inorganic film. As a rubbing film
Polyvinyl alcohol, nylon, polyimide
Which polymer substance is spin coated, dipped, rolled
A thin film is formed by a method such as a coating method or a spray method, and the surface is formed.
By rubbing in one direction with a cloth (rubbing treatment)
Is used. The substrate is a plastic substrate
In such a case, the substrate itself may be subjected to a rubbing treatment. Also,
In the oblique deposition method, SiO_x, TiO_TwoSuch as inorganic oxides
Diagonal columnar set by evaporation from the diagonal direction to the substrate
Form a weave to give orientation ability. For applying shear to a liquid crystal while applying an electric field to the liquid crystal
In the method, the orientation control layer is not required. like this
In a simple element configuration, when no voltage is applied between the electrodes
Are liquid crystal molecules uniformly inclined at an angle θ to the layer normal
Each smectic layer is arranged perpendicular to the substrate surface,
The helical axis is parallel to the substrate plane and perpendicular to this layer.
It is an array of aligned positions. For applying voltage between electrodes
The helical structure disappears, and the liquid crystal molecules
At + θ or -θ, the entire cell is uniformly oriented in parallel.
Performs "dark" display. That is, the helical structure of the liquid crystal disappears
Critical electric field is E_cIn the case of, the liquid crystal optical element
And the applied electric field E <−E_cLength in the molecular sequence of
If the axis direction is aligned with one of the polarization axes, the incident light will pass through the cell.
Since it does not receive birefringence at an excessive time, the display is “dark”. mark
When the polarity of the applied electric field is reversed, the tilt azimuth of the long axis of the molecule becomes
2θ changes, the incident light is birefringent, and the light interference phenomenon
The display will be “bright”. When the voltage is turned off,
It returns to the initial arrangement state with a helical structure. (2) Element configuration A-2 (memory type) The element configuration in the memory system is based on the ferroelectric
Except that it is narrower than the helical pitch of the crystalline liquid crystal,
This is the same as the element configuration A-1. However, in this case
Is already spiraled without applying voltage due to the substrate.
Molecular sequence corresponding to the smectic C structure whose structure has disappeared
A state has been formed. Changes in molecular arrangement when voltage is applied
The display of “bright” and “dark” is the same as in the element configuration A-1, but
Even if the voltage is turned off, the molecular alignment state is maintained by applying the voltage
You. B. Liquid crystal material: Nematic liquid crystal (1) Element configuration B-1 (twisted nematic method) The twisted nematic method is currently the main liquid crystal display device.
TN (twisted nematic) cell and STN (supply)
er twisted nematic) applies to cells. With this method
Is a nematic with positive dielectric anisotropy as a liquid crystal material
When a liquid crystal is used and no voltage is applied between the electrodes,
The material is distributed in the same direction in each plane parallel to the upper and lower substrates.
And the substrate is twisted between the upper and lower substrates. Immediately
That is, when no voltage is applied, the liquid crystal molecules face the substrate surface.
Are arranged almost parallel and uniformly in the thickness direction of the liquid crystal layer.
In the structure, the orientation direction is continuously twisted
You. For example, when the twist angle between the upper and lower substrates is 90 ° (TN
Cell), two polarizing plates whose polarization axes are orthogonal to the outside of both substrates
When the voltage is not applied, “Bright” is displayed.
When a voltage is applied, the liquid crystal molecules are aligned vertically.
Indicates "dark". Method for making such a uniform twist orientation
as, An alignment control layer in contact with the liquid crystal layer is provided on the electrode surfaces of the upper and lower substrates.
The orientation direction by the desired twist angle.
Method, or At least one substrate has an orientation control layer on the electrode surface.
The optically active substance (Chiral Dopan)
G) there is a method of mixing. The method of the above is applied to the case where the twist angle is 90 ° or less.
This is an effective and easy method. As the orientation control layer,
The rubbing film and the inorganic oblique deposition film described in
You. In such a method, the liquid crystal molecules are slightly
Orientate slightly (with pretilt), but if necessary
The pretilt angle by increasing the angle between the deposition direction and the substrate.
The viewing angle can be increased by increasing
Wear. Commercially available products such as alignment control layer materials
Can be used. In the method, at least one of the substrates is
A similar orientation control layer is provided. And to nematic liquid crystal
The liquid crystal material itself is twisted by mixing the optically active substance
Can give power. In this way, the liquid crystal material is fixed.
Since it has a helical pitch, it depends on the cell thickness
To adjust the twist angle between the upper and lower substrates. Therefore, one
Even if the alignment control layer is only on the substrate,
Crystal orientation direction is uniformly twisted in the thickness direction of the liquid crystal optical element
You. In addition, the helical pitch itself is
It can also be adjusted by the type and the amount of addition. Optical activity
The compounding amount of the substance is usually 0.5 to the nematic liquid crystal.
10 to 10% by weight, preferably 1 to 5% by weight. 0.5
If the amount is less than 10% by weight, the effect may be insufficient.
When the amount exceeds%, the helical pitch becomes too short,
It may be difficult to control the cell thickness to obtain a twist angle.
You. As can be seen from the above, the method of STN is 90
Suitable for making twist angles of more than °. In addition,
The default is given as necessary. (2) Element Configuration B-2 (Random Domain)
Twisted nematic method) The basic operation itself of this method is the same as that of the element configuration B-1.
However, without uniform alignment throughout the liquid crystal optical element,
The alignment direction differs depending on the location in the plane of the liquid crystal optical element
Form a multi-domain. That is, the orientation of this method is
When no voltage is applied between the electrodes, the upper and lower
The orientation direction in each plane parallel to the plate is uniform and
Multiple orientation holes penetrating between substrates whose orientation direction is twisted
Main (multi-domain), parallel to upper and lower substrates
In each plane, the orientation directions of adjacent domains are
Different, the orientation direction is the same in all domains between substrates
It is a random domain twist orientation that is twisted by degrees. With such an orientation state,
The display operation itself is the same in the domain of
Since the orientation direction differs for each in,
The decrease in trust is reduced. Create random domain
Because it is not necessary to align the liquid crystal in one direction,
As for the element configuration, there is nothing on the electrode surface of the upper and lower substrates.
It is not provided, or there is no effect of aligning the liquid crystal in one direction.
A dielectric film on at least one substrate electrode surface
You. This dielectric film prevents conduction defects between the upper and lower electrodes.
Is provided as an insulating film for
Which organic film, inorganic film, etc. can be selected without particular limitation
it can. Specifically, polyamide, nylon, polyvinyl
A method such as coating a polymer film of alcohol or the like as a solution
Film formation or SiO_x, Ta_TwoO_Three, TiO_TwoMetal acids such as
Oxide film at a relatively low temperature
be able to. Of course, processing such as rubbing is not required. As the size of the random domain,
Usually, the average diameter is 2 to 50 μm, preferably 4 to 20 μm.
μm. If smaller than 2μm, visible light
Scatters light near domain boundaries to approach line wavelength
However, in the birefringent liquid crystal optical element as in the present invention, the light transmission
The excess rate may decrease significantly. Conversely, over 50 μm
Then, the domain can be seen visually, and the display quality
May lower. Usually, as the thickness of the liquid crystal layer,
About 2 to 10 μm in terms of display color and drive characteristics
In this case, the liquid crystal material is sandwiched between the substrates as described above.
Alone, a multi-domain size of about the cell thickness can be obtained.
You. If you want to control this size further,
The nematic liquid crystal is heated once to the temperature at which the nematic liquid crystal shows an isotropic phase.
It can be performed by adjusting the cooling rate. General
In general, the faster the cooling rate, the smaller the domain size
You. (3) Element Configuration B-3 (Random Domain)
method) In this method, the orientation in each domain is uniform.
From multiple orientation domains that penetrate between the upper and lower substrates.
Landers with different orientation directions of adjacent domains
Domain orientation. The alignment by this method is
In terms of multi-domains with different orientations,
Almost the same as domain twisted nematic orientation
There is a twisted structure in the thickness direction of the element.
The difference is that the orientation direction is aligned in one direction in the domain.
You. The operation is, for example, a liquid crystal between orthogonal polarizing plates.
When an optical element is arranged, when no voltage is applied,
Domains whose orientation is tilted with respect to each polarization axis
Light is transmitted through the birefringence effect only in the "bright", voltage is applied
Liquid crystal molecules are aligned vertically in all domains
Does not transmit light and becomes "dark". Figure 2 shows the random domain
FIG. In FIG. 2, the paper surface is the substrate surface.
It becomes. 8 is a domain having a unique orientation direction
Arrows in each domain indicate the orientation direction, and 6 indicates
3 shows islands of a cured product of a non-liquid crystalline polymer substance. Polarization axis and orientation
The domain whose angle with the direction is 45 ° is the brightest
To Penetrate. As is clear from FIG.
Does not transmit light in domains with an orientation parallel to the polarization axis of
The brightness of “bright” is higher than that of the element configurations B-1 and B-2.
Although all become slightly darker, the structure of the element is simplified. The element structure of this system is applied to a nematic liquid crystal.
Device configuration B-2 except that the optically active substance was not mixed
Is the same as That is, it is oriented on the electrode surface of any substrate
Either do not provide a control film, or
Liquid crystal in one direction on the electrode surface of at least one substrate
A dielectric film having no orientation effect is provided. In addition, de
The method of adjusting the main size and domain size depends on the element structure.
Same as Composition B-2. (4) Element Configuration B-4 (Uniaxial orientation method) In the uniaxial alignment method, the liquid crystal material is all parallel to the upper and lower substrates.
Uniformly distributed in one direction in the plane and in the thickness direction between the upper and lower substrates.
Is facing. The alignment direction can be horizontal or vertical
May be. As an example, a liquid crystal optical element is placed between orthogonal polarizers.
The operation in the case of arrangement will be described. In the case of horizontal orientation,
A liquid crystal material having a positive electric anisotropy is used. No voltage is applied
If not, the angle between the orientation direction and the polarization axis must be 45 °.
The brightest light is transmitted through the
Display. Next, when a voltage is applied, the liquid crystal has dielectric anisotropy.
Since it is positive, it is vertically aligned and does not transmit light between orthogonal polarizers.
“Dark” is displayed. On the other hand, in the case of vertical alignment, this operation
Use liquid crystal with negative dielectric anisotropy to reverse
It should be “bright” when pressure is applied. As an orientation method, at least one of the substrates is used.
Can be easily achieved by providing an orientation control layer on the electrode surface of
You. In the case of horizontal alignment, the type of the alignment control layer is the element structure.
It may be the same as that described in Section 1, and do not twist.
Therefore, it is not necessary to add an optically active substance to the liquid crystal. vertical
In the case of orientation, for example, a silane coupling agent is formed
Or a vertically deposited inorganic oxide.
No. Next, the present invention is applied to the construction of the liquid crystal optical element of the present invention.
The respective materials will be described. As the material of the substrate,
There is no particular limitation as long as at least one substrate is transparent,
Well known are glass plates and plastic
Plates, plastic films, etc. Preferably plastic
By using a stick plate or film, the weight of the element can be reduced.
Or apply a highly productive manufacturing method as described below.
Can be The thickness of the substrate is 50 μm to 1 m
m is preferred. If it is thinner than 50 μm, the substrate itself
Problems such as unnecessary deformation and tearing during the manufacturing process
May occur. Conversely, if it exceeds 1 mm,
Or the distance between the polarizing plate and the liquid crystal layer is large.
Therefore, the viewing angle characteristics may be deteriorated. As a material for a plastic plate or film
Is commonly referred to as an optically isotropic plate or film
PC (Polycarbonate), PAr (Polyarelay)
G), PS (polysulfone), PES (polyethers)
Ruhon), APET (Amorphous Polyethylene Telef)
Tarrate), APO (amorphous polyolefin) and the like are preferable.
These are commercially available and readily available.
You. These plastic plates or films may be used alone
Or may be used in liquid crystal resistance, heat resistance, moisture resistance,
Even if different types of films are used in multiple layers for the purpose of
Good. As the electrodes, optically transparent or translucent
Use electrodes. Specific examples of such electrodes include, for example,
For example, tin oxide film called NESA film, indium oxide
Film, IT consisting of a mixture of indium oxide and tin oxide
O film, deposited film of gold or titanium, or other thin film
Examples thereof include metals and alloys such as minium.
The shape of these electrodes is not particularly limited and is intended.
Depending on the driving method of the liquid crystal optical element, display contents, etc.,
select. Liquid crystal material used in the liquid crystal optical element of the present invention
The charge is particularly limited if the liquid crystal is capable of birefringent display.
Although there is no limit, ferroelectric liquid crystals and nematic liquid crystals are usually preferred.
Appropriately used. These liquid crystals are low-molecular liquid crystals.
Or polymer liquid crystal may be used, but it is usually inexpensive and has excellent responsiveness.
Low molecular liquid crystal is suitably used. As ferroelectric liquid crystal
Is not particularly limited as long as it exhibits ferroelectricity. For example,
Only one kind of low-molecular or high-molecular liquid crystal having electrical conductivity may be used.
And high-molecular liquid crystal and / or low-molecular liquid crystal 2 exhibiting ferroelectricity
It may be a liquid crystal composition composed of more than one kind. In addition, liquid crystal
Shows ferroelectricity to improve the response speed of optical elements
Low molecular weight liquid crystal may be blended. The ferroelectric polymer liquid crystal is not particularly limited.
For example, polyacrylate main chain, polymethacrylate
Main chain, polychloroacrylate main chain, polyoxirane
Main chain, polysiloxane main chain, polyester main chain, policy
It consists of a main chain such as oxane-olefin main chain and liquid crystal side chains.
Side chain type ferroelectric polymer liquid crystal is preferably used. Forcing
As the conductive polymer liquid crystal, the weight average molecular weight is usually 10
100 to 100,000, preferably 1000 to 100,000
It is preferably used. Side chain type ferroelectricity suitably used in the present invention
Specific examples of the polymer liquid crystal are shown below. Polyacrylate main
Examples of the chain-based ferroelectric polymer liquid crystal include the following
And those having a return unit. [0040] Embedded image Polymethacrylate main chain ferroelectric polymer
As the liquid crystal, for example, those having the following repeating units
And the like. [0042] Embedded image Polychloroacrylate main chain based ferroelectricity
The molecular liquid crystal has, for example, the following repeating unit
And the like. [0044] Embedded image Polyoxirane main chain ferroelectric polymer liquid crystal
As, for example, those having the following repeating units
And so on. [0046] Embedded image Polysiloxane Main Chain Ferroelectric Polymer Liquid Crystal
As, for example, those having the following repeating units
And so on. [0048] Embedded image Polyester main chain ferroelectric polymer liquid crystal
For example, for example, those having the following repeating units
Is mentioned. [0050] Embedded image Polysiloxane-Olefin Main Chain Ferroelectric
As the reactive polymer liquid crystal, for example, the following repeating unit
And the like. [0052] Embedded imageHere, x: y = 19: 1 to 7: 3 (mole
Ratio). The above ferroelectric polymer liquid crystal is repeated.
In the unit, the side chain skeleton is biphenyl skeleton, phenylben
Zoate skeleton, biphenyl benzoate skeleton, phenyl
May be replaced by -4-phenylbenzoate skeleton
The benzene ring in these skeletons is
Gin ring, pyridazine ring, pyrazine ring, tetrazine ring,
With chlorohexane ring, dioxane ring, dioxaborinane ring
Halogen groups such as fluorine and chlorine which may be replaced
Or 1-methylalkyl which may be substituted with a cyano group.
Group, 2-fluoroalkyl group, 2-chloroalkyl group,
2-chloro-3-methylalkyl group, 2-trifluoro
Methylalkyl group, 1-alkoxycarbonylethyl
Group, 2-alkoxy-1-methylethyl group, 2-alkoxy
Xypropyl group, 2-chloro-1-methylalkyl group,
2-alkoxycarbonyl-1-trifluoromethyl
It may be replaced by an optically active group such as a ropyl group. Ma
The length of the spacer is in the range of 2 to 30 methylene chains.
It may change in the box. These ferroelectric polymer liquid crystals are used alone.
Or two or more of them may be used in combination. Ferroelectric
As the low-molecular liquid crystalline compound, for example, a compound represented by the following formula:
-Based ferroelectric low-molecular liquid crystal compounds, azo and azoki
Biferroelectric low-molecular liquid crystal compound, biphenyl and aroma
Tixester ferroelectric low-molecular liquid crystal compound, halo
Ferroelectric low-molecular-weight molecules with ring substituents such as gen and cyano groups
Liquid crystal compounds, ferroelectric low molecular weight liquid crystal compounds having a heterocyclic ring
And the like. A Schiff base ferroelectric low molecular weight liquid crystal compound;
Examples thereof include the following compounds (1 to 4)
You. [0056] Embedded imageAzo- and azoxy-based ferroelectric low-molecular liquid crystal
Examples of the compound include (5) and (6) shown below.
It is. [0058] Embedded image Biphenyl and aromatics esters
Examples of the ferroelectric low-molecular liquid crystal compound include the following:
Compounds (7) and (8). [0060] Embedded image A ring substituent such as a halogen or a cyano group is introduced.
Examples of ferroelectric low-molecular liquid crystal compounds include the following:
Compounds (9) to (11). [0062] Embedded image A ferroelectric low-molecular liquid crystal compound having a heterocyclic ring
Are, for example, the following compounds (12) and (13)
Is mentioned. [0064] Embedded image These ferroelectric low-molecular liquid crystal compounds have the following properties:
Species may be used alone or in combination of two or more.
In the present invention, a ferroelectric polymer liquid crystal or a ferroelectric low molecular liquid
With ferroelectric properties that can be used in combination with crystalline compounds
No liquid crystal compounds include, for example, the following smectic
And low-molecular liquid crystal compounds. [0066] Embedded imageThese liquid crystal compounds may be used alone.
Or two or more of them may be used in combination. With nematic liquid crystal
For example, high-molecular or low-molecular
Valent low molecular nematic liquid crystals are preferred. Nematic liquid
Most crystals have a positive dielectric anisotropy.
What is necessary is just to select suitably according to the operation mode of an optical element.
At present, many nematic liquid crystals and nematic liquid crystal compositions
Are commercially available and have various properties including their dielectric anisotropy.
Is disclosed. Further, when the twist orientation is performed as described above,
In the case where only one side of the substrate is
Uses an optically active substance for the purpose of
It is preferred to add. Particularly effective as an optically active substance
There is no limit, usually purchased with nematic liquid crystal composition
Known ones such as those that can be used can be used. Departure
Low molecular nematics suitably used in bright liquid crystal optical devices
Examples of tic liquid crystals are roughly divided into Schiff bases,
Zo, azoxy, benzoate, biphenyl,
Cyclohexyl carboxylate, phenylcyclo
Hexane, pyrimidine, dioxane, cyclohexene
A typical example is a silcyclohexane type. That
Specific examples of such a low-molecular nematic liquid crystal are shown below. Tool for Schiff base low molecular nematic liquid crystal
Examples of the body include the following. [0070] Embedded image Azo, azoxy low molecular nematic liquid crystal
Specific examples include the following. [0072] Embedded imageBenzoic acid ester type low molecular nematic liquid
Specific examples of the crystal include, for example, the following. [0074] Embedded image Biphenyl and terphenyl low molecular weight compounds
The following are specific examples of the matic liquid crystal.
I can do it. [0076] Embedded image Cyclohexylcarboxylic acid ester based low
Specific examples of the molecular nematic liquid crystal include, for example,
Is included. [0078] Embedded image Phenylcyclohexane, biphenyl
Specific examples of low molecular nematic liquid crystals based on chlorohexane
Examples thereof include the following. [0080] Embedded image Pyrimidine and dioxane low molecular weight nemas
Specific examples of the tic liquid crystal include, for example,
Can be [0082] Embedded image Cyclohexylcyclohexane ester type
Specific examples of low molecular nematic liquid crystal of the following, for example,
One. [0084] Embedded image Cyclohexylethane-based low molecular nematic
Specific examples of the liquid crystal include the following.
You. [0086] Embedded image Other cyclohexane-based low molecular nematic
Specific examples of the backlit liquid crystal include the following.
It is. [0088] Embedded image Specific examples of trans-type low molecular nematic liquid crystal
Examples thereof include the following. [0090] Embedded image An alkenyl low molecular nematic liquid crystal material
Examples of the body include the following. [0092] Embedded image2,3-difluorophenylene-based low molecule
Specific examples of the nematic liquid crystal include, for example,
No. [0094] Embedded image In the present invention, the low molecular nematic liquid crystal is
One kind may be used alone, but plural kinds may be mixed and used.
Is also good. Practically adjust the driveable temperature range and other characteristics.
A large number of well-mixed liquid crystals are commercially available.
May be used. In the present invention, the low molecular nematic
Optically active substances that can be used in combination with
And low-molecular compounds having biologically active groups.
There may be no substance or liquid crystal. As an optically active group
Is, for example, a group having the following structure. [0096] Embedded image Optically active substance having liquid crystallinity (optically active substance)
As the body, for example, cholesteric liquid crystal (chiralnet)
Liquid crystal). This has a cholesteric ring
Examples of the steric liquid crystal include the following:
You. [0098] Embedded imageCholesteric having no cholesteric ring
Examples of the liquid crystal include the following. [0100] Embedded image In the present invention, a non-liquid crystalline high
Non-liquid used to form islands of hardened molecular material
Thermosetting resins, thermoplastic resins or
Is a photocurable resin. In the present invention, as described below,
Grow phase-separated islands and adjust island distribution
High strength, regardless of the type of non-liquid crystalline polymer
The liquid crystal optical element of the degree can be manufactured. However,
To make it easier to grow isolated island sizes
In addition, the non-liquid crystalline polymer material is not
A material that separates phases, that is, a material having low compatibility is used. As the thermoplastic resin, a number average molecular weight is usually used.
With an amount of 1500 or more, preferably 1500 to 100,000
Is preferably used. Number average molecular weight of thermoplastic resin is 1
If it is smaller than 500, its glass transition temperature or melting point is low.
The mechanical stability of the liquid crystal optical element
is there. That is, as a thermoplastic resin, the glass transition temperature is
Those having a temperature of -50 ° C to + 100 ° C are preferred. From 100 ° C
Too high, the island is difficult to grow or very long to grow
May require time. The thermoplastic resin preferably used in the present invention
Specific examples include polyvinyl chloride, polyvinyl bromide,
Vinyl fluoride, vinyl chloride-vinyl acetate copolymer, salt
Vinyl chloride-ethylene copolymer, vinyl chloride-propylene
Copolymer, vinyl chloride-vinylidene chloride copolymer, chloride
Vinyl-butadiene copolymer, vinyl chloride-acrylic acid
Ester copolymer, vinyl chloride-acrylonitrile copolymer
Merged, vinyl chloride-styrene-acrylonitrile ternary
Polymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer
Coalescing, polyvinylidene chloride, polytetrafluoroethylene
, Polytetrafluorochloroethylene, polyvinyl fluoride
Vinyl halide polymers or copolymers such as nilidene;
Rivinyl alcohol, polyallyl alcohol, polyvinyl alcohol
Unsaturated alcohols such as toluene ether and polyallyl ether
Or ether polymers or copolymers; acrylic acid
Or a polymer of unsaturated carboxylic acid such as methacrylic acid or
Is a copolymer; polyvinyl ester such as polyvinyl acetate,
Alcohol residue such as polyallyl ester such as polyphthalic acid
Polymers or copolymers having unsaturated bonds in the group;
Liacrylic acid esters, polymethacrylic acid esters,
Polymer of oleic acid ester or fumaric acid ester, etc.
An unsaturated bond between the acid residue or the acid residue and the alcohol residue
Acrylonitrile polymers or copolymers
Or a polymer or copolymer of methacrylonitrile,
Polyvinylidene cyanide, malononitrile or fuma
Weight of unsaturated nitrile such as lonitrile polymer or copolymer
Copolymer or copolymer; polystyrene, poly α-methyl
Styrene, poly p-methylstyrene, styrene-α-me
Styrene copolymer, styrene-p-methylstyrene
Copolymer, polyvinylbenzene, polyhalogenated polystyrene
Polymers or copolymers of aromatic vinyl compounds such as
Vinylpyridine, poly-N-vinylpyrrolidine, poly-
A polymer of a heterocyclic compound such as N-vinylpyrrolidone or
Copolymer; polyester condensate such as polycarbonate;
Polyamide condensate such as nylon 6, nylon 6,6, etc.
Water maleic acid, fumaric anhydride and its imidized products
Polymers or copolymers; polyamide imides, polyethers
Polyimide, polyimide, polyphenylene oxide,
Liphenylene sulfide, polysulfone, polyether
Heat-resistant organic polymers such as sulfone and polyarylate
No. Among them, polycarbonate, polystyrene
, Polyacrylate, polymethacrylate, nylon
Etc. are preferably used. EPO is a thermosetting resin
Commercially available, such as xy adhesive and acrylic adhesive
Various types including those can be used. Photocurable
As resin, it cures with visible light, UV light, electron beam, etc.
Use a variety of things, including those that are commercially available, such as adhesives
Can be. These non-liquid crystalline polymer substances are
From the viewpoint of the manufacturing method of the crystal optical element and the required durability.
You may choose it. Thermal or photocurable materials suitably used in the present invention
Specific examples of the resin include an epoxy adhesive,
Ril adhesive, unsaturated polyester adhesive, polyurethane
Tan type adhesive, hot melt type adhesive, elastomer type
An adhesive can be used. Examples of epoxy adhesives
Therefore, bisphenol A type is preferred as the main ingredient.
No. Bisphenol A is replaced with bisphenol
A base compound of a knol compound can also be used. [0106] Embedded image That is, in the above epoxy compound, R¹
And R^TwoIs a methyl group (bisphenol A type), R¹Is methyl
With R^TwoIs an ethyl group, R¹Is a methyl group and R^TwoIs isopropyl
R group, R¹Is a methyl group and R^TwoIs an isobutyl group, R¹But
R^TwoIs a heptyl group, R¹Is a methyl group and R^TwoIs nonyl
Group, R¹And R^TwoIs a propyl group, R¹And R^TwoAre each
A den group, a pentylidene group, a 2-methylpentylidene group,
3-methylpentylidene group, R¹And R^TwoIs a methyl group and X
Y is a methyl group. As a curing agent for the epoxy compound,
Lentriamine, triethylenetetramine, xylylene
Diamine, diaminodiphenylmethane, polyamide tree
Fat, dicyandiamide, boron trifluoride-amine complex,
Triethanolamine borate, without hexahydro
Water phthalic acid, phthalic anhydride, maleic anhydride, polysal
Fido, resol and the like can be used. Epoxy adhesive
May be one-pack type or two-pack type. As an example of the acrylic adhesive, acrylic
A mixture of acid ester and polymerization initiator (this is
Cured by light irradiation. ) Or modified acrylate
And primer combination (these are connected to each other
Hardens when touched. ). Unsaturated port
As an example of the ester-based adhesive, a maleic acid unit
Polyester containing vinylbenzene, acrylic acid S
Monomers such as ter, methacrylate and vinyl acetate
And a mixture of polymerization initiators (these are heated or irradiated with light
To cure. ). Examples of polyurethane-based adhesives include
Methylene bis (p-phenylenediene) as a cyanate component
Isocyanate), tolylene diisocyanate, hexa
Methylene diisocyanate, 1-chlorophenyldiiso
Cyanate, 1,5-naphthylene diisocyanate,
Odipropyl diisocyanate, ethylbenzene-α-
2-di-isocyanate, 4,4,4-triphenylmethyl
And tantriisocyanate.
Ethylene glycol, propylene glyco
, Triethylene glycol, tetraethylene glycol
, Glycerol, hexanetriol, xylylene
Diol, lauric acid monoglyceride, stearic acid
Monoglyceride, oleic acid monoglyceride, poly
Ethylene glycol, polypropylene glycol, poly
Examples include esters and polyamides. In the case of these heat or photocurable resins, the phase
The growth of the size of the isolated islands is due to the viscosity before the resin is cured.
This can be done at low temperatures, so most resins are
It can be selected from products for sale. Liquid crystal optics of the present invention
In the method of manufacturing the device, a non-liquid crystalline polymer
Includes growing islands. The growth of this island is
This is usually done by heating the liquid crystal panel.
To prevent the thickness of the crystal layer from changing more than necessary
Mix spacer with Spacer is not necessarily on the substrate
There is no need to fix it, just mix it with the liquid crystal material
No. The spacer is usually used for a liquid crystal optical element.
There is no particular limitation as long as it can be used.
Or spacer made of plastic with solvent resistance
Can be used. In particular, glass, plastic
Products are easy to obtain. As the shape of the spacer
Are mainly spherical or cylindrical (fiber),
Beads are suitable for manufacturing liquid crystal optical elements by a continuous process.
And is preferred. Suitable as material for spherical spacer
Specific examples of the thing, for example, inorganic materials such as silica
Materials, divinylbenzene and polystyrene-based polymer beads
And the like. The particle size of the spherical spacer is
The thickness may be adjusted to the thickness of the liquid crystal cell of the crystal optical element.
About 20 μm, preferably about 4 to 10 μm
Used. The mixing amount of the spacer is usually
0.05-1% by weight, preferably 0.1-0.5% by weight
Mix in the% range. Note that a dichroic dye is added to the liquid crystal material.
You may. As dichroic dyes, anthraquinones,
Zo, merocyanine, styryl, azomethine,
And dyes such as tolazine-based dyes. Next, the liquid crystal of the present invention
A method for manufacturing an optical element will be described. [Production method of liquid crystal optical element] Production of liquid crystal optical element of the present invention
The manufacturing method is suitable for manufacturing the liquid crystal optical element of the present invention.
Method, and by applying this method, the mechanical strength
Easily produce birefringent liquid crystal optical elements with excellent element performance
Can be manufactured. 1. Film forming process In the method of the present invention, first, the two substrates with electrodes are
Liquid crystal material and liquid crystal
Common to materials and non-liquid crystalline polymeric substances that are practically incompatible
The solution dissolved in the solvent and the space dispersed in this solution
A coating solution consisting of sir and then evaporating the solvent
A liquid crystal layer material layer is formed. As the substrate, electrode and spacer,
What is described in the description of the clear liquid crystal optical element is preferably
Used. As liquid crystal materials, various low molecular liquid crystals, high
A molecular liquid crystal or the like can be used without any particular limitation. The present invention
When manufacturing liquid crystal optical elements of
Liquid crystals and low molecular nematic liquid crystals are preferably used. As the solvent, most of the liquid crystal material itself is used.
Non-liquid crystalline polymer mainly used because it dissolves in solvent
It is appropriately selected from those that dissolve the substance. Liquid crystal in coating liquid
The amount of material, non-liquid crystalline polymer and spacer is
Although there is no limitation, the amount of non-liquid crystalline polymer used is usually
Total amount of liquid crystal material, non-liquid crystalline polymer substance and spacer
2 to 20% by weight, preferably 2 to 10% by weight
And If the amount of the non-liquid crystalline polymer is less than 2% by weight,
Film formation of liquid crystal layer when low molecular liquid crystal is used as liquid crystal material
And the average of islands of non-liquid crystalline polymer
Even if the diameter is in the range of 2 to 50 μm,
Mechanical strength may be insufficient. On the other hand, over 20% by weight
In other words, the size of the island of the cured product of the non-liquid crystalline polymer is large.
It is too sharp and can be seen directly by the naked eye, and unnecessary light scattering
May occur and the light transmittance of the liquid crystal optical element is reduced
Sometimes. The amount of spacer is usually
0.05-1% by weight, preferably 0.1-0.5% by weight
And As the solvent, a substrate and, if necessary,
Do not dissolve the alignment control layer or insulating film
There is no particular limitation as long as it dissolves the liquid crystalline polymer.
Absent. Usually acetone, methyl ethyl ketone, toluene
, Xylene, dichloromethane, chloroform, tetra
Hydrofuran, ethyl acetate, or a mixed solvent thereof
It is preferably used. The amount of the solvent depends on the liquid crystal material and the non-liquid crystalline polymer.
The substance can dissolve, and the coating liquid has a viscosity suitable for coating.
There is no particular limitation as long as the amount is
The sum of the non-liquid crystalline polymer material and the spacer is 5 to 90.
% By weight, preferably 10 to 60% by weight.
To Spin coating, dip coating
Method, roll coating, spray method, brush coating method, Kisco
Can use any method such as coating method, bar coating method, electrodeposition method, etc.
However, the above-mentioned plastic plate or film is used as a substrate.
When used, continuous coating becomes possible, and productivity is significantly improved.
You. Suitable methods for continuous coating include roll coating,
Kiss coat method, bar coat method, etc.
It is possible to use various types of coating equipment available on the market.
Wear. By evaporating the solvent from the coating film,
A liquid crystal layer material layer is formed on the electrode surface of the plate. Required
The liquid crystal layer material layer is formed according to the alignment state of the liquid crystal material.
Beforehand, if necessary, on the electrode surface of at least one substrate.
A mounted orientation control layer may be provided. Plastic as substrate
When a backing plate or film is used, an orientation control layer is provided.
Instead of rubbing, the substrate itself may be rubbed to form an alignment control film.
No. Also, when forming a twisted alignment of a nematic liquid crystal
Even if the optically active substance is further mixed and dissolved in the coating liquid,
Good. If the substrate does not have an orientation control layer,
Insulating layer to prevent conduction between electrodes, that is, liquid crystal
May be provided with a dielectric layer that does not have the effect of aligning
No. The alignment control layer, the optically active substance, the material of the dielectric layer, etc.
As described above. [0120] 2. Lamination process After the liquid crystal layer material layer has been formed, the two substrates are
The layers are laminated so as to face each other via the material layer. This stack is
Immediately after evaporation of the solvent,
It is preferable to perform it. As a lamination method, air bubbles etc.
A method of placing the opposite substrate gently so that it does not
Pure lamination method, lamination method using rolls
and so on. As a substrate, a flexible plastic plate or
When using plastic film, etc.,
And a method of laminating the same. For laminating
The roll is made of metal or rubber and is shown in FIGS. 3 and 4.
Thus, one or two rolls can be used. FIG.
In the method shown in (1), the liquid crystal layer material layer 9 is formed on the electrode surface.
The plate 1 is placed on the surface plate 12, and the liquid crystal
The counter substrate 1 on which the layer material layer is not formed is rolled into one roll 1
1 is used for lamination. Move the roll 11
Or the upper and lower substrates with the position of the roll 11 fixed.
It is moved in the same direction to advance lamination. In the method shown in FIG.
And a liquid crystal layer material layer 9 is formed on the electrode surface.
Substrate 1 having no liquid crystal layer material layer formed thereon
And between the roll pair while pressing with the roll pair
It is moved in the direction and stacked. Usually such a roll
A laminating device using
Process, evaporation of solvent and lamination continuously
It is preferable from the viewpoint of preventing contamination. 3. Growing process and island of non-liquid crystalline polymer
And curing process By heating the laminated body obtained in the laminating step,
Non-liquid crystalline polymer phase separated from liquid crystal material in liquid crystal layer material layer
An island of material is applied to each of the two substrates with an average diameter of
m and grow into a columnar shape that is in uniform contact with the surface
You. Usually, the compatibility between the liquid crystal material and the non-liquid crystalline polymer
If not, the above-mentioned film-forming process alone will not
The quality is phase-separated from the liquid crystal material to the cell thickness,
Form an island. However, the size and shape of the island in that case is
It is generally amorphous and varies greatly depending on the drying conditions of the solvent.
In addition, the contact area between the island and the upper and lower substrates is
Not always enough, and the mechanical strength of the resulting liquid crystal optical element
The degree may not improve enough. Therefore, in the present invention,
The average diameter of the islands is preferably 2 to 5 in view of display characteristics.
Of non-liquid crystalline polymer material islands so as to be in the range of 0 μm.
Grow size. The growth of the island is specifically as follows.
Done. When the non-liquid crystalline polymer is a thermoplastic resin
Is a temperature at which the resin once softens the laminate obtained in the laminating step.
Heat to a degree. In this way, phase separation can be achieved only by solvent evaporation.
Isolated amorphous non-liquid crystalline polymer islands gradually become cylindrical
Combine with nearby islands while growing
I do. Furthermore, the non-liquid crystalline polymer material softens once
And the strength of the obtained liquid crystal optical element is brought into close contact with the upper and lower substrates.
Significantly improved. The heating temperature depends on the resin
However, it is usually about 50 to 150 ° C. The heating time is
Once the resin has softened, it can be quite short, usually 1
It is about 60 minutes. The heating or cooling rate depends on the phase separation state.
Does not matter much, normal heating equipment, such as an oven
No problem at any capacity of about 0.1-20 ° C / min
No. In the case where the non-liquid crystalline polymer is a thermosetting resin
Before curing, the viscosity of the resin is usually low enough before curing.
The island grows sufficiently before the temperature is raised to the processing temperature.
The heating rate for ensuring island growth is 0.1 to
The temperature is 10 ° C./min, preferably about 1 to 5 ° C./min. resin
After curing, it may be cooled rapidly, and the mechanical strength of the liquid crystal optical element
Is big enough. When the non-liquid crystalline polymer is a photo-curable resin
But the viscosity is low enough before curing by irradiating light
Then, the temperature is raised at a temperature rising rate of 0.1 to 20 ° C./min.
Slightly higher, i.e., about 40-60 ° C. for a short time, for example, 1
What is necessary is just to heat for 10 minutes. After this treatment,
By irradiating light such as external light to cure the resin, mechanical
A liquid crystal optical element having high strength can be obtained. Compare with this
Phase separation of the resin by light irradiation as is known
Before curing, the liquid crystal and resin are compatible.
It is difficult to completely cure the resin even when irradiated with light,
Changed the phase transition temperature and other properties of the liquid crystal
And grow to an island large enough to gain strength
In order to achieve this, it is necessary to precisely control the light irradiation intensity, irradiation time, etc.
And generally reduces productivity. Whether these resin islands have grown sufficiently
An inspection process may be provided to confirm
No. Specifically, observation with an optical microscope is sufficient.
You. The liquid crystal optical element produced in this way has a mechanical strength
Is extremely high, and the liquid crystal can be
Is not so spilled. Of course, chemical stability
Some sealing treatment may be performed in order to ensure the above. [0128] EXAMPLES Hereinafter, examples of the present invention and comparative examples will be described.
The present invention will be described more specifically with reference to
It is not limited to the embodiment. Example 1 Low-molecular-weight strength marketed by Merck as a liquid crystal material
Dielectric liquid crystal composition ZLI-4655-100 (trade name)
It was used. The phase transition temperature of this liquid crystal composition is as follows
It is. [0129] Embedded image (Iso: isotropic phase, Ch: cholesteric)
Phase, SA^*: Chiral smectic A phase, SC^*: Kaira
Lusmectic C phase, K: crystalline phase) This liquid crystal is provided with a UV curable resin 3026 manufactured by ThreeBond.
8% by weight of B (trade name) based on liquid crystal, and Ube Nitto Ka
Spherical silica spacer (2.1 μm in diameter) manufactured by Nari Corporation
Was added to the mixture, and the mixture was added with methyl ethyl keto.
33% by weight for liquid crystal layer
Liquid (coating liquid). The substrate used was Sumitomo Bakelite Co., Ltd.
PES with ITO electrode (Polyether
Sulfone) film (trade name: Sumilite, thickness: 10)
0 μm, width: 300 mm, length: 50 m)
I prepared this book. First, an insulating film is formed on the electrode surface of one of the substrates.
5% by weight of nylon (F30K) manufactured by Teikoku Chemical
Sol solution with a microgravure coater,
After evaporation, it was wound up once. The thickness of this insulating film is measured by the stylus method.
When measured, it was about 0.3 μm. Then nothing yet
On the electrode surface of the uncoated substrate,
Applying the liquid crystal layer coating liquid using a lab coater,
Laminate roll installed at the point where the solvent finishes drying
Pair (one is 80mm in diameter and made of iron, the other is 80m in diameter
m silicone rubber, and each other by air cylinder
Pressurized. ) On the side where the insulation film is coated
It was continuously laminated and wound on a substrate. In addition, the real
In the embodiment, rubbing treatment is performed on the substrate and the insulating film.
The insulating film is provided to prevent conduction defects between the upper and lower electrodes.
Was. From the obtained laminate, a liquid crystal panel having a length of 90
0 mm was cut out and the film thickness was measured by optical interference method.
On the other hand, it was 2.1 μm, which is the same as the spacer diameter. In addition,
When observing the structure with a microscope, the liquid crystal and the UV curable resin
Separate, but their shapes are complex and intricate
Met. In this state, the liquid crystal is not yet aligned
The orientation of the liquid crystal panel can be changed by placing it between orthogonal polarizers.
But no light or dark. Next, this panel was heated to 70 ° C. using a thermostat.
After heating and leaving for 10 minutes, immediately take out to room temperature atmosphere
When the structure was observed again with a microscope, the resin was found to be a circular island.
And its diameter was about 4 μm. Island of
Approximately 6600 pieces / mm^TwoWas
And NL^Two= 26400. Furthermore, this resin is still
± 30 V, 100
Hz square wave voltage while applying one side to the entire liquid crystal panel.
Orientation treatment by giving a small amount of shear due to
went. After this treatment, UV (ultraviolet) irradiation device
Ushio Electric Co., Ltd. spot light irradiation device (UIS-1
0101), while manually moving the irradiation location
The entire surface of the crystal panel is irradiated with ultraviolet light to cure the resin.
Was. This process obviously hardens the LCD panel
Was. When the microscope is again observed, the resin is slightly sheared.
It stretched and became almost oval, but its average diameter and number
There was no change. This panel was used as an orthogonal polarizing plate (Sanritz Co., Ltd.)
, 92-18), and a DC voltage of 5 V is applied.
Switch its polarity and use a photodiode to control the transmitted light intensity.
When measured, the ratio of transmitted light intensity between dark and light, that is, contrast
Is 40 or more over the entire surface of the liquid crystal panel.
It was clear that the axes were horizontally oriented. Then get
Two evaluations were made to evaluate the mechanical strength of the
Value. The first is a vertical load test, shown in FIG.
The liquid crystal panel 13 is raised on the surface plate 12 as shown in FIG.
On Recon rubber 14 (diameter 10mm, height 10mm)
10 kgf. As a result, the LCD panel
Even after 24 hours, despite not being sealed
No liquid crystal flow was observed. As a second test, as shown in FIG.
Test to wrap a liquid crystal panel 90 ° around a round bar 15 made of
went. As a result, until the diameter of the round bar is up to 5 mm,
No change in contrast (contrast)
Was. Thus, a liquid having a strength not previously considered
A crystalline panel was obtained. Example 2 Rodic's nematic liquid crystal composition R as liquid crystal material
It is also marketed by the company under DN-0775 (trade name).
Optically active substance (chiral dopant) S-110
1 (trade name) was added to the liquid crystal at 3% by weight and twisted
It will be a chiral nematic liquid crystal with a pitch of about 16μm
Was prepared. For this liquid crystal, a non-liquid crystalline polymer
Acrylic UV curable resin 30 manufactured by ThreeBond
26B (trade name) based on 15% by weight of the liquid crystal
Spherical silica space manufactured by Ube Nitto Kasei Co., Ltd.
0.1% by weight of sir (4 μm in diameter)
Is dissolved in MEK and a 40% by weight solution for liquid crystal layer (coating
Liquid). Using the same substrate as used in Example 1,
The steps up to the formation of the edge film were performed in the same manner as in Example 1. Substrate is also insulated
The film is not rubbed, and the insulating film is between the upper and lower electrodes.
To prevent conduction defects. Again as in Example 1
Then, apply the liquid crystal to one substrate with a microgravure coater.
After coating the layer coating solution and evaporating the solvent, the opposite substrate is continuously
Laminated. A liquid crystal panel having a length of 800
mm, and measure the thickness of the liquid crystal layer by optical interference method.
As a result, it was 4.2 μm. The liquid crystal panel in this state
The whole is cloudy and observed with a polarizing microscope.
Although the liquid crystal and the resin were phase-separated, the shape of the resin island was not
In many cases, there were many fine ones having a diameter of about 1 to 2 μm. liquid
In the crystal part, the domain boundaries were unclear, but in the thickness direction
Had a TN orientation twisted about 90 °. In this state, a rectangular wave (5 V, 2 V) is applied between the upper and lower electrodes.
0 Hz), the liquid crystal was vertically aligned, and
When the microscope polarizer was made orthogonal, it became “dark”. Mark voltage
The intensity of the transmitted light with and without
And the ratio, that is, the contrast was measured.
Of course, it was 7 in this state. Then, the phase separated resin
LCD panels in a high-temperature bath to grow the size of the island
Heat treatment was performed at 50 ° C. The heating rate was 10 ° C./min and 5
After leaving at 0 ° C. for 1 minute, it was immediately taken out of the room. This process
Thus, the appearance of the liquid crystal panel became transparent. In this state
Has not cured the resin yet, so carefully
And observed with a polarizing microscope, the resin was a circular island
And the diameter is about 5 μm.
Was. When counting the number of islands, about 7500 / mm^Two
It was NL^Two= 187,500. Also,
The liquid crystal has a multi-domain (running) having an average diameter of about 3 μm.
(Dumb domain twist orientation). Next, the same spot as used in Example 1 was used.
A UV irradiator is applied to the entire surface of the liquid crystal panel as in the first embodiment.
The resin was irradiated with light to cure the resin. This process gives the appearance
There was no change, but the feel I picked up by hand was a liquid crystal panel
It was becoming harder. This liquid crystal panel is
When observed with a microscope, the phase separation state has not changed at all.
Was. The polarizer of the polarizing microscope is made orthogonal to form a rectangular wave.
(5V, 20Hz), it becomes "dark"
When the voltage is not applied (“bright” state)
When I calculated the ratio, the contrast increased to 18.
Was. This LCD panel is a random domain twisted nematic
Evaluates the superiority of viewing angle characteristics due to the tick system
White fluorescent lamp sandwiched between two orthogonal polarizing plates
And put it on the lighting box of square wave voltage (5V, 20H
z) was turned on and off, and the contrast was measured. First
Turned the panel to the orthogonal polarizer,
Is always between 17 and 20
This was practically sufficient at all angles.
This is the advantage of being a dumb domain. Next, a photodiode for measuring the intensity of transmitted light
Position of the LCD panel gradually from the vertical direction of the LCD panel.
When the viewing angle characteristics were evaluated, the contrast was almost
The angle of halving is about 60 °, and the viewing angle characteristic is usually 30 °.
It is better than TN element which is said to be about °
Was. In this state, rotate the LCD panel in the panel plane.
However, the contrast is always between 8 and 12,
Confirm that it has good viewing angle characteristics in all directions
Was. Further, the load test and the bending were performed in the same manner as in Example 1.
Load test, but no change after 24 hours in load test
There is no appearance in the bending test until the diameter of the round bar is up to 6 mm.
No change was observed in both display (contrast) and 3
If it is less than mm, the upper and lower substrates peeled off. The above for comparison
300 mm x 800 mm from the laminate after the lamination process
Cut out one panel and heat-treat it without UV curing
And evaluated the strength of the panel manufactured by the same method
At the time of the load test, the liquid crystal flowed in about 5 minutes,
Color (birefringence interference color) differs between the pressing part and its surroundings
It became Then immediately remove the load and remove the panel
It was left for 4 hours but did not recover. Next, in this load test
When a bending test was performed using the undamaged part,
Even if the diameter of the round bar is 100 mm, the upper and lower substrates are separated.
Was. For comparison, the phase-separated resin island
Same equipment without heat treatment to grow the size
UV cured. Square wave with polarized light microscope with orthogonal polarizer
(5 V, 20 Hz) was applied, but the contrast was 8
there were. 24 hours after the same load test as above
After that, traces of columnar rubber were slightly recognized visually
And the load resistance was insufficient. Next, the bending test
When the diameter of the round bar was 20 mm or less, the upper and lower substrates
Has peeled off. Embodiment 3 A liquid crystal panel was manufactured in substantially the same manner as in Example 2, except that one
When an insulating film is applied to a substrate, its dry surface is continuously
It was rubbed. Rubbing is made of iron with a diameter of 100mm.
Substrate with a rubbing cloth wrapped around it
Without rotating the insulating film surface of the
I went to. Thereafter, the liquid crystal was produced in the same manner as in Example 2.
A panel was prepared. After UV curing, observe with a polarizing microscope
And the island of the cured resin is about 7μm in diameter and its size
Was relatively constant. Island density is N = 4000 / m
m^TwoIt was NL^Two= 190000
won. Also, from the rotation of the polarizer of the polarizing microscope, the liquid crystal
Orientation twisted about 90 ° uniformly over the entire liquid crystal panel
(Normal TN formula). Next, a liquid crystal panel is interposed between orthogonal polarizing plates.
ON / OFF of rectangular wave (5V, 20Hz) voltage
However, when the longitudinal direction of the liquid crystal panel and the polarization axis are about 45 °
Has the highest contrast of about 40. LCD panel
The same test as in Example 1 was performed as the strength evaluation of
At this time, the load test showed no change even after 24 hours.
It was found that the liquid crystal flow was sufficiently suppressed.
Was. Also, in the bending test, the round bar was completely outside up to 6 mm in diameter.
The view did not change. Embodiment 4 Do not mix any chiral dopants in the liquid crystal material
A liquid crystal panel was fabricated in exactly the same manner as in Example 2 except for the above.
did. After UV curing, observation with a polarizing microscope shows that the resin
The compound island is about 7 μm in diameter and its size is relatively constant
Met. The density of the island is N = 3900 / mm^TwoMet
So NL^Two= 191100. LCD is average
Although it was a multi-domain with a diameter of about 4 μm,
Liquid crystal has uniform orientation in each domain
I knew I was doing it. Next, as in Example 2, the liquid was applied between the orthogonal polarizing plates.
The crystal panel was placed and the viewing angle characteristics were evaluated.
The angle at which the contrast 16 is reduced by half is 55 °,
It was almost the same in all directions. LCD panel strength
As an evaluation, the same test as in Example 1 was performed.
In the heavy test, no change was observed after 24 hours.
It was found that the flow of crystals was sufficiently suppressed. Also,
In the bending test, there is no change in appearance at all up to a round bar diameter of 5 mm.
won. Embodiment 5 As in Example 4, the liquid crystal material contains a chiral dopant.
No rubbing treatment was performed on the surface of the insulating film as in Example 3.
Was done. Others are the same as in the second embodiment.
Was prepared. After UV curing, when observed with a polarizing microscope,
The island of hardened fat is about 7μm in diameter, and its size is compared.
It was consistent. Island density is N = 4000 / mm^Twoso
NL^Two= 196000. The rotation of the polarizer of the polarizing microscope indicates that the liquid
Crystals are uniaxially horizontally aligned over the entire LCD panel
I understood. Next, sandwich the liquid crystal panel between the orthogonal polarizing plates.
ON / OFF of square wave voltage (5V, 20Hz)
However, when the longitudinal direction of the panel and the polarization axis are about 45 °, the maximum is obtained.
Also had a high contrast of about 35. The evaluation of the strength of the liquid crystal panel was performed in the same manner as in Example 1.
After performing the same test, 24 hours passed in the load test
After that, no change was observed and the flow of the liquid crystal was sufficiently suppressed.
I understood that. In the bending test, the diameter of the round bar
There was no change in appearance up to 7 mm. Example 6 Chiral nematic liquid crystal group manufactured by Merck as liquid crystal material
The product ZLI-2222-100 (trade name) was used.
This liquid crystal already contains a chiral dopant.
The twist pitch is about 20 μm. This liquid crystal
Is a thermoplastic resin as a non-liquid crystal polymer material
6% by weight of polystyrene (molecular weight 4000)
Fiber spacer (diameter 10 μm, Sumita Optical Co., Ltd.)
Was added to MEK, and the mixture was dissolved in MEK.
After dissolving and dispersing, a 45% by weight solution (coating solution) for the liquid crystal layer is obtained.
did. The same substrate as in Example 1 was used. I
The polyimide on the electrode surface is also on the misaligned substrate (Nissan Chemical Co., Ltd.)
2% by weight of NMP (N-ME)
Tilpyrrolidone) solution with a microgravure coater
Coating, using the same rubbing roll as in Example 3
Rubbing in the longitudinal direction to form an orientation control layer and winding
Was. Next, in the same manner as in Example 1, the substrate on one side
Coating the liquid crystal layer coating liquid on the alignment control layer of
It was laminated with a counter substrate. Long from the obtained laminate
Cut out a liquid crystal panel of 600 mm in length, and
When the crystal layer thickness was measured, it was 10.5 μm. This
After all, the whole liquid crystal panel is cloudy,
A rectangular wave (5 V, 10 H) is sandwiched between upper and lower electrodes sandwiched between polarizing plates.
z) was turned on and off, but the contrast was 2 or less.
The reading was very dark. Observe with a polarizing microscope
The polystyrene islands are irregular, and enter the liquid crystal
I was involved. In this state, a test piece (50 mm x 100 m
m), a bending test was performed.
The upper and lower substrates peeled off. Next, the size of the resin (polystyrene) island
90 is the temperature at which this resin softens for growth.
The liquid crystal panel was heated to ° C. Heating using a thermostat
Temperature rate 10 ° C / min., Leave at 90 ° C for 5 minutes, then up to 50 ° C-
The temperature was lowered at a rate of 10 ° C./min, and the liquid crystal panel was taken out to room temperature.
The liquid crystal panel is transparent on the whole visually,
When observed with a polarizing microscope, the polystyrene islands
It has a round shape and its diameter is about 15μm
Was something. Furthermore, when the number of islands was counted, N = 380
Pieces / mm^TwoIt was NL^Two= 69500
I understood. Also, from the rotation of the polarizer, the liquid crystal
180 ° twist in thickness direction, twisted nematic orientation
I understood that. This liquid crystal panel is interposed between the aforementioned orthogonal polarizing plates.
So that the rubbing direction is at 45 ° to the polarization axis.
Place a rectangular wave voltage (5 V, 10 Hz) between the upper and lower electrodes.
Voltage was applied and its on-off contrast was measured.
However, it was about 30. Implement the strength of this liquid crystal panel
When evaluated in the same manner as in Example 1, 24 hours passed in the load test.
There was no change in appearance after a while. 8 in bending test
There was no change in both appearance and display in bending up to mm.
As described above, even thermoplastic resins have excellent mechanical strength.
It has been clarified that a crystal optical element can be produced. Embodiment 7 Epoxy resin, a thermosetting resin made of a specific liquid crystal polymer
[Made by Yuka Shell Epoxy Co., Ltd., main ingredient: Epikote 82
8 (trade name), curing agent: Epomate QX-11 (trade name)
Name), the mixing weight ratio is (base agent) :( curing agent) = 95: 5]
Except that the mixture was 10% by weight with respect to the liquid crystal.
Laminate and cut out the LCD panel in the same manner as in Example 6.
I went in. The thickness of the liquid crystal layer was 11 μm. When observed with a polarizing microscope, the epoxy resin
Although the phases are separated, the shape of the island is irregular.
Was. A liquid crystal panel is placed between orthogonal polarizers,
Apply rectangular wave voltage (5V, 10Hz) between poles to control
When the last was measured, it was about 4. Next, the thermostat
The LCD panel is heated using a
Was done. The rate of temperature rise is 10 ° C./min.
After holding for a minute, it was immediately taken out of the room. In this state
The crystal panel is placed between orthogonal polarizers, and the contrast is measured.
As a result, it was improved to 22. Observe with a polarizing microscope
Then, the average diameter of the epoxy resin island was 22 μm.
Was something. The number of islands is N = 280 / mm^TwoAnd
NL^Two= 134520. Also, the rotation of the polarizer
The liquid crystal is twisted 180 ° in the panel thickness direction.
It turned out that it was nematic alignment. The same strength test as in Example 1 was performed.
Of course, in the load test, appearance and display change after 24 hours.
No, even in bending test and bending to 4mm in diameter,
There was no change in the display. [0159] According to the liquid crystal optical element of the present invention, display can be performed by pressing or the like.
With high mechanical strength that does not cause
In addition, it can be manufactured by an easy process. In addition, the present invention
The method for manufacturing a liquid crystal optical element of
This method is suitable for manufacturing, and according to this method, the mechanical strength
Easy production of liquid crystal optical elements with excellent display characteristics
be able to.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partial cross-sectional view showing one embodiment of the liquid crystal optical element of the present invention. FIG. 2 is a schematic view showing one embodiment of an alignment state of liquid crystal in a liquid crystal optical element of the present invention. FIG. 3 is a partial cross-sectional view showing a laminating step in one embodiment of the method for manufacturing a liquid crystal optical element of the present invention. FIG. 4 is a partial cross-sectional view showing a laminating step in one embodiment of the method for manufacturing a liquid crystal optical element of the present invention. FIG. 5 is a perspective view showing a method for measuring the mechanical strength of a liquid crystal panel. FIG. 6 is a diagram showing a method for measuring the mechanical strength of a liquid crystal panel. [Description of Signs] 1 Substrate 2 Electrode 3 Liquid crystal layer 4 Liquid crystal material 5 Spacer 6 Island of cured material of non-liquid crystalline polymer substance 7 Polarizer 8 Domain 9 Liquid crystal layer material layer 11 Roll 12 Surface plate 13 Liquid crystal panel 14 Columnar shape Silicon rubber 15 round bar

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-25414 (JP, A) JP-A-5-61051 (JP, A) JP-A-6-301039 (JP, A) JP-A-6-301039 331968 (JP, A) JP-A-7-43695 (JP, A) JP-A-7-104249 (JP, A) JP-A-7-120728 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02F 1/13-1/141

Claims (1)

(57) Claims 1. A liquid crystal material and a non-liquid crystalline polymer that is substantially incompatible with the liquid crystal material on an electrode surface of at least one of the two substrates with electrodes. A step of applying a solution in which a substance is dissolved in a common solvent and a coating liquid comprising a spacer, and then evaporating the solvent to form a liquid crystal layer material layer. Heating the obtained laminate so that islands of the non-liquid crystalline polymer material phase-separated from the liquid crystal material in the liquid crystal layer material layer are formed on each of the two substrates. Average diameter 2
A method for producing a liquid crystal optical element, comprising the steps of: growing a non-liquid crystalline polymer substance in a columnar shape that is in uniform contact with a surface of an area of about 50 μm, and then curing the non-liquid crystalline polymer substance.