JPH03161715A - Liquid crystal display element and device - Google Patents

Abstract

PURPOSE:To obtain the liquid crystal display element which has high contrast, low voltage driving, high visual field angle, durability and other characteristics in combination by adding an orientation treating material of liquid crystal material molecules into or onto the fibrous aggregate of a layer of an object to be penetrated formed of the fibrous aggregate forming a liquid crystal layer together with a liquid crystal material. CONSTITUTION:The orientation treating material is incorporated into the surface layer or the inside of the fibrous aggregate 8. If the blank materials are so selected that the refractive index of the polymer forming the fibrous aggregate 8 and contg. the orientation treating material of the liquid crystal molecules and the ordinary light refractive index of the liquid crystal material coincide in this case, the refractive index difference between the blank materials is eliminated and a transparent state is shown when the major axes of the liquid crystal molecules are unified in the electric field direction by impressing voltages to the device. On the other hand, the liquid crystal material molecules orient along the surfaces of the individual fibrous materials and the refractive index difference arises between the polymer and the liquid crystal material 7 while the voltages are not impressed. Incident light is scattered by this refractive index difference and the domain of the liquid crystal material itself. The optical characteristics are enhanced in this way and the high contrast at the time of the on and off of the voltages is attained. The display part of the liquid crystal display element to allow the low-voltage driving is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a liquid crystal display element and device. More specifically, the present invention utilizes the properties regarding light scattering, absorption, and transmission of a permeable object layer made of fibrous aggregates permeated with a liquid product, and the permeable object layer is subjected to various tonnage pressures. Regarding liquid crystal display elements that perform display with or without application of energy or that constitute part or all of display boards, windows, doors, walls, etc. using a shutter effect, especially optical characteristics. , relates to a liquid crystal display element or device with improved durability and heat-and-moisture resistance.

(Prior Art and Its Disadvantages) Conventional liquid crystal display devices use a twisted nematic method (in which a liquid crystal layer is supported by a transparent substrate such as glass with a transparent conductive film attached, and polarizing plates are attached on both sides of the transparent substrate). TN method) is often used. Such liquid display elements require expensive polarizing plates;
In terms of performance, there were also drawbacks such as insufficient brightness and viewing angle of the device. In addition, when using a glass substrate for the display element of Dai II[]IFIt, the element is fragile and a glass plate that is not completely flat is used to sandwich the fluid liquid crystal layer to a uniform thickness inside and outside the 104. Since it is extremely difficult to do so, it is easy to cause unevenness in appearance or properties due to uneven thickness.

To solve these problems, a method has been proposed in which a polarizing plate is not required and the *Jil refractive index of the liquid crystal is used to electrically control the 22I bright or cloudy state. This method basically matches the ordinary refractive index of the liquid crystal molecules with the refractive index of the supporting medium, and when a voltage is applied and the orientation of the liquid crystal molecules is aligned, a transparent state is displayed, and when no voltage is applied, a transparent state is displayed. , which displays the state of light scattering due to disordered arrangement of liquid molecules. Two methods have been proposed based on this principle. One method is to disperse liquid crystal microstructures in a polymer. This is also called a capsule-type liquid product, and because the liquid crystal microdroplets are individually encapsulated in the polymer, they do not flow, and the actual thickness of the liquid crystal layer can be controlled by the coating thickness of one polymer layer. Therefore, large-screen display elements can be manufactured relatively easily. There is a method of emulsifying water-soluble polyvinyl alcohol as a polymer component, spreading it on a substrate, and drying it to obtain a polymer skin in which liquid droplets are dispersed.

As another example of this method, patent publication 1988 2231
Sa bulletin. A portion of the liquid crystal is dissolved in an uncured resin such as epoxy resin or acrylic ultraviolet curable resin described in U.S. Pat. There is a way to break it out.

This method has a problem in that it is difficult to control the diameter of the formed liquid crystal microdroplets. In addition, we also need a resin that satisfies all of the following conditions, such as the condition that the liquid product is sufficiently separated during curing before curing proceeds, and that the cured resin has a refractive index that is almost the same as the ordinary light refractive index of the liquid crystal. No assembly was obtained.

Another method that has been proposed is in Appli Physics Letters Volume 40, No. 1, January 1982.
edPhysics Letter Vow. 40
Ha 1, Jan. In this method, as reported in (1982) and others, liquid crystal is poured into porous micropores and sandwiched between transparent substrates on both sides.

Although this method is also useful in principle, it has problems such as variations in the size of the pores and grooves of the porous material used, and it is difficult to respond at low voltages. It had drawbacks such as difficulty in obtaining a highly transparent state. In addition, in both of these two methods, in order to obtain excellent optical properties, it is necessary to strictly match the ordinary refractive index of the resin layer and the liquid crystal, but these properties and liquid crystal grain formation It was technically extremely difficult to select a resin composition that had all of the following properties: durability, heat resistance, etc. Furthermore, even when the refractive indexes are matched, the transparency during voltage application decreases as the display element is viewed diagonally. There was also the problem of a narrow viewing angle.

In order to improve these problems, the present inventor previously disclosed in Japanese Patent Application No. 1-128000 a liquid crystal display element having a permeable object layer consisting of a fibrous aggregate impregnated with liquid crystal. We proposed a device. The present invention further improves the conventional liquid crystal display element and device described above, and provides an excellent liquid crystal display element and device that can achieve high contrast and low bulk pressure when an electric field is turned on and off, and can be put to practical use. The purpose is to

(Means for Solving the Problems) The present inventor has perfected the present invention as a result of various studies to solve the problems encountered by the conventional liquid crystal display elements and devices. Therefore, according to the present invention, the present invention comprises at least two conductive substrates including at least l transparent conductive substrates and a liquid layer supported between them, and the liquid layer is in contact with a liquid crystal substance. In a liquid crystal display element and device, the surface of the fibrous material, etc. of the permeable material layer is composed of a permeable material layer mainly composed of #a fibrous aggregates, which exist uniformly dispersed in the surface of the permeable material layer. A liquid product indexing element and device characterized in that the layer or inside thereof contains an alignment treatment agent are provided.

The present invention will be explained in more detail below with reference to the drawings.

The basic structure of the liquid crystal display element of the present invention is shown in FIG.

In the liquid display element shown in Figure 1, transparent
! Between the transparent substrates 1.2 with poles 3, 4, a liquid crystal substance 7
A permeable object layer 8 made of a fibrous aggregate of a polymer containing the same and a spacer (used as necessary) 9 are dispersed, and a drive circuit IO is connected to the transparent electrode 3. , 4, and 5 and 6.
This is a sealing polish to keep the liquid crystal layer isolated from the outside world, and it is bonded and sealed with an appropriate sealant.

In Fig. 1, when the material is selected so that the refractive index of the polymer forming the fibrous aggregate and containing the alignment agent of the liquid product matches the ordinary light refractive index of the liquid product, the voltage is applied. Sometimes, when the long axes of liquid crystal molecules are aligned in the direction of the electric field, the difference in refractive index within the material disappears, resulting in a transparent state.

On the other hand, when no voltage is applied, the liquid molecules are oriented along the walls of the individual fibrous substances inside the fibrous aggregate, and the polymer and liquid that form the aggregate and contain the liquid crystal alignment agent A refractive index difference is generated between the liquid product and the liquid product, and the incident light is scattered due to this refractive index difference and the domain of the liquid product itself inside the fibrous aggregate. Good contrast can be produced by increasing the difference between the transparent state and the scattering state when voltage is applied and when no voltage is applied.

In the present invention, the refractive index of the polymer containing the alignment treatment agent of the liquid product is matched with the ordinary refractive index of the liquid crystal used, but the degree of this matches depending on the diameter of the fibrous material used. As the diameter becomes smaller according to the wavelength of visible light, the degree of coincidence of the refractive indexes becomes more relaxed (for example, the difference is up to about 0.10). Therefore, the diameter of the fibrous material made of a polymer containing a liquid alignment treatment agent used in the present invention is between 5/Jl and o. There is no restriction as long as it is within the range of oosμ, but from the viewpoint of selecting the fibrous aggregate and liquid product that should be put to practical use, it should be at least 50% or more (more preferably 70% or more). The fibrous material is O. SIIm
Hereinafter, it is convenient that the diameter is preferably 0.34 or less. The permeable object layer constituting the liquid crystal display element and device of the present invention is an object layer treated with 4W of a permeable substance. It is a substance that easily exhibits a wetting phenomenon in the liquid crystal and excludes substances between the substance and the liquid crystal, such as air-only gases, and includes general polymers6. is hollowed out with a permeable substance to form a space for receiving the liquid crystal therein so as to efficiently and purposefully configure the liquid crystal display element and device of the present invention. Alternatively, the liquid layer of the present invention can be constructed by accepting liquids with low boiling points while excluding them.

The above-mentioned polishing of permeable objects is mainly made of fibrous aggregates, but in addition to the fibrous aggregates, this object also contains adhesive layers, adhesive spacers, etc. It may further contain MAT (particles that adhere j1 fibrous aggregates), spacer intersections, and the like.

The liquid display element of the present invention, which has as one of its structural elements a permeable object layer mainly composed of fibrous aggregates formed from a polymer containing a liquid crystal alignment agent, is manufactured by the following method. obtain.

That is, after adjusting the viscosity of the polymer used to form the fibrous aggregate of the present invention, or the heptamer or oligomer for forming the polymer, by diluting with a solvent or heating, appropriate spinning is performed. The fibers are spun using a technique and deposited to a certain thickness on a transparent electrode of a transparent conductive substrate to form a fibrous aggregate. The fibrous aggregate may be cured immediately before and/or after being deposited on the transparent conductive substrate, if necessary.
Provides liquid crystal resistance and durability.

The liquid orientation treatment agent can be added to the polymer or the monomer or oligomer forming the polymer during spinning, or can be applied to the surface of the fibrous aggregate after it is formed into a fibrous aggregate.

A permeable object layer made of a fibrous aggregate formed by the above method and deposited on a transparent conductive substrate is coated with a liquid in which liquid crystal is infiltrated by coating, spraying, etc., or a permeable object layer is applied. For example, after the object layer is impregnated with a liquid by immersion in a liquid crystal, opposing conductive substrates are stacked on top of each other. Note that the opposing conductive substrate does not necessarily have to be transparent, and may have a reflective layer.

The proportion of the liquid alignment agent contained in the fibrous material is
It goes without saying that it depends on the orientation effect of the treatment agent, but the amount is 0.01 to 10%, preferably 0.01 to 10% of the weight of the fibrous material.
．． 02-5%. If the proportion of the alignment treatment agent is more than 10%, it is not preferable because the spinning conditions of the fibrous material or the physical properties of the formed fibrous material change greatly. In addition, when treating the surface of a fibrous material, it is preferable to use a solution in which the concentration of the treatment agent is at least 0.05%. As is well known, liquid crystal alignment agents are broadly divided into horizontal alignment agents and directional alignment agents. Basically, any of them can be used, but it is more preferable to use a vertical alignment treatment agent in order to achieve low furnace pressure driving.

The vertical alignment treatment agent that can be used in the present invention includes N,N-
Silane coupling agents such as dimethyl-N-octadecyl-3-aminopropyltrimethoxysilyl chloride, decyltrimethoxysilane, octadecyltriethoxysilane, and 3-phenylaminopropyltrimethoxysilane, and monobasic compounds such as chromium myristate complexes. Surfactants such as carboxylic acid chromium complexes, hexadecyltrimethylammonium bromide, octadecylamine hydrochloride, cetyltrimethylammonium bromide, cetyl pinoresinium bromide, and dialkyl (hexadecyl, heptadecyl and/or octadecyl) dimethylammonium chloride may be mentioned.

Examples of the horizontal alignment agent that can be used in the present invention include polymers such as polyvinyl alcohol, polyoxyethylene, polyimide, and poly p-phenylene, and dibasic carboxylic acid chromium complexes such as brassylic acid chromium complex. Among these alignment agents, those that can be used as polymers that form fibrous aggregates form fibrous aggregates by themselves and exhibit performance as an alignment agent. By mixing with other polymers at a certain mixing ratio or more, liquid crystal orientation can be imparted to the polymer surface.

The fibrous aggregate used in the present invention is formed by a suitable spinning technique, such as electrostatic spinning, centrifugal spinning, solution blow spinning or melt blow spinning.

In any of these methods, the polymer forming the fibrous aggregate must exhibit appropriate fluidity in the state of a solution diluted with a solvent or a molten product during the spinning process, and at the same time, it must be transparent. When deposited on a conductive substrate and formed into a fibrous aggregate, it already has the properties of a solid that does not exhibit stickiness in order to maintain the fibrous material self-retention and prevent the fibrous materials from adhering to each other. It is necessary.

In order to satisfy these contradictory properties, the following method is adopted in the present invention. The method of the first step is to dissolve a solid polymer exhibiting a thin film in a solvent in a solvent-free state, and spin the resulting solution by the above-mentioned electrostatic spraying method, centrifugal spinning method, solution blowing method, etc. After the solvent is evaporated and destroyed, a fibrous aggregate is formed on a transparent conductive substrate, and then, if necessary, cured to impart liquid crystal resistance and durability. Polymers suitable for use in this process include polyvininoleanolecol, polyvinyl butyral, polyvinyl formal; cellulose derivatives such as carboxymethyl cellulose, carboxyethyl cellulose; polystyrene; polyvinyl chloride; polymethyl methacrylate; polyether, polyether sulfone. , curable acrylic monomers, oligomers or mixtures of curable acrylics, polymers, and curable epoxy resins.

The second method is to cure a photocurable vinyl compound that exhibits liquid properties in a solvent-free state using a method such as ultraviolet crosslinking in the space immediately before forming a fibrous aggregate using the above-mentioned spinning technique. , while providing self-supporting and non-degrading properties,
This method provides liquid crystal resistance and durability.

The photocurable vinyl compound suitable for this method and forming the polymer used in the present invention is not particularly limited as long as it can be polymerized and cured by radicals, such as styrene, divinylbenzene, vinyl acetate, etc., but particularly suitable ones include: (meta) at the end or side of the molecule as shown below.
Examples include curable acrylic compounds having one or more acryloyl groups.

The first is polyol (meth)acrylates, which are the reaction products of polyols such as ethylene glycol, diethylene glycol, trimethylolpropane, etc., and (meth)acrylic acid. The third type is polyester di(meth)acrylates, which are reaction products of a polyester having 2 to 20 terminal hydroxyl groups and (meth)acrylic acid. It is a (meth)acrylic acid addition reaction product of a compound, and as a polyepoxy compound, it is a polyglycidyl ether derived from a polyhydric alcohol or a hydroxyl group-containing compound such as bisphenol A, and epichlorohydrin, or a polyhydric carboxylic acid and ebichlor. Examples include polyepoxy compounds such as polyglycidyl ethers derived from polyisocyanate compounds and hydroxyl group-containing (meth)acrylic monomers. Alternatively, it is obtained by reacting an oligomer containing a (meth)acryloyl group and a hydroxyl group.

The fifth type is (meth)acrylic monomers, examples of which are ethyl (meth)acrylate, probyl (meth)acrylate, and hexyl (meth)acrylate.

The sixth type is a so-called unsaturated polyester obtained by condensing an unsaturated polycarboxylic acid such as maleic anhydride with another polycarboxylic acid and a polyhydric alcohol.

In addition, the photopolymerization initiators used in the present invention include benzoin methyl ether, benzoin n-butyl ether, penzoin phenyl ether, naphthoquinone, penzophenone, bivaloin ethyl ether, penzoyl peroxide, 1,1-dichloroacetophenone. ,2,2-
Diethoxyacetophenone, benzophenone amines (
(N-methyldiethanolamine, triethylamine, etc.), and the blending amount is approximately 1 to 1 in the composition.
Select an appropriate amount from the range of 10% by weight. The third method used to form fibrous aggregates is to spin a polymer that exhibits solid properties in the absence of a solvent using melt spinning technology, solidify it by cooling in space, and create a transparent material. In this method, a fibrous aggregate is formed on a conductive substrate, and then, if necessary, cured using an ultraviolet curing device or the like to impart liquid crystal resistance, durability, and heat resistance.
Polymers suitable for use in this method are those that are insoluble or poorly soluble in solvents, e.g.
polyethylene terephthalate. Polyamide, polypropylene, polyethylene, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, trifluoroethylene polymer, tetrafluoroethylene-ethylene copolymer, curable epoxy resin, polyp- Examples include phenylene.

The curable epoxy resin used in the above method is preferably substantially colorless when forming the fibrous aggregate, such as bisphenol A diglycidyl ether or bisphenol F having an epoxy equivalent in the range of 150 to 5000.
Diglycidyl ether, hexahydride bisphenol A
Difunctional epoxy resins such as diglycidyl ether, neopentyl glycol diglycidyl ether, phthalic acid diglycidyl ester, propylene glycol diglycidyl ether, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, having an epoxy equivalent in the range of 130 to 350, Examples include polyfunctional epoxy resins such as tetraglycidyl metaxylene diamine.

In addition, the curing agent for the above epoxy resin is similar to that of epoxy resin.
Those in the form of fibrous aggregates, sometimes substantially colorless, are preferred; examples of such curing agents include polyaddition types such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, and modified products thereof; Mencendiamine, isophoronediamine, N-aminoethylpiperazine, bis(4-amino-3-methylcyclohexyl)methane and its modified products; m-xylenediamine, diaminodiphenylmethane,
Polyamines such as diaminodiphenylsulfone and its modified products; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, chlorendic anhydride,
Acid anhydrides such as pyromellitic anhydride, penzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimate), and methylcyclohexenetetracarboxylic anhydride; Types include 2,4.6-tris(dimetalaminomethyl)phenol, 2-ethyl-4-methylimidazole, BF. -monoethylamine complex and the like.

In any of the above methods, in order to obtain the fibrous material with a small diameter used in the present invention by the spinning technique, the polymer used in the production of the fibrous material or the heptanomer or oligomer forming this polymer must be used. After dissolving or diluting with a solvent, it is important that the resulting solution has a viscosity within a certain range, and especially when electrospinning is employed, the above solution has a viscosity of 20 to 1500
cps. In particular, it is preferable to have a viscosity of 50 to 1300 cps. It is of course necessary that the heptanomer or oligomer used in the production of the fibrous material not evaporate at the above-mentioned spinning temperatures. In the present invention, the above-mentioned polymer or the monomer or oligomer forming the polymer is selected from among various materials satisfying the above-mentioned requirements, taking into consideration the refractive index of the liquid crystal and the viscosity during spinning. In addition, the above polymers, monomers, or oligomers may be used as modifiers necessary for the production of devices or modifiers for the created devices, such as crosslinking agents, surfactants, diluents, thickeners, ultraviolet absorbers, pigments, etc. It may contain a polymerization accelerator, a chain transfer agent, a polymerization inhibitor, etc.

Furthermore, as mentioned above, the organic solvent used in the production of the fibrous aggregate needs to evaporate and scatter in the space immediately before forming the fibrous aggregate after spinning. It is not preferable to use a single solvent with a boiling point of 150° C. or higher, which is difficult to exhibit, or a mixture containing 20% or more of such a solvent. Organic solvents that can be used for the above purpose include ethanol, n-propanol, isopropanol, n-butanol, see-butanol. Alcohols such as alcohol, diacetone alcohol, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, isoprobyl acetate, n-butyl acetate, acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethers such as tetrahydrofuran and dioxane, N,N'-dimethylacetamide, N,N'-
Examples include amides such as dimethylacetamide, chlorinated solvents such as methylene chloride, and chloroform, and these may be used alone or as a multi-component mixture.

The liquid crystal used in the present invention is a nematic, cholesteric, smectic, etc. liquid crystal, and includes either a single compound or a mixture of multiple compounds. It also includes products that have a cholesteric structure by adding cholesteric components to nematic liquid products. Similarly, it also includes cases where liquid crystals with one phase are added with substances with other phases.
Furthermore, one or more dichroic dyes may be dissolved in these liquid crystals. In this case, various displays between a cloudy colored state and a transparent colored state can be performed.

The ordinary refractive index of liquid mixtures available on the market is usually l. 4
9~l. 52, and a value between these can be selected as appropriate, but the ordinary refractive index can be further finely adjusted by further mixing liquid crystal mixtures having different ordinary refractive indices. .

On the other hand, since the fibrous aggregate of the present invention uses a fibrous material with a small diameter as described above, the degree to which the refractive index of the fibrous material matches the ordinary refractive index of the liquid crystal used is
(For example, the difference is O.lOa
degree), the refractive index can be more easily tuned over a wide range by choosing the appropriate polymer.

The permeable object M impregnated with liquid crystal produced by the method described above can operate with a thickness of 2 to 100 μm, but when considering the applied voltage and contrast during on-off, it can be reduced to 4 to 40 μm. It is preferable to set

If the permeable object layer into which the liquid crystal is permeated is too thin, the driving voltage may be low, but W! Light scattering properties cannot be obtained when no pressure is applied. On the other hand, if it is too thick, the driving voltage will become too high, which is undesirable. As the transparent substrate, glass,
0 such as polymethyl methacrylate, epoxy curing resin, etc.
．． Relatively rigid substrates with a thickness of 1 to 4 mm, or flexible film substrates with a thickness of 0.01 to 0.5 am that are chemically stable for liquid crystals such as polyester films, epoxy resin cured films, polyethersulfone films, etc. can be used. Note that a barrier layer having an effect of blocking air and water vapor, a reflective film, an antireflection film, a hard coat layer, an ultraviolet absorbing layer, a passive layer, etc. may be formed on the surface of the substrate. A display element is constructed by sandwiching a permeable material layer impregnated with liquid crystal by combining two of these sheets, either the same or different ones. Reflective display panels that utilize reflective substrates are particularly important for large display panels. Reflective substrates include a pure reflective type that uses a metallic mirror surface, a colored reflective type that uses various types of light absorption, a black reflective type that mainly absorbs light, and reflections such as specular reflection, satin, matte, etc. depending on the condition of the reflective surface. There are various milky-white and various emulsion-colored reflectors that utilize surface, light absorption, and scattered transmitted light. When directly utilizing a metal surface or a conductive film, the transparent conductive film treatment may be omitted. The gold-plated surface can be etched in the same way as a transparent conductive film, and can be adapted for various display purposes. Metals such as aluminum, gold, silver, platinum, nickel, and palladium are used as reflective substrates that are coated on appropriate substrates by methods such as plating, vapor deposition, sputtering, and ion plating. In this case, a reflective display element is constructed by combining the reflective substrate, the polymer layer, and one more conductive transparent substrate. In the case of a reflective type, a double-sided reflective substrate with reflective film treatment on both sides and two transparent conductive substrates are used to sandwich two liquid crystal impregnated polishing bodies, forming a double-sided reflective display element. can do.

Transparent conductors are required on the liquid layer side of the opposing transparent substrate to apply voltage to the liquid crystal, and this is done by vapor deposition, sputtering, or CVD of tin oxide or a mixture containing indium oxide as the main component. Or 20% by pie mouth sol method etc.
~Roat to a depth of 5,000 people and practice form. The transparent electrode can be etched into a predetermined shape by photolithography or photoresist printing to display a local display, or to form a segment or dot matrix.

Note that it is preferable that a seal portion be provided around the outer periphery of the liquid display element to prevent the liquid crystal substance from seeping out. Epoxy adhesives, silicone adhesives, urethane adhesives, acrylic adhesives, cyanoacrylate adhesives, and other adhesives that harden at relatively low temperatures can be easily used as sealing materials. Acrylic adhesives, epoxy adhesives, or hot melt adhesives for each spike can also be used. These can be used by applying them to the outer periphery of the liquid display element after fabrication using a dispenser or screen printing method, or they can be applied near the outer periphery of one side of the substrate before laminating two substrates, and then It can also be made by laminating it. These adhesives may contain additives for improving M1 fabric properties, printability, adhesion, water resistance, heat resistance, and ultraviolet resistance. Alternatively, as another sealing method, the outer periphery of the substrate may be fused and sealed using a method such as heater heating, ultrasonic heating, high frequency heating, laser heating, etc. after the element is fabricated. The liquid crystal display element thus produced can be used alone as is, or it can be used as a laminated glass by covering one or both sides with a glass plate or the like. In this case, overall smoothness, rigidity, surface hardness, durability, design, etc. are improved.

As described above, according to the present invention, by containing a liquid crystal alignment agent in the fibrous aggregate or on its surface, it is possible to achieve high contrast, high viewing angle, and low voltage driving when an electric field is turned on and off. Liquid crystal display elements and devices with these excellent properties can be put to practical use. The liquid crystal display device of the present invention can be used for many purposes of conventional liquid crystal display devices, such as calculators, watches, ECRs, automobile instrument panel displays, and other information displays.

In addition, since the display element for display devices of the present invention is suitable for manufacturing larger display devices than conventional ones, it is possible to electrically change the state between bright and cloudy or between transparent and colored. It can be applied to windows, doors, partitions, automobile sunroofs, etc. that can be controlled in a controlled manner, as well as large double-sided reflective advertising time display boards.

(Example) Examples of the present invention are shown below, but the present invention is not limited thereto.

Prior to describing embodiments, the following terms used in this specification will be explained.

“Haze value” is expressed as a percentage, and haze (Ov) and haze (IOOV) are values measured, for example, with voltages of zero volts (i.e., no applied electric field) and 100 volts applied between the electrodes of the device; These haze values are measured according to ASTM Standard 01003 using a haze meter such as manufactured by Tosou Keiki Co., Ltd.

``Contrast''; This is [Haze (Ov)
IOOV)/Haze (OV).

"Average fiber diameter": This is the scanning electronic BJ microscope (SEX
) shall mean the statistical average of the diameter values obtained from sample measurements. ``Proportion of fibers with a diameter less than or equal to Xo+m''; This means a statistically calculated value based on sample measurement using a scanning electron microscope (SEM); ``Refractive index evaluation method by immersion method'' Isotropic liquids with various refractive indices (CARGILL
E.L. A fibrous aggregate is immersed in a fibrous aggregate (AB Company; USA), and the refractive index of the isotropic liquid with the highest transparency of the immersed fibrous aggregate is determined by appearance judgment to be the refractive index of the fibrous aggregate. This is the way to do it.

″″Viscosity measurement″ A Tokyo Keiki Co., Ltd. I1B type viscometer BL-old was used.

``Viscosity strength'' Determined from shear peel strength using a Tensilon type pull-side tester manufactured by Toyo Baldwin. The adhesive part of the sample piece used for the measurement was medium lOIII1. The length was 10 mm, and the peeling speed was 10 am/min.

゛Threshold voltage (V.
It is expressed as the voltage that gives ov))). 12 Polyvinyl butyral (PVB) as a polymer for forming fibrous aggregates (manufactured by West German Hoechst, BGO)
T) was dissolved in isopropyl alcohol to obtain a 6% solution. Coronate HL
(manufactured by Nippon Polyurethane Industries Co., Ltd., abbreviated as NPU) 0.25 g was added as a crosslinking agent to 50 g of polyvinyl butyral solution and stirred until uniformly dissolved. Thereafter, a transparent conductive film based on indium oxide:tin oxide (15:5) was sputtered to a thickness of 500 μm on the polyester olefin.
, cut into pieces measuring 7 cm x 7 cm. Thereafter, using an electrospinning device, the polyvinyl butyral solution was applied at a flow rate of 2.0 cc/hour and a nozzle voltage of 25 kV DC.
The mixture was separated onto the above conductive polyester film for 3 minutes to obtain a transparent fibrous aggregate and polyester film aggregate. Thereafter, this assembly was placed in an oven and maintained at 50°C for one week to perform crosslinking treatment of polyvinyl butyral. When the diameter of the fibers of the aggregate of the fibrous aggregate obtained by crosslinking treatment and the polyester film was measured using a scanning electron microscope, the average diameter was 0.
32-, and the proportion of fibers with a diameter less than 0.5p was 63%.

In addition, the refractive index of this fibrous aggregate was determined to be 1.515 by the refractive index evaluation method using the immersion method.
．． The crosslinked aggregate was immersed in a 5% aqueous solution for IO minutes, taken out, air-dried, and heat-treated in an oven at 90° C. for 5 days. The ordinary refractive index is still 15.
17 (ZLI manufactured by Merck Co Ltd)
1289) was infiltrated into the permeable object layer made of the above fibrous aggregate.

Following the infiltration of the liquid, another transparent conductive polyester film was placed on the existing polyester aggregate, and the permeable object layer impregnated with the liquid was sandwiched between the layers. The electrical and optical properties of the liquid crystal display element thus obtained are shown in Table 1. As is clear from Table 1, the threshold voltage (VS.) of the liquid display element obtained above is 7V.
, which shows a lower value than that of Comparative Example t described later, and . Good contrast values were obtained.

Comparative Example ↓ A liquid product display element was produced in the same manner as in Example 1, except that the immersion and heat treatment of the chromium myristate complex in Example 1 were not performed. Electricity of the obtained liquid crystal display element
The optical properties are shown in Table 1. As is clear from Table 1, the threshold voltage (VS.) of the liquid crystal display element obtained above was 15V, which was higher than that of Example 1. A liquid crystal display element was prepared in the same manner as in Example 1, except that N,N-dimethyl-N-octadecyl-3-aminopropyltrimethoxysilyl chlorite was used as the direct alignment treatment agent. did. The electrical and optical properties of the liquid crystal display element thus obtained are shown in Table 1. As is clear from Table 1, the threshold pressure (
VS. ) is 9V, which is a lower value than that of Comparative Example 1, and has a good contrast value of 9! } was given.

A liquid crystal display element was produced in the same manner as in the example except that chromium brassylate was used as the main horizontal alignment agent. The electrical and optical properties of the liquid crystal display element thus obtained are shown in Table 1. As is clear from Table 1, the threshold voltage (VS.) of the liquid crystal display element obtained above is 9
v, which was lower than that of Comparative Example 1, and a good contrast value was obtained. After soaking the chromium myristate complex in the form of fibrous aggregates,
Instead of painting. A liquid display element was prepared in the same manner as in Example 1, except that 3% (volume ratio) of the polymer was added to the polymer solution for forming the m-fibrous aggregate. Table 1 shows the electro-optical characteristics of the liquid display element thus obtained. As is clear from Table 1, the threshold voltage Cvs of the liquid display element obtained above. )teeth,
8v, which was found to be lower than that of Comparative Example 1. It was also confirmed that a good contrast value could be obtained.

50 parts of behenyl methacrylate, epoxy ester 3002A (manufactured by Kyoeisha Buxu, bisphenol A
Using a mixture of 25 parts of acrylic acid adduct of 2 moles of polyoxyethylene adduct to diglycidyl ether, 10 parts of pentaerythritol tetraacrylate, and 15 parts of polymethyl methacrylate (Sumipex B Mll, manufactured by Sumitomo Chemical), this was A 10% solution was obtained by dissolving in beer alcohol. The viscosity of this solution is 15.5 cps
Met. 0.1 g of benzoin ethyl ether as a photopolymerization initiator was added to 100 g of the above curable vinyl compound solution, and stirred until uniform.

The liquid crystal to be penetrated using this polymer solution is different (ZLI 1691 manufactured by MERCK Co. Ltd.
A liquid crystal display element was produced in the same manner as in Example 1 except that the ordinary light refractive index was 1.499. Table 1 shows the electro-optical properties of the liquid crystal display element thus obtained. As is clear from Table 1, the threshold voltage (VS.) of the liquid display element obtained above was 7V, which is a lower value than that of Comparative Example 2 described later. Also, good contrast values were obtained.

Comparative Example 2 A liquid crystal display element was produced in the same manner as in Example 2, except that the immersion and heat treatment of the chromium myristate clamps in Example 2 were not performed. The electrical and optical properties of the liquid crystal display element thus obtained are shown in Table 1.

As is clear from Table 1, the threshold voltage (VS-) of the liquid crystal display element obtained above was 17 V, which was higher than that of Example 5.

A fibrous aggregate was formed in the same manner as in Example 4, except that 20% (volume ratio) of the chromium myristate complex was added to the polyvinyl butyral.

When observed with SEM, no uniform fibrous material was observed and the fibrous materials were fused together.

Polymer solution (A) for forming a fibrous aggregate, similar to that used in Example 1 for viewing lost salmon, and 3% (volume ratio) of chromium myristate complex added to this polymer solution. A polymer solution (B) was prepared.

These two types of polymer solutions were mixed using two electrostatic spinning apparatuses similar to those used in Example 1 and in the same manner as in Example 1, and the polymer solution (A) and polymer Solution (8) was dispersed on the transparent conductive substrate alternately for 3 seconds at a time ratio of 575 and a total dispersion time of 3 minutes. Thereafter, a liquid display element was produced in the same manner as in Example 4. Table 1 shows the electro-optical properties of the liquid crystal display element thus obtained. As is clear from Table 1, the threshold value (v, was gotten.

[Brief explanation of the drawing]

Figure 1 shows the basic structure of the liquid crystal display element of the present invention. 1, 2... Transparent substrate, 3, 4... Transparent electrode, 5, 6
...Sealant, 7.Liquid crystal substance, 8.Fibrous aggregate, 9.Spacer IO...Drive circuit procedure RL3IE document (self-published) February 13, 1991

Claims (1)

[Claims] 1. Consisting of at least two conductive substrates including at least one transparent conductive substrate and a liquid crystal layer sandwiched between them, the liquid crystal layer is in contact with a liquid crystal substance. In liquid crystal display elements and devices that are composed of a permeable substance layer mainly composed of fibrous aggregates that are uniformly dispersed, the surface layer or the interior of the fibrous substance of the permeable substance layer A liquid crystal display element and device, characterized in that the liquid crystal display element and device contain an alignment treatment agent. 2. The liquid crystal display element and device according to claim 1, wherein the alignment treatment agent is a vertical alignment treatment agent.