KR20020016829A - Electro-optical device and variable transparent article with such device - Google Patents

Abstract

The present invention provides an electro-optical device 29 of variable transmittance, with or without a power source, comprising an electro-optic cell containing a chromophore component with a battery-optical converting component. The color developer components may be photochromic, thermochromic and / or dichroic materials and mixtures thereof. The color developer component may be a coating, film or layer of one or more of the transparent substrates 37 and 39 in the electro-optical cell or may be part of the cell's electro-switching material 43. The electro-optical device may be a liquid crystal cell having one or more dichroic dyes present in the liquid crystal material. In another aspect of the invention, the chromogenic component may be a chromophore guest material that is retained or present within the electro-optical device. Electro-optical devices containing color developer materials include automotive transparency, such as privacy glass, sun visor bands and screens for passenger compartments; Architectural windows such as skylights and other windows; And for applications such as eyewear.

Description

ELECTRO-OPTICAL DEVICE AND VARIABLE TRANSPARENT ARTICLE WITH SUCH DEVICE

Optically switchable solids, liquids and gases are known in the art of exhibiting reversible spectral colors in the visible region by electrochromic, thermal, piezoelectric or photochromic. The subject matter relating to film is described in "Optically Switchable Thin Films: A Review" by Charles B. Greenberg, Thin Solid Films, 251 (1994) pp. 81-93, Elsevier Science S. A.]. The use of such materials in optically convertible products to limit the transmission of light is an ambitious attempt. Optically convertible eyewear using photochromic materials for glass and plastic substrates is commercially available. In addition, mirrors using electrochromic materials are commercially available. In addition, many recent patents refer to the activation of areas of electrochromic materials in automotive and architectural windows and mirrors and eyewear. An example of a variable transparent electro-optic device for eyewear that uses an electro-optic material to form a cell having an optical chromic material as one of the additional components of the glass or cell transparent plate is described in US Pat. No. 5,608,567 to Grupp. Is disclosed.

In addition, electrochromic devices using a variety of composites, such as monolithic multilayer electrochromic composites with complementary layers, are disclosed in PCT Publication WO 96/37809, which have a suitable electrochromic cell and an electric power source and a circuit. Coloring eyewear is discussed in US Pat. No. 5,455,637 and US Pat. No. 5,455,638. Also disclosed in the art is a liquid crystal display having a chiral nematic liquid crystal display for homeotropic alignment and negative dielectric anisotropy, as shown in US Pat. No. 5,477,358. All the foregoing documents and patents are incorporated herein by reference.

Industrial efforts continue to develop such technologies and apply them to useful products such as eyewear and windows and partition windows in automobiles, homes and / or buildings. For example, for photochromic substrates used as eyewear, these products require UV or actinic radiation to initiate and express optical convertibility. Thus, under circumstances where this type of light beam is minimal, the conversion is impaired. For example, photochromic eyewear used in vehicles such as automobiles does not receive sufficient UV light for conversion. Electrochromic glasses are operable in automobiles, but require a portable power source. In addition, the photochromic conversion cannot control its variability, and the conversion cannot be stopped at various viewpoints.

The object of the present invention is not only to provide transmittance variability in a product where the requirements of the power source and the circuit are conveniently provided, but also to have optical convertibility even when such power source and circuit elements are not available or other power sources are available. The present invention provides an electro-optical device for a variable transparent product.

Summary of the Invention

One embodiment of the present invention relates to an electro-optical device that constitutes an electro-optic cell that holds a colorant component in addition to the electro-optic converting component. The color developer components may be photochromic materials, thermochromic materials and / or dichroic materials and mixtures thereof. The colorant component as a coating, film or layer may be one or more of the transparent substrates of an electro-optic cell having the electrochromic component as an electroconverting component. In addition, the color developer component as a coating, film or layer can be a transparent substrate of one or more electro-optical devices, which is a liquid crystal cell having one or more dichroic dyes present with the liquid crystal material. In another aspect of the present invention, the color developer component is an electro-optical device (e.g., liquid crystal host material) as an electro-convertible (including magnetically convertible) component disposed in the gap between two or more electrodes in the electro-optical device. ) Or a colorant guest material present in the device. The liquid crystal host undergoes molecular rearrangement under the influence of the applied electric and / or magnetic fields in the electro-optical device. The color developer guest material is rearranged to provide improved optical convertibility or flexibility for the total convertible effect. One way in which this can occur is caused by structural or coordination changes imparted by coercion or rearrangement of the chromophore guest molecules to incident light. The chromophore component as a photochromic or thermochromic coating, film or layer located on a substrate of an electro-optical cell or device improves the optical convertibility or flexibility of the overall convertible effect. The thin film deposition method allows a polymer or hybrid hard coating material to be used to access the host and guest colorants to a glass or plastic substrate having transparent features. This application method does not require any individual glue adhesive material for coating the substrate, which may have additional action coatings or layers. For example, the guest material may be a dichroic material, such as a cobalt (II) complex, a photochromic material or a thermochromic material. An electric or magnetic field is provided to the electro-optical device from the electroconductive layer, film and / or coating to affect the change in the guest material contained in the liquid crystal host material with the change in the host material. As host material one or more liquid crystal materials of one or more smectic liquid crystal layers, one or more nematic liquid crystal layers and / or one or more lyotropic liquid crystal layers or combinations and mixtures thereof may already be arranged. Photochromic and / or thermochromic materials in the convertible material of the electro-optic cell may be converted to a darker state when the electro-optic cell is exposed to UV or actinic sources or heat.

Electro-optical devices containing colorimetric materials include automotive transparencys such as privacy glass in automobiles, sunshade bands and screens for passenger compartments; Architectural windows such as skylights and other windows; And for applications such as eyewear. As an electro-optical device, a variable transparent or transmissive product for the application is adaptable to accommodate a suitable power source consisting of a power source and a control circuit. In the case of eyewear, the power source may consist of a battery inside one or more frame members of the eyewear, and the control circuit may be located differently inside the vehicle, for example. Further, the power supply from the vehicle itself or in the vehicle can be used when the control circuit is located in or in the vehicle or from the vehicle. For example, the control circuitry and / or power supply may be connected to the spectacle frame from the seat belt of the vehicle and to the spectacles. This manner in which the electro-optical component of the eyewear is used inside the vehicle limits the photochromic response. Eyewear can be used outside of the vehicle by a photochromic material or a thermochromic material without being connected to a power source and control circuit.

This application takes precedence over the filing date of Provisional Application No. 60 / 138,197, filed June 11, 1999 in the name of Charles B. Greenberg.

The present invention relates to an electro-optical device, such as a liquid crystal or electrochromic cell, and a variable transparent article containing the device together with suitable battery elements and control circuit elements.

1 is a side elevational view of eyewear with a cut portion of a variable transparent lens removed from a frame, the frame being cut to show conductive wires and ports or batteries inside the frame.

FIG. 2 is a top sectional view of the transparent lens of FIG. 1 along the line A-A '(the line is perpendicular to the major surface of the transparent body of FIG. 2).

3 is an optional top cross-sectional view of FIG. 2.

In the description and claims of this specification, the description of a range of numbers includes the word "about" at the lower or upper limit of the range, unless otherwise stated. In addition, specific references to patents and publications with respect to particular disclosures and teachings include disclosures and teachings referencing such patent applications.

In FIG. 1, the eyewear frame 11 can be any eyeglass frame of typical construction having a lens holder portion 13 engaged with a hinge or the like on the side members 15 and 17. The side member 15 is hingedly engaged with the lens holder portion 13 via the hinge 19 and the side member 17 is hingedly engaged with the lens holder portion 13 via the hinge 21. For example, the side members can be hingedly engaged through a plate string lying obliquely in one or more arrangements with respect to the lens holder portion. The cut surface of the side member 15 shows an electrical connection 23 connected to the port 25 and the lens holder portion for moving current from the port 25 to the lenses 27 and 29. Side member 17 shows a cross-sectional view of electrical connection 31 electrically connected to battery 33 in member 17. If the battery 33 is present inside the eyewear of FIG. 1, the port 25 may be a connection for an electrical circuit to control power supply (current and / or voltage) to the lenses 27 and 29. In such a case, there may also be an electrical connection between the ports 25 through the electrical connection 23 around the lenses 27 and 29, but not shown in FIG. 1. If battery 33 is not present inside the eyewear, port 25 is used for power and electrical control circuitry to provide adequate power transport and convertible electricity to lenses 27 and 29.

In FIG. 1, the lens 27 is shown with a cross section of the coating 35 on the major surface outside of the transparent body. Such a coating may be present on lens 29 and the coating may be a photochromic coating that retains a photochromic material. Non-limiting examples may be photochromic polyurethane coating compositions in which the light beam exhibits photochromic performance when exposed to activating light. That is, the photochromic compound may be, for example, ultraviolet light of mercury light of daylight or halogen lamps. When exposed to light, including the same ultraviolet light, it exhibits a reversible color change. Other polymeric materials such as acrylic, polyester, polyamide based materials and the like can be used in the coating.

Photochromic materials useful in coatings are known in the art and are those synthesized and suggested for applications in which daylight induced reversible color change or darkening is desired. The classes most broadly disclosed as photochromic compounds are oxazine, pyran and fulzide, any of which may be used. A common mechanism of action that can be explained by reversible color change, namely the change in the absorption spectrum of the visible region of light (400 to about 770 nanometers) generated by different types of photochromic compounds, is described by John C. Crano. It is described and classified in "ogenic materials (Photochromic)" in KirK-Othemer Encyclopedia of Chemical Technology Fourth Edition, 1993, pp 321-332. Other classes of photochromic compounds include indolino spiropran and indolino spiroxazine. Materials of this type that are activated by UV light are transformed from colorless closed ring compounds to colored open ring species. The electrocyclic mechanism for the fused zide chromophoric compounds may include a modification from the colorless open ring form to the colored closed ring form. Compounds of this type can be used in applying the coating to the lens 27 or 29 of FIG. 1 by any application technique known to those skilled in the art, including thin film deposition.

Other photochromic compounds that can be used with the coating compositions of the present invention are organic photochromic compounds that generally have one or more active maximum absorptions in the range of 400 to about 770 nanometers that can be introduced as dissolved or dispersed in the coating composition. . Any of the foregoing photochromic compounds, including examples such as spiro (indoline) naphthography, as described in US Pat. No. 3,562,172, US Pat. No. 3,578,602, US Pat. No. 4,215,010 and US Pat. Can be mentioned. Spiro (indolin) pyridobenzoxazines and spiro (benindolin) naphthoxazines can also be used as disclosed in US Pat. No. 4,931,219. U.S. Patent 4,816,584, U.S. Patent 4,880,667, U.S. Patent 4,818,096, and "Spiro (Indoline) Pyrans Techniques in Chemistry", Vol. III, “Photochromism” Other photochromic compounds disclosed in Chapter 3 by Glen H. Brown, editor, John Wiley and Sons, New York, 1971 can be used.

Other organic photochromic materials that can be used may use materials having one or more maximum absorptions, preferably two maximum absorptions, in the visible region below 400-525 nanometers. Many of these chromosomes are described in U.S. Patent 3,567,605, U.S. Patent 4,826,977, U.S. Patent 5,066,818, U.S. Patent 5,238,931, U.S. Patent 5,272,132, U.S. Patent 5,384,077, U.S. Patent 5,466,398, U.S. Patent 5,552,090, US Pat. No. 5,565,146, US Pat. No. 5,573,712 and US Pat. No. 5,578,252.

Other groups of photochromic materials contemplated for use in the coatings of the present invention include materials having a maximum absorption in the visible range of 400 to 500 nanometers and other maximum absorption in the visible range of 500 to 700 nanometers. Can be mentioned. Examples of such materials include specific benzopyran compounds having substituents at two positions of the pyran ring, including dibenzo-conjugated 5-membered heterocyclic compounds and substituted or unsubstituted heterocyclic rings, for example benzopyrans. And pyran rings including benzothieno or benzofuran rings conjugated to benzene moieties. Such materials are disclosed in US Pat. No. 5,429,774, US Pat. No. 5,514,817, US Pat. No. 5,552,091 and WO 96/14596. Other photochromic compounds and materials usable in coatings include mercury ditizonates such as in US Pat. No. 3,361,706. Fulzides and fuzamides as described in US Pat. No. 4,931,220, paragraphs 5 to 21 of paragraph 38 can be used.

In addition to photochromic materials, thermochromic materials can be used. The material may be a material that exhibits changes in physical properties, such as absorbance, reflectance and refractive index, as a result of thermodynamic state changes, such as between semiconductor and metal states. Thermochromic materials of this type include certain vanadium oxides and titanium oxides, which exhibit relatively low absorbance in the semiconductor state but high absorbance and high reflectivity in the metal state. The thermodynamic transition between the semiconductor and metal states is reversible and the transition proceeds rapidly so that thin films of these materials are available. In the present invention, other suitable thermochromic materials are known thermochromic dyes, such as thermochromic liquid crystals, electron donating chromophoric organic compounds, as described in US Pat. No. 4,028,118 and US Pat. No. 4,732,810. It contains a thermochromic substance containing the aforementioned components in a three-component system or resinous solid solution composed of a color developer and a compound inducing color expression between the two components described above. The above-mentioned materials exhibit one state before and after the color change in the normal temperature range, and the other state exists when heating or cooling is applied, and when the heating or cooling is terminated, the state in the normal temperature range Recover.

Photochromic compounds of coatings, such as polyurethane coatings, are described in German Republic Patent No. 116,520, European Patent Application No. 0 146 136, US Patent No. 4,889,413, Japanese Patent Application No. 3-269507 and Japanese Patent Application No. 5-28753. Initiated by. Other suitable polyurethanes usable in the coatings are compounds prepared by the reaction of an isocyanate or polyisocyanate component with an organic polyol component that can provide a polyurethane component having a Fischer microhardness of about 50 to 150 Newtons per square foot. to be. Such polyurethane reactants and reactions are known to those skilled in the art. For example, methods for producing polyurethanes are described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edtion, 1992, Vol. A21, pp 665-716. Polyurethanes are compounds having segments of soft blocks and hard blocks that give rise to Fischer microhardness values in the aforementioned ranges. The relative content of the components is usually expressed as the ratio of the effective number of reactive isocyanate groups to the effective number of reactive hydroxy groups, ie the equivalent of NCO: OH. Suitable examples of ratios include a ratio of NCO: OH of 1.0: 1.0, but the range of values may be 0.3: 1.0 to 3.0: 1.0. Free isocyanates are not stable because they react with water or compounds containing reactive hydrogen atoms, and therefore the NCO groups are preferably blocked with specifically selected organic compounds that make the isocyanate groups inert to the reaction of hydrogen atoms at room temperature. Suitable blocking compounds include volatile alcohols, epsilon-caprolactam or ketoxime compounds and compounds known to those skilled in the art. Isocyanate compounds may be aliphatic, aromatic or aralkyl isocyanates. Organic polyols useful for preparing polyurethanes may be polyacrylic polyols, polyester polyols and / or polyether polyols or polyoxyalkylene polyols or organic polyols such as aliphatic diols, triols and polyhydric alcohols. Also suitable are epoxy polyols, polyhydric polyvinyl alcohols, urethane polyols and any mixtures of such polyols. In addition, amide-containing polyols can be used.

The amount of photochromic material or thermochromic material present in the composition alone or in a mixture with the photochromic compound in a proportion is such that the coating composition to which the photochromic compound (s) is applied or incorporated will exhibit the desired final color. For example, when activated with unfiltered daylight, a substantial neutral color, such as a gray or brownish hue, is provided as the color of the activated photochromic compound, possibly using a color similar to that of the neutral, and using standard photochromic reaction assays. When tested at 95 ° F. after activation for minutes, the optical density (delta OD) is determined to vary by more than 0.4, indicating the desired intensity. Generally, the amount of photochromic material or thermochromic material incorporated into the coating composition may be 0.1 to 40% by weight based on the weight of the coating composition.

In addition, commercially available tints or other additives such as dyes and auxiliaries may be incorporated into the coating composition. Some of the latter may include rheology modifiers, labeling agents, surfactants, initiators, cure inhibitors, free radical scavengers and adhesion promoters. Other adjuvants include the UV absorbers and stabilizers disclosed in US Pat. No. 4,720,356 and US Pat. No. 5,391,327, such as hindered amine light stabilizers, asymmetric diaryloxalamides and similar stabilizers.

Transparent substrates such as lenses 27 and 29 can be made of transparent or glass, such as plastic, such as the polymerization product of CR-39 monomers commercially available from PPG Industries, Inc. Clearing bodies, such as in transparent lenses 27 and 29, are generally for any ophthalmic, such as thermoplastic polycarbonate-like polymers and copolymers, and thermosetting and thermoplastic organic polymeric materials such as homopolymers or copolymers of polyols (allyl carbonates). It can be made of glass and / or plastic material. In some aspects, the electro-optic cell may retain encapsulation material other than the second substrate in a spaced opposing arrangement, preferably in a matched arrangement. The encapsulating material may be a material that is more flexible than the substrate, enclosing or encapsulating the substrate rather than providing a support similar to or similar to the substrate.

Examples of organic polymeric materials that may be substrates for the coating compositions of the invention include (a) diacrylate or dimethacrylate compounds of formula (I), (b) diacrylate or dimethacrylate compounds of formula (II) And (c) a polymer prepared from a mixture of individual monomers or monomers selected from acrylate or methacrylate compounds having an epoxy group of formula III:

Where

R ₁ and R ₂ may be the same or different and are hydrogen or methyl,

A is methylene (CH ₂ ),

n is an integer from 1 to 20.

Where

D is CH ₂ CR ₁ CR ₂ ,

p is 1 to 50.

Where

R ₃ is hydrogen or methyl.

In the above formulas (I), (II) and (II), the same letters used for the definition of different substituents have the same meaning.

Examples of diacrylate or dimethacrylate compounds of formula (I) and (II) include butanediol dimethacrylate and poly (oxyalkylene dimethacrylate), such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and the like. ), For example, polyethylene glycol (600) dimethacrylate. Examples of acrylate or methacrylate compounds of formula III include glycidyl acrylate and glycidyl methacrylate.

Further examples of organic polymeric materials that may be coated with the photochromic / thermochromic coating compositions as described above include polymers, ie monomers of Formula I, Formula II and Formula III, such as bis (allyl carbonate) monomers, diiso Propenyl Benzene Monomer, Ethoxylated Bisphenol A Dimethacrylate Monomer, Ethylene Glycol Bismethacrylate Monomer, Poly (ethylene Glycol) bis Methacrylate Monomer, Ethoxylated Phenolic Bis Methacrylate Monomer, Alcoholized Polyhydric Alcohol Polyacrylate Monomers such as ethoxylated trimethylol propane triacrylate monomers, urethane acrylate monomers as described in US Pat. No. 5,373,033, monomers of vinylbenzene monomers and styrene as described in US Pat. No. 5,475,074, and their Homopolymers and copolymers of mixtures; Multifunctional, for example monofunctional, difunctional or multifunctional acrylate and / or methacrylate monomers, polymers of poly (C _1-12 alkyl methacrylates), ie homopolymers and copolymers such as poly (Methyl methacrylate), poly (alkoxylated phenol methacrylate), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride ), Poly (vinylidene chloride), polyurethane, thermoplastic polycarbonate, polyester, poly (ethylene terephthalate), polystyrene, poly (alphamethylstyrene), copoly (styrene-methyl methacrylate), copoly (styrene Acrylonitrile), polyvinyl butyral; And polymers of diallylidene pentaerythritol, ie homopolymers and copolymers, specifically polyol (allyl carbonate) monomers such as diethylene glycol bis (allyl carbonate) monomers such as diethylene glycol bis (allyl carbonate) And copolymers with acrylate monomers such as ethyl acrylate and butyl acrylate.

Blends of transparent copolymers and transparent polymers are also suitable as substrates. Preferably, the host material is a thermoplastic polycarbonate resin, such as carbonate-linked resins derived from bisphenol A and phosphrps available under the trade name of LEXAN; Polyesters such as those sold under the trade name of MYLAR; Poly (methyl methacrylate), for example a material commercially available under the trade name PLEXIGLAS; A polyol (allyl carbonate) monomer, specifically a polymerized product of diethylene glycol bis (allyl carbonate), which is marketed under the trade name CR-39, and a polyol (allyl carbonate), for example diethylene glycol bis (allyl carbonate); Polymerization of copolymers of other copolymerizable monomer materials, for example copolymers of vinyl acetate, for example copolymers of diethylene glycol bis (allyl carbonate 80-90% and vinyl acetate 10-20%, in particular bis (allyl) Carbonate) copolymers of 80 to 85% and vinyl acetate 15 to 20% and terminal diacrylate functional polyurethanes as described in US Pat. Nos. 4,360,653 and 4,994,208; and US Pat. Aliphatic urethanes with terminal allyl or acrylyl functional groups as described in US Pat. No. 5,200,483. Copolymer with poly (vinyl acetate), polyvinyl butyral, polyurethane, diethylene glycol dimethacrylate monomer, diisopropenyl benzene monomer, ethoxylated bisphenol A dimethacrylate monomer, ethylene glycol bismetha Polymers of a component selected from the group consisting of acrylate monomers, poly (ethylene glycol) bismethacrylate monomers, ethoxylated phenol bismethacrylate monomers and ethoxylated trimethylol propane triacrylate monomers; cellulose acetate, cellulose propionate, Optically clear polymeric organic materials prepared from cellulose butyrate, cellulose acetate butyrate, thermoplastic polycarbonate, polystyrene, and copolymers of styrene and methyl methacrylate, vinyl acetate and acrylonitrile.

Suitable coatings, such as photochromic polyurethane coating compositions, are suitable for optical applications such as organic polymeric materials, for example optically clear polymerisation, ie optical components, for example plano and ophthalmology ophthalmology. Lens, window, transparent polymer film, automotive transparent material, for example, windshield, airplane transparent material, plastic sheet and the like. Such optically clear polymerizates have a refractive index of about 1.48 to about 1.75, such as about 1.495 to about 1.66. Specifically, optical components made of thermoplastic polycarbonate can be intended. The application of the photochromic polyurethane coating composition of the present invention to a "applique" polymer film was carried out using the method described in paragraphs 17 to 28 of paragraph 57 of US Pat. No. 5,198,267. Can be achieved.

The lenses 27 and 29, which are transparent substrates, are matched to the spectacle frames such that the lenses are generally matched to the spectacle frames, such as perforations 37 and 39. When mated to the spectacle frame, the lens can be connected by electrical connections 23 and / or 31. This connection provides an electric or magnetic field for the electro-optical components of the lenses 27 and 29 as fully described in FIG. 2.

In FIG. 2, the electro-optical device 29, which may be a transparent lens or a variable transparent lens, has conductive substrates 37 and 39 having two major surfaces, respectively. The substrates 37 and 39 are in a matched arrangement as shown in Figure 2 to form the space 41. For example, the space 41 may be 0.01 to 50 mm, more suitably 0.01 to 15 mm. Maintain the distance of the range. The space 41 contains a polymer-electrolyte or variable electro-optical converting material 43 for electrochromic electro-optic cells useful with photochromic and / or thermochromic materials as described above. For the substrate 37, which may be any of the aforementioned substrates, the major surface facing the other conductive substrate 39 may have one or more electrochromic layers 45. Various known electrochromic materials for layer 45 include molybdenum (MoO ₃ ), tungsten (WO ₃ ), vanadium (V ₂ O ₅ ), niobium (Nb ₂ O ₅ ), titanium (TiO ₂ ), chromium ( Cr ₂ O ₃ ), oxides of praseodymium (PRO ₂ ) and ruthenium (RuO ₂ ), such as compounds of tungsten oxide and tungsten, and tungsten oxide is preferred. In addition, triple metal oxides and tungsten bronzes, such as Mo _1-y W _y O ₃ , H _x WO ₃ , H _x MoO ₃ , K _x WO ₃ , and Na _x WO ₃ , where x and y are less than 1 Im) can be used. The major surface of the conductive substrate 39 facing the conductive substrate 37 has a counter electrode layer 47 known to those skilled in the art, for example iridium oxide or Prussian Blue. A space 41 holding the convertible material or polymer electrolyte 43 may be sealed between the two conductive substrates 37 and 39 by stacking or sealing or sealant 49A and 49B. The electrochromic cell also has bus bars 51 and 53 to provide current to the electrochromic layer and the counter electrode layer, respectively.

In the case of producing an electrochromic device, the substrate is preferably coated as part of layer 47 with an electrochromic film, depositing an electroconductive film thereon. Electroconductive and electrochromic films can be present in substantial portions of the surface of the substrate and the encapsulant material. This substantial part is part of the substrate and encapsulation material that can make the electro-optical variable transmissive component useful as a product. For example, portions of the substrate and encapsulant material present in the frame do not require such a film, but such uncoated portions may be masked to avoid coating or remove the film. Preferably, the film is present in a matched opposing arrangement of the electro-optical cells of the invention on the entire major surface of the substrate and / or the encapsulant material. The electroconductive film can be any known in the art, used as an electroconductive film in electrochromic devices. Such films are transparent films of metals or metal oxides, for example fluorine doped tin oxide or tin toped indium oxide (commonly referred to as ITO (indium / tin oxide)), preferably indium to tin ratio of about 90 It may be ITO having a weight ratio of: 10. Other materials, such as antimony-doped tin oxide and aluminum doped zinc oxide, can be used as the electroconductive film. Suitable sheet resistance for such films can range from 10 to 30 ohms per square foot. Suitable thicknesses for the electrically conductive film can be from about 1300 to about 4000 mm 3, for example 2000 to 4000 mm 3. The electrically conductive film can be deposited by various methods known in the art, so long as it does not adversely affect the substrate. Although high temperature pyrolysis methods can be used to deposit electrically conductive films on glass, these methods are generally not suitable for low melting polymer substrates. Suitable methods for depositing electrically conductive films, such as ITO, on polymeric substrates are described, for example, in US Pat. No. 4,851,095, US Pat. No. 5,225,057 and WO Publication No. 96/06203 (European Patent 776383). DC magnetron reactive sputtering (MSVP), such as direct current (DC) sputtering, for example the MetaMode sputtering system, which is the high deposition rate and low temperature process described. Coating of vacuum webs with cooling drums is another method of coating ITO on plastic substrates. Using this technique, an ITO film having at least 80% visible light transmittance and sheet resistance per 18-20 ohms / square foot can be prepared at about 20 ° C.

In addition, abrasion improving polymer primers are disposed at the interface of the substrate and the electroconductive film to assist in preventing residues of the substrate and the electroconductive film and / or cracking of the substrate and the electroconductive film for improved environments. Improve the adhesion of the electroconductive film to the surface of the plastic substrate for durability and long time cycling (coloration / bleaching cycle). Copolymers of acrylic acid and substituted acrylates such as cyanoethyl acrylate, hydroxyethyl acrylate, methyl methacrylate and mixtures of such substituted acrylates can be used. Application and curing of the primer may be performed as described in US Pat. No. 5,618,390.

A transparent electrochromic device is manufactured using a pair of transparent substrates coated with a primed electroconductive film. Preferably, the electrochromic film is deposited on the electroconductive film of one plastic substrate and the complementary electrochromic or counter electrode film is deposited on the electroconductive film of the other plastic substrate. Tungsten oxide may be deposited on the substrate by thermal evaporation of tungsten oxide, but it is preferred to deposit it by direct current (DC) magnetron sputtering of tungsten under high total gas pressure (greater than 20 mTorr) in a rare gas / oxygen atmosphere. The counter substrate also has a counter electrode or electrochromic layer coating on the electroconductive film in addition to the primed layer. This additional film may be one of nitrogen-containing iridium oxides as disclosed in US Pat. No. 5,618,390.

In one embodiment, the structure of the electrochromic cell 29 has three electrodes, namely working electrode WE, reference electrode RE and counter electrode CE. The working electrode may be a nitrogen-containing iridium oxide film, the reference electrode may be a standard calomel electrode (SCE), and the counter electrode may be a platinum foil having an area of 25 cm ² . Using potentiostatic conditions with applied voltages in the range of -0.5 to -0.1 V compared to standard caramel electrodes, the amount of charge inserted and removed is about 13 to 40 mC / cm ² . In addition, the electrochemical reduction can be performed under constant current conditions, including an applied current of about 1.5 x 10 ^-3 A and a voltage limit set to 1.5 V. The amount of charge inserted and removed under these conditions is about 23 mC / cm ² . The charge can be measured using a photometer wound in series with WE. The accumulated charge may range from about 1 to 40, preferably from 15 to 29, more preferably from 20 to 29 mC / cm ² .

After priming the two substrates, they are coated with an electroconductive and electrochromic or counter electrode film as needed, and the pair of substrates are assembled to form a cell having an electrochromic film in a frontal relationship. Cell 29 can be made by placing a preformed sheet of ion-conducting polymer between two half cells and stacking the resulting assembly in an autoclave. An ion-conductive material, preferably an ion-conductive polymer layer, combines with both coated surfaces to form a laminated article.

Also useful for such cells are ion-conducting polymer electrolytes which are proton-conducting polymers. Pre-formed homopolymers of 2-acrylamido-2-methylpropanesulfonic acid (AMPS® from Lubrizol) and copolymers of AMPS materials with various monomers can be laminated between substrates It may be used in the form of a sheet or in the form of a liquid reaction mixture of monomers which is cast and cured in place. Suitable proton-conducting polymer electrolytes according to the invention are copolymers of AMPS material with N, N-dimethylacrylamide (DMA), which are preferably cast and cured in place. Suitable examples of copolymers of AMPS and DMS are those prepared from AMPS and DMA monomers in molar ratios of about 1: 3 to 1: 2. The thickness of the polymer electrolyte may range from about 0.001 to about 0.025 inches (0.254 to 0.625 mm), more suitably 0.005 to 0.015 inches (0.127 to 0.381 mm) or as described in US Pat. No. 5,327,281. The AMPS / DMA copolymer proton-conducting electrolyte is preferably cast in place as a monomer solution in 1-methyl-2-pyrrolidinone (NMP) and water. The monomer solution comprises a photoinitiator that polymerizes the monomer upon exposure to actinic radiation, preferably ultraviolet (UV) radiation. Preferred UV initiators include benzoin, methyl ether and diethoxyacetophenone. The monomer solution was held in place by a commercially available sealant such as Torr Seal (trademark) from Varian Vacuum Products Teflon (0.005 to 0.025 inch (0.381 to 0.508 mm) held in place. TEFLON®) can be injected between two separate electroconductive and electrochromic coated substrates assembled with spacers 49A and 49B. Curved lenses are typically about 70 mm in diameter and 1 to 2 mm thick. In the case of a pair of curved lens substrates, the monomer solution can be formed into a thin film between the lens substrates by injecting a monomer solution onto the concave surface of one lens substrate and placing the convex surface of the other lens substrate in contact with the monomer solution. Exposure to ultraviolet light sufficient to cure the polymer electrolyte is typically about 30 minutes for mercury lamps and about 1 to 3 minutes for xenon lamps. In addition to the ion-conducting polymer electrolyte, other materials may also be used, for example hydrogen uranilphosphate or polyethylene oxide / LiCl0 ₄ . Further, LiNbO ₃ , LiBO ₃ , LiTaO ₃ , LiF, Ta ₂ O ₅ , Na ₂ AlF ₆ , Sb ₂ O ₅ nH ₂ O + Sb ₂ O ₃ , Na ₂ O × 11 Al ₂ O ₃ , MgF ₂ Inorganic films such as, ZrO ₂ , Nb ₂ O ₅ and Al ₂ O ₃ can be used as the electrolyte material. The electrochromic lens obtained has a meaningless haze (0.3 to 0.4%) and is generally free of cracks. The electrical connection to the electrochromic device is preferably made using an electrically conductive bus bar. The light transmittance of the lens at 550 nm is typically at least about 75% in bleached state and at least about 10% in dark state, in the voltage range of about +1.5 to -1.5 V for charges in the range of about 23 to 29 mC / cm ^2. Can be. The charge capacity of such films can range from less than 3 mC / cm ^{2 to more} than 30 mC / cm ² . For electrochromic products other than glasses, the transmittance in the bleached state may be lower and the transmittance in the dark state may be higher or lower.

The bus bars 51 and 53 may be powered by a power source 33 which is a battery of the eyeglass frame, or may be supplied from a power source in an automobile or on an automobile while appropriately adjusting the voltage and amperage of the power source. The power source from the motor vehicle may be one or more solar cells located on an automotive battery and / or motor vehicle, for example in a windshield, in which the current and voltage are appropriately regulated. Power is controlled by the electronic circuit 55 for electrochromic or liquid crystal manipulation as described later. The circuit 55 can be functionally controlled through a connection at the port 25 as shown in FIG. 1, along with the electrical connections 31 and 32. Both the power source and the electronic circuit for controlling the electrochromic cell may be present in the side member 15 or 17 of the spectacles of FIG. 1. Such electrochromic cells are described in US patent application Ser. No. 08 / 970,031, filed Nov. 13, 1997 for "Suspension Lamination Method and Device," and also in PCT Patent Publication. It can be prepared by the suspension lamination method which is also the subject of WO 97/43089.

The electrochromic cell, shown as a variant in the solid state in FIG. 2, is a stack of two substrates sandwiching a polymer-electrolyte in space 41. 3 shows another solid state variant of an electrochromic cell having a complementary thin film using a thin film stack on a substrate. One or the other electrode in FIG. 2 or 3 may be pre-charged by the insert-extraction ion J + of Scheme 1 below for cycling.

_{M n O m · y H 2} O + X e- + X j + ⇔ J x M n O m · H 2 O

In the reaction scheme, the right side represents the dark state and the left side represents the bright state. The scheme is for inorganic oxide films that exhibit cathodic coloring by reversible double insertion of electrons and monovalent charge-compensating ions. In Scheme 1, M is a polyvalent cation of a film having a valence of 2 m divided by n. m and n are both nominal integers. The ions inserted while forming the color center are J +. Typically X is greater than 0 and less than 0.5, and as X approaches 0.5, the film reversibly changes from the transparent transmission state in normal illumination to even darker shades of the same hue. In FIG. 3, the conductive substrate 39 may have a tungsten oxide coating 45 electrically connected to the bus bar 53. The tungsten oxide film is in contact with the electrolyte film 57. In contact with the film 57 is the counter electrode film 47, and in contact with the counter electrode film is the indium tin oxide coating 59. Coating 59 is a thin film coating that can be deposited by any thin film technique known to those skilled in the art, like other coatings in electrochromic cells. Coating 59 has a bus bar 51 that carries power to the electrode film.

Suitable examples of power and control components are micro-electronics that are useful for lightweight battery-operated electrochromic (EC) glasses. These components are hybrid, power-sharing lithium-type primary cells and sealed lead-acid that can provide the low energy, high current (pulse) drain requirements of microelectronics, eg, convertible electrochromic ("EC") lenses. It may include a secondary cell. The switch-mode power supply controller regulates the power-sharing load on the hybrid battery system such that the secondary cell is charged by the primary cell. The system can meet the short term pulse drain requirement of converting the EC lens from light to completely dark at an acceptable speed as fast as a long term operating life of about 1500 cycles. Suitable lead-acid batteries have a long, uniform, rectangular cross section and can provide a capacity of 20 mA-hr or more. Suitable lead-acid batteries also have a long, uniform, rectangular cross section and can provide a capacity of 180 mA-hr or more, all of which have a very small volume compatible with one or more volume-limited spaces such as the side members 15 and 17. . Lithium-type and lead-acid batteries may have approximately the same form factor and volume to symmetrically place within the voids in either of these members. Dual cell battery structures can be used with flexible circuits that form one or more frame mounted transmittance switches. The controller electronics can be a microcontroller that fits into a micro void formed in the lens holder at the bridge. Finally, external battery-powered battery charger cases and circuits can also be used with EC glasses powered by dual batteries. Such power sources and controllers are those as described in US Pat. Nos. 5,455,637 and 5,455,638.

The electro-optical cells of FIGS. 2 and 3 as described above for electrochromic cells with photochromic coatings can be modified as another type of electro-optical device. Such a modified form is an electro-optical device having a liquid crystal cell, wherein the liquid crystal material has photochromic, thermochromic and / or dichroic materials. In this embodiment of the invention, a cell similar to one of the cells of FIGS. 2 and 3 has a liquid crystal material, compound or polymer in which photochromic, thermochromic and / or dichroic substances are dispersed. The latter can be formed by dispersing smectic, nematic and / or lyotropic liquid crystals, etc. in the polymer matrix or using liquid crystal polymers. These liquid crystal containing materials will be the convertible material 43 in the space 41 rather than the polymer electrolyte discussed above. The material 43 of the space 41 may have, in addition to the liquid crystal material, one or more dichroic dyes and / or thermochromic materials in a guest-host relationship with the liquid crystal. Alternatively, the material 43 may have one or more photochromic materials. This is facilitated by a change in the orientation order of the liquid crystal molecules that varies between homeotropic or uniform and irregular alignment states by heat, electric and / or magnetic fields. For the electro-optical device of FIGS. 2 and 3, no tungsten oxide or counter electrode coating, film or layer would be needed. The substrate or substrates will be conductive in the composition and / or presence of one or more conductive coatings, layers or films on the substrate. Also, in the case of liquid crystals, the counter electrode coatings or layers of FIGS. 2 and 3 may be one or more polyimide coatings, layers or films, or one or more other similar alignment coatings to orient the liquid crystals.

Suitable examples of photochromic and thermochromic materials are those as described above for electrochromic cells. Suitable examples of dichroic materials are dichroic dyes useful as chromogenic materials either alone or in mixtures thereof or in the form of photochromic and / or thermochromic materials. These materials have the ability to absorb light of a particular polarization when molecules are aligned in the liquid crystal material. Dichroic dyes allow the material to absorb only one polarization of light when used in a film or other material that mainly scatters only one polarization of light. Suitable dichroic dyes include Congo Red (sodium diphenyl). -Bis-α-naphthylamine sulfonate), methylene blue, stilbene dye (color index (CI) = 620), and 1,1'-diethyl-2,2'-cyanine chloride (CI = 374 (orange) ) Or CI = 518 (blue)). The properties of these dyes and their preparation are described in Colloid Chemistry (1946) of E. H. Land. These dyes have significant dichroism in polyvinyl alcohol and less dichroism in cellulose. Other suitable dyes include Kirk Othmer Encyclopedia of Chemical Technology, Vol. 8, pp. 652-661 (4th Ed. 1993) and references cited therein, including those listed with their properties and methods of preparation.

One or more chromophoric components with or without dichroic dye may be used in the liquid crystal material in an amount of generally 0.05 to 15% by weight, preferably 0.5 to 5% by weight, based on the amount of the liquid crystal material.

Other useful guest compounds include aromatic compounds such as mono-substituted benzene derivatives, di-substituted benzene derivatives, tri-substituted benzene derivatives, tetra-substituted benzene derivatives, mono-substituted biphenyl derivatives, di- Substituted biphenyl derivatives, tri-substituted biphenyl derivatives, tetra-substituted biphenyl derivatives, mono-substituted naphthalene derivatives, di-substituted naphthalene derivatives, tri-substituted naphthalene derivatives, tetra-substituted naphthalene derivatives, Mono-substituted pyridine derivatives, di-substituted pyridine derivatives, tri-substituted pyridine derivatives, tetra-substituted pyridine derivatives, mono-substituted pyrazine derivatives, di-substituted pyrazine derivatives, tri-substituted pyrazine derivatives, tetra -Substituted pyrazine derivatives, mono-substituted pyrimidine derivatives, di-substituted pyrimidine derivatives, tri-substituted pyrimidine derivatives, tetra-substituted pyrimidine derivatives, Mono-substituted azulene derivatives, di-substituted azulene derivatives, tri-substituted azulene derivatives, tetra-substituted azulene derivatives, mono-substituted pyrrole derivatives, di-substituted pyrrole derivatives, tri-substituted Pyrrole derivatives, tetra-substituted pyrrole derivatives, mono-substituted thiophene derivatives, di-substituted thiophene derivatives, tri-substituted thiophene derivatives, tetra-substituted thiophene derivatives, mono-substituted furan derivatives, di -Substituted furan derivatives, tri-substituted furan derivatives, tetra-substituted furan derivatives, mono-substituted pyryllium salt derivatives, di-substituted pyryllium salt derivatives, tri-substituted pyryllium salt derivatives, tetra-substituted pyryllium salts Derivatives, mono-substituted quinoline derivatives, di-substituted quinoline derivatives, tri-substituted quinoline derivatives, tetra-substituted quinoline derivatives, mono-substituted pyridazine derivatives, di-substituted pyridazine derivatives, tri-substituted blood Ridazine derivatives, tetra-substituted pyridazine derivatives, mono-substituted triazine derivatives, di-substituted triazine derivatives, tri-substituted triazine derivatives, tetra-substituted triazine derivatives, mono-substituted tetraazine derivatives Derivatives, di-substituted tetrazine derivatives, tri-substituted tetrazine derivatives, tetra-substituted tetrazine derivatives, mono-substituted anthracene derivatives, di-substituted anthracene derivatives, tri-substituted anthracene derivatives, or tetra- Substituted anthracene derivatives are included. Examples of electron donating groups attached to the guest compound as discussed above include amino groups, alkyl groups (methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, sec-butyl, n-octyl, t-octyl , n-hexyl, cyclohexyl, etc.), alkoxy group (methoxy, ethoxy, propoxy, butoxy etc.), alkylamino group (N-methylamino, N-ethylamino, N-propylamino, N-butylamino, etc.) ), Hydroxyalkylamino group (N-hydroxymethylamino, N- (2-hydroxyethyl) amino, N- (2-hydroxypropyl) amino, N- (3-hydroxypropyl) amino, N- ( 4-hydroxypropyl) amino, etc.), dialkylamino group (N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-dibutylamino, N-methyl-N -Ethylamino, N-methyl-N-propylamino, etc.), hydroxyalkyl-alkylamino group (N-hydroxymethyl-N-methylamino, N-hydroxymethyl-N-ethylamino, N-hydroxymethyl- N-Pro Amino, N- (2-hydroxyethyl) -N-methylamino, N- (2-hydroxyethyl) -N-ethylamino, N- (3-hydroxypropyl) -N-methylamino, N- ( 2-hydroxypropyl) -N-ethylamino, N- (4-hydroxybutyl) -N-butylamino and the like), dihydroxyalkylamino group (N, N-dihydroxymethylamino, N, N-di -(2-hydroxyethyl) amino, N, N-di- (2-hydroxypropyl) amino, N, N-di- (3-hydroxypropyl) amino, N-hydroxymethyl-N- (2 -Hydroxyethyl) amino, etc.), a mercapto group and a hydroxy group. Meanwhile, examples of the electron attracting group may include a nitro group, a cyano group, a halogen atom (fluorine, chlorine, bromine), a trifluoromethyl group, a carboxyl group, a carbonyl ester group, a carbonyl group, and a sulfonyl group. Examples of the bulk of guest compounds that may be used are as follows: 3-nitro-4-hydroxy-3-sodiumcarbonyl-azobenzene, 4-chloro-2-phenylquinazolin, aminoadipic acid, aminoanthracene, amino Biphenyl, 2-amino-5-bromobenzoic acid, 1-amino-5-bromobenzoic acid, 1-amino-4-bromonaphthalene, 2-amino-5-bromopyridine, amino-chlorobenzenesulfonic acid, 2-Amino-4-chlorobenzoic acid, 2-amino-5-chlorobenzoic acid, 3-amino-4-chlorobenzoic acid, 4-amino-2-chlorobenzoic acid, 5-amino-2-chlorobenzoic acid, 2-amino-5 -Chlorobenzonitrile, 2-amino-5-chlorobenzophenone, amino-chlorobenzotrifluoride, 3-amino-6-chloromethyl-2-pyrazinecarbonitrile-4oxide, 2-amino-4-chloro-6 -Methylpyridine, 1-amino-4-chloronaphthalene, 2-amino-3-chloro-1,4-naphthoquinone, 2-amino-4-chloro-5-nitrophenol, 2-amino-4-chloro- 5-nitrotoluene, 2-amino-4-chloro-4-phenol, 2-amino-5-chloropurine, 2-amino-5-chloropyridine, 3-amino-2-chloropyridine, 5-amino-2-chloropyridine, aminocream Sen, 2-amino-p-cresol, 3-amino-p-cresol, 4-amino-p-cresol, 4-amino-m-cresol, 6-amino-m-cresol, 3-amino Crotononitrile, 6-amino-3-cyano-2,4-dimethylpyridine, 5-amino-6-cyano-2-pyrazinyl acetate, 4- [N- (2-methyl-3-cyano- 5-pyrazinylmethyl) amino] -benzoic acid, 3,5-dinitroaniline, 4- (2,4-dinitroanilino) phenol, 2,4-dinitroanisole, 2,4-dinitrobenzaldehyde , 2,6-dinitrobenzaldehyde, 3,5-dinitrobenzamide, 1,2-dinitrobenzene, 1,3-dinitrobenzene, 3,4-dinitrobenzoic acid, 3,5-dinitrobenzoic acid , 3,5-dinitrobenzonitrile, 2,6-dinitro-p-cresol, 2,6-dinitro-o-cresol, 2,4-dinitrodiphenylamine, dinitrodurene, 2, 4-dinitro-N-ethyl Nilin, 2,7-dinitrofluorenone, 2,4-dinitrofluorobenzene, 1,3-dinitronaphthalene, 1,5-dinitronaphthalene, 1,8-dinitronaphthalene, 2,4-di Nitrophenol, 2,5-dinitrophenol, 2,4-dinitrophenylhydrazine, 3,5-dinitrosalicylic acid, 2,3-dinitrotoluene, 2,4-dinitrotoluene, 2,6-dinitro Toluene, 3,4-dinitrotoluene, 9-nitroanthracene, 4-nitroanthranylic acid, 2-amino-5-trifluoromethyl-1,3,4-thiazole, 7-amino-4- (trifluor Romethyl) -coumarin, 9-cyanoanthracene, 3-cyano-4,6-dimethyl-2-hydroxypyridine, 5-cyanoindole, 2-cyano-6-methoxybenzothiazole, 9- Cyanophenanthrene, cyanuric chloride, 1,2-diaminoanthraquinone, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,4-diaminobenzophenone, 2,4-diamino- 6- (hydroxymethyl) pteridine, 2,6-diamino-4-nitrotoluene, 2,3-dicyanohydroquinone, 2,6- Nitroaniline, 2-amino-5-iodobenzoic acid, aminomethoxybenzoic acid, 2-amino-4-methoxybenzothiazole, 2-amino-6-methoxybenzothiazole, 5-amino-2-methoxy Phenol, 5-amino-2-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 4- Amino-3-methylbenzoic acid, 2-amino-4-methylbenzophenone, 7-amino-4-methylcoumarin, (100) 3-amino-5-methylcoumarin, (101) 7-amino-4-methyl-1 , 8-naphthylidene-2-ol. Suitable guest compounds include 4-aminoacetophenone, 4-aminobenzoic acid, 4-amino-α, α, α-trifluorotoluene, 4-aminobenzonitrile, 4-aminocinnamic acid, 4-aminophenol, 4- Bromotoluene, 4-bromoaniline, 4-bromoanisole, 4-bromobenzaldehyde, 4-bromobenzonitrile, 4-chlorobenzonitrile, 4-chlorotoluene, 4-chloroaniline, 4-chloro Anisole, 4-chlorobenzaldehyde, 4-chlorobenzonitrile, 4-cyanobenzaldehyde, α-cyano-4-hydroxycinnamic acid, 4-cyanophenol, 4-cyanopyridine-N-oxide, 4-fluorotoluene, 4-fluoroaniline, 4-fluoroanisole, 4-fluorobenzaldehyde, 4-fluorobenzonitrile, 4-nitroaniline, 4-nitrobenzamide, 4-nitrobenzoic acid, 4 -Nitrobenzyl alcohol, 4-nitrocinnamaldehyde, 4-nitrocinnamic acid, 4-nitrophenol, 4-nitrophenetol, 4-nitrophenyl acetate, 4-ni Phenylhydrazine, 4-nitrophenyl isocyanate-4-nitrotoluene 4-Nitro include toluene -α, α, α- trifluoromethyl.

Examples of liquid crystal compounds for use in the present invention include compounds represented by the following general formula (IV):

X-A-R-B-Y

Wherein A and B are aromatic or aliphatic hydrocarbon six-membered rings or substituted six-membered rings, or nitrogen or oxygen-containing six-membered rings (the oxygen or nitrogen being in the ring with carbon) and mixtures of any of these Can; R is a single bond between two rings A and B, (-C≡C-) (which represents a triple bonded carbon), CH ₂ CH ₂ or COO. In Formula (IV), X and Y are alkyl group, alkoxy group, alkoxyalkyl group, alkylphenyl group, alkoxyalkylphenyl group, alkoxyphenyl group, alkylcyclohexyl group, alkoxyalkylcyclohexyl group, alkylcyclohexylphenyl group, cyanophenyl group, cyano group , Halogen atom, fluoromethyl group, fluoromethoxy group, alkylphenylalkyl group, alkoxyphenylalkyl group, alkylcyclohexylalkyl group, alkoxyalkoxycyclohexylalkyl group, alkoxyphenylalkyl group or alkylcyclohexylphenylalkyl group, wherein the alkyl chain and alkoxy The chains may each have an optically active site therein; The substituent for the ring may be a halogen atom or a cyano group in addition to the hydrogen atom. Phenyl or phenoxy groups which may be contained in X and Y may be substituted with one or more substituents selected from the group consisting of cyano groups and halogen atoms such as fluorine and chlorine. The phenyl group contained in formula IV may be substituted with up to 4 substituents each selected from the group consisting of halogen atoms (eg fluorine and chlorine) and cyano groups.

In addition, fluorinated liquid crystal compounds having one or more fluorine atoms or fluorinated groups such as --F, --CF ₃ and --OCF ₃ may be used in place of conventional cyano-containing liquid crystal compounds.

The liquid crystal composition may also include various additives including ultraviolet absorbers and antioxidants.

Also useful as a guest host composition for the space 41 in FIGS. 2 and 3 is a solid solution of an organic guest compound having an electron donating group or an electron attracting group. The organic guest compound may be contained in a nonlinear optical material, such as a form oriented through orientation under melting by application of a DC electric or magnetic field. An example of such a guest compound is a para-di-substituted benzene derivative in which one substituent is an electron donating group and the other substituent in the para position relative to the first substituent is an electron attracting group.

Other suitable examples described in the literature include polymer liquid crystals as hosts and polar molecules as guests and polymers as indicated in Meredity, GR et al. (Macromolecules, 15, 1385 (1982)). Aligning the said polar molecule | numerator is used using the electric charge orientation of a liquid crystal.

In addition, examples of aligning polar molecules in an amorphous polymer include forming a polymethyl methacrylate resin in which an azo colorant is dissolved into a film, heating to a temperature above the glass transition point, and supplying a voltage to align the azo colorant. There is further cooling and fixation of the structure (Singer, KD, Shon, JE and Lalama, SJ, Appl. Phys, Lett. 49, p. 248 (1986)). ]). In addition, mixtures of nonlinear optical-reactive organic compounds in the polymer may be useful to obtain polymeric nonlinear optical materials (US Pat. No. 4,428,873 and JP-1982-45519). Nonlinear optical materials that contain acrylamide resins known in Japanese Patent Laid-Open No. 1987-84139 as host polymers and which contain nonlinear optical-reactive organic compounds as guests are useful. It is also useful to obtain crystal growth of a compound having an asymmetric center in the polyoxyalkylene matrix as in Japanese Patent Laid-Open No. 1987-246962. Furthermore, polyoxyalkylenes alone or polyoxyalkylenes and other polymers such as poly (methyl methacrylate), poly (vinyl acetate), polystyrene, poly (vinylidene fluoride), poly (vinylidene cya Amide-vinyl acetate), poly (vinylidene fluoride-tetrafluoroethylene), poly (vinylidene cyanide-vinyl propionate), poly (vinylidene cyanide-vinyl benzoate), poly (vinyl alcohol), Polyoxyalkylene matrices composed of mixtures with polyamides and the like, polymeric liquid crystals, liquid crystals, and inorganic compound powders can be used.

The electro-optical product is constructed when the liquid crystal composition with the color developer is a switchable material 43 located in the space 41 of FIGS. 2 and 3.

The transparent electrode as the coating, layer or film 45 and 47 of FIGS. 2 and 3 is transparent on a substrate which is a plate or glass plate of any of a variety of synthetic resins including acrylic resins, polycarbonate resins and epoxy resins as described above. It can manufacture by forming an electrode layer. The transparent electrode layer may be made of, for example, a metal oxide such as indium oxide, indium oxide-tin (ITO), or tin oxide. The surface of the transparent electrode layer which comes into contact with the liquid crystal can be aligned as required.

In the cell apparatus of Figs. 2 and 3, there is a difference that occurs as a result of using an approach by liquid crystal rather than an approach by electrochromic. The difference is that the electrode layer, which is preferably transparent and located on the two substrates or on the substrate and encapsulation layer, has an aligned electrode surface before adding the liquid crystal to the space 41.

The alignment treatment is, for example, octadecyldimethyl [3- (trimethyloxysilyl) propyl] ammonium chloride, hexadecyltrimethylammonium bromide or the like in the case of vertical alignment, polyimide or cotton in the case of parallel alignment. , By rubbing with an absorbent side or the like, or by depositing SiO _x with a small tilt angle. This sorting technique can be used suitably. Another alignment method is disclosed and described in a co-pending patent application of the name “Electrodes for Liquid Crystal Cells” of the invention filed identically to this application by Patricia Ruzakowski Athey. Another alignment method, for example, a liquid crystal compound containing a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound is aligned in a liquid crystal state, and then irradiated with an energy ray such as ultraviolet light while the material is kept in a liquid crystal state. You can also use

As another method for semi-permanently fixing the uniform orientation of the mesogenic core of the liquid crystal, a method involving the use of a liquid crystal polymer compound is already known. In more detail, this method applies a solution of liquid crystalline polymer exhibiting thermotropic liquid crystalline to a substrate, treating the substrate to align the liquid crystalline polymer, and then heating the material at a temperature at which the liquid crystalline polymer compound exhibits a liquid crystal phase. To obtain a mesogenic core of the desired orientation of the liquid crystal polymer. In this way, the oriented polymer compound is kept in a free state to fix the desired orientation therein.

Several liquid crystal cells were constructed according to the following procedure for the materials shown in Table 1. The cells were made into various transparent devices and tested as shown in Table 1.

1. Cut the Sungate® 500 glass into 2 "x 2" pieces. Construct a liquid crystal cell using a pair of pieces. The Sungate 500 glass functions as an electrode for the device and also provides an alignment layer for the liquid crystal-dye mixture.

2. Clean Sungate 500 glass: Spray 50/50 (volume ratio) 2-propanol / deionized water on the Sungate 500 glass and wipe with Technicloth® (TEXWIPE) polyester / cellulose wiper Dries

3. Rub the conductive surface of the Sungate 500 glass: A conductive side of one of two pieces of Sungate 500 glass with a cotton pad (VWR Scientific) soaked in 2-propane and wrapped in an aluminum rod. Rub in one direction.

4. Spin coat the spacer material on the conductive side of one piece of Sungate 500 glass: dilute mixture of 8 micron glass fiber spacer material (EM Industries, Inc.) in 2-propanol To prepare. This mixture should appear blurred. Compressed nitrogen is used to blow off all dust from the conductive surface of the sungate glass before spin coating. Glass samples were mounted on a vacuum chuck of a spin coater (Headway Research, Inc.), followed by 5 glass drops of glass fiber spacer / 2-propanol mixture per glass area (in ² ). It is placed on the conductive side of. The spin coater is set to rotate at 1090 rpm for 21 seconds. A piece of Sungate 500 glass is removed from the spin coater.

5. Liquid Crystal Cell Assembly / Initial Sealing: Place two pieces of Sungate 500 glass (one with fiberglass spacers and one without) with the conductive side facing and the rubbing direction opposite 180 °. Offset about 1/4 "from a pair of opposing edges for electrical conduction and charging. The other pair of opposing edges should be evenly aligned. Secure the cell with two binder clips. UV-curable epoxy adhesive for initial sealing (Loctite® 349) is applied to the two horizontally aligned edges. The cell is passed through a high intensity UV reactor (RPC Industries) to cure the UV epoxy. Remove the binder clip when the epoxy has cured. This forms a cell with a fillable volume of about 1 to 3/4 "x 2" x 8 microns.

6. Prepare a liquid crystal / dichroic dye / photochromic dye mixture: E7 liquid crystal (EM Industries, Inc.) and G-472 blue dichroic dyes (Nippon, Kanko, Shikiso, Genkyuso (Nippon, Kankoh) , Shikiso, Kenkyusho)) are mixed in a glass bottle at the following weight percent: E7 liquid crystal 95 weight percent; 1 weight percent of G-472 blue dichroic dye; 4.0 weight% of 7-120 photochromic dye. The mixture is heated on a hotplate set at a temperature above the isotropic state of the E7 liquid crystal, ie 90 ° C., and occasionally stirred and stirred until all the dye particles are dissolved.

7. Charge the liquid crystal cell: Place the unfilled cell on a hotplate set at 90 ° C. (Thermolyne Mirak ^™ ). The cell should be placed on a hotplate so that it can be loaded dropwise along one of the unsealed edges. Pipette the warm liquid crystal / dichroic dye / photochromic dye mixture into a pipette and deposit a continuous line of the mixture along the open edge starting at one corner along the filling edge and up to the opposite corner. The device is charged when the preceding liquid crystal / dye mixture has moved across the unsealed opposing edge of the cell.

8. Cool the charged liquid crystal cell: Remove the cell from the hotplate and cool to room temperature. As the mixture cools, the E7 liquid crystal changes from the isotropic to the nematic state.

9. Final Seal of Liquid Crystal Device: Epoxy (Loctite 100CL) is applied to two unsealed edges for 5 minutes and cured. This completes the production of the guest-host liquid crystal device in which the photochromic dye is incorporated.

10. Electrical switching of the liquid crystal device: The liquid crystal device manufactured as described above is in a dark state when no electric field is supplied to the device (showing blue with low visible light transmittance (about 41% Lta) when viewed under fluorescent lighting). . When the electric field is supplied to such a liquid crystal device, the device is bleached (showing a higher visible light transmission (about 63% Lta) or light blue when viewed under fluorescent lighting). Although 0-6 VDC was initially used to switch these devices, it is desirable to switch all liquid crystal devices using 0-6 VAC to avoid any cell degradation that may be due to the use of DC voltage.

11. Photochromic Effect: The photochromic dye in the liquid crystal device is not activated by an electric field and is required to be exposed to UV rays in order to cause the photochromic reaction. UV rays are absorbed by the photochromic dye molecule, followed by a change in the chemical structure of the dye molecule resulting in a visible color change of the dye from almost colorless to dark blue (as seen in fluorescent lighting). When the liquid crystal device in the dark state is exposed to long wavelength UV rays for less than 1 minute, the device becomes much darker (in fluorescent lighting) with dark blue of low visible light transmittance value (not measured). When the long wavelength UV light source is removed, the device is bleached back to the transmittance value of the dark state cell within 1 minute. This photochromic effect has been reproduced many times with the same device.

12. The results of some liquid crystal cells are shown in Tables 1A, 1B and 1C below.

Table 1 shows a liquid crystal device incorporating a photochromic component, wherein SG500 is Sungate 500 commercially available from PPG Industries Inc. and IPA is isopropyl alcohol or 2-propanol.

code Board 1 Surface Treatment 1 LCD Dichroic dye Photochromic A SG500 50:50 (volume ratio) IPA: Sprayed with deionized water, wiped with a technical cloth wiper, and scrubbed 10 times in one direction with black velvet moistened with IPA. E7 - 7-120,0.1% B SG500 50:50 (volume ratio) IPA: Sprayed with deionized water, wiped with a technical cloth wiper, and scrubbed 10 times in one direction with black velvet moistened with IPA. E7 - 7-120,0.1% C SG500 50:50 (volume ratio) IPA: Sprayed with deionized water, wiped with a technical cloth wiper, and scrubbed 10 times in one direction with black velvet moistened with IPA. E7 Blue G-472 (Nippon 95-1), 0.8% 7-120,0.06% D SG500 50:50 (volume ratio) IPA: Sprayed with deionized water, wiped with a technical cloth wiper, and scrubbed 10 times in one direction with black velvet moistened with IPA. E7 Blue G-472 (Nippon 95-1), 0.8% 7-120,0.06% AA SG500 50:50 (volume ratio) IPA: Sprayed with deionized water, wiped with a technical cloth wiper, and scrubbed 10 times in one direction with black velvet moistened with IPA. E7 Blue G-472 (Nippon # 95-1), 1% 7-120,2% BB SG500 50:50 (volume ratio) IPA: Sprayed with deionized water, wiped with a technical cloth wiper, and scrubbed 10 times in one direction with black velvet moistened with IPA. E7 Purple G-471 (Nippon # 95-1), 1% 7-120,4% CC SG500 50:50 (volume ratio) IPA: Sprayed with deionized water, wiped with a technical cloth wiper, and scrubbed 10 times in one direction with black velvet moistened with IPA. E7 Purple G-471 (Nippon # 95-1), 1% 7-120,1.3% AAA SG500 50:50 (volume ratio) IPA: Sprayed with deionized water and wiped with a technical cloth wiper, reciprocated five times in one direction with a cotton pad soaked with IPA, and finally reciprocated five times in one direction with a dry cotton pad By cleaning E7 - 7-120,3.8% BBB SG500 50:50 (volume ratio) IPA: Sprayed with deionized water and wiped with a technical cloth wiper, reciprocated five times in one direction with a cotton pad soaked with IPA, and finally reciprocated five times in one direction with a dry cotton pad By cleaning E7 Blue G-472 (Nippon 95-1), 1.0% CCC SG500 50:50 (volume ratio) IPA: Sprayed with deionized water and wiped with a technical cloth wiper, reciprocated five times in one direction with a cotton pad soaked with IPA, and finally reciprocated five times in one direction with a dry cotton pad By cleaning E7 Blue G-472 (Nippon 95-1), 1.1% 7-120,3.9%

code Board 2 Surface treatment 2 Angle 1-2 (clockwise) Charging method Spacer (μm) % T change A SG500 Same as Example 1 180 capillary 8 - B SG500 Same as Example 1 180 capillary 8 - C SG500 Same as Example 1 180 capillary 8 - D SG500 Same as Example 1 180 capillary 8 - AA SG500 Same as Example 1 180 capillary 8 - BB SG500 Same as Example 1 180 capillary 8 - CC SG500 Same as Example 1 180 capillary 8 - AAA SG500 Same as Example 1 180 capillary 8 - BBB SG500 Same as Example 1 180 capillary 8 22 CCC SG500 Same as Example 1 180 capillary 8 -

code Board 1 Board 2 Remarks A One One Weak photochromic effect B One One Weak photochromic effect C One One Too bright in the dark, weak light effect D One One Too bright in the dark, weak light effect AA One One Significant photochromic effect BB One One Significant photochromic effect CC One One Significant photochromic effect AAA 2 2 Significant photo-coloring effect, no bubble during charging BBB 2 2 Bubbles during charging CCC 2 2 Significant photochromic effect, liquid crystal-dye mixture vacuum degassed for 5 minutes, no bubble during filling

Claims (13)

An electro-optical device having an optically active material for a variable transparent article, At least one transparent substrate having at least one major surface; One or more encapsulation materials matched to cover a substantial portion of the substrate in a spaced manner to form a space therebetween; At least one gap component having an electro-optical switchable material that occupies a space substantially covering the major surface of the opposing substrate, and combining at least one substrate and the encapsulant to form a space occupied by the gap component; At least one electrically conductive layer located on at least a substantial portion of the major surface that effectively opposes the gap component for the at least one substrate and the encapsulant; And One or more coatings on one side of the major surface of the one or more substrates, and an electro-optical cell having a colorant active component selected from among the electro-optical converting materials present as a gap component or as a guest material in a host material of the gap component. Electro-optical device. The method of claim 1, An electro-optical device having a colorimetric active component that is a guest material in a liquid crystal composition wherein the gap component is a host material and wherein the major surface and encapsulant of the substrate opposite the gap component are conductive. a) frame; b) at least one transparent substrate having at least one major surface; One or more encapsulation materials matched to cover a substantial portion of the substrate in a spaced manner to form a space therebetween; At least one gap component having a convertible guest material that occupies space substantially covering the major surface of the substrate opposite the encapsulant; A sealant that combines one or more substrates with the encapsulant to form a space occupied by the gap component; At least one electrically conductive layer located on at least a substantial portion of the major surface that effectively opposes the gap component for the at least one substrate and the encapsulant; And at least one coating on one side of the major surface of the at least one substrate and a chromophore active component selected from guest materials in the host material of the gap component and capable of converting visible light transmission. -Optical cell; c) one or more switches mounted to the frame and at least one operatively connected to the cell; And d) an electro-optical tunable transparent system comprising a power source for the cell and a switch comprising a controller and at least one battery for supplying current to the controller and through the switch associated with the cell. The method of claim 3, wherein Said transparent body is a lens for eyewear. The method of claim 3, wherein The transparent body is a window. The method of claim 3, wherein The transparent body is a sunshade band for a vehicle window. The method of claim 3, wherein The transparent body is a partition between the front and rear of the vehicle. The method of claim 3, wherein Wherein said optically active material is selected from photochromic and dichroic materials. The method of claim 3, wherein The encapsulant is the same as the substrate, such that the cells have two substrates matched with each other to form a space, wherein the substrate is selected from the crowd consisting of glass, transparent plastic and translucent plastic. The method of claim 3, wherein And wherein the gap component containing the convertible guest material is a liquid crystal material or mixture thereof having an optically active material selected from among photochromic, thermochromic, dichroic and mixtures of two or more thereof. The method of claim 3, wherein A power source, including the switching and cell controller, supported by the frame. The method of claim 3, wherein A system in which a controllerless power supply is supported by the frame and a controller circuit is connected to the frame. The method of claim 3, wherein A system in which a power source and a controller are electrically connected to a frame.