A method of manufacturing electrochromic devices and electrochromic device

 

The invention relates to the field of devices that change color under the influence of electric current, namely, the electrochromic device and method of its manufacture. Describes a method of manufacturing electrochromic devices containing at least two electrodes, at least one of which is optically transparent, thus hermetically closed space between the electrodes is filled electrochromic composition. Get the initial electrochromic composition in the form of electrochromic dispersed system containing at least a suspension and/or colloid, in this system the dispersion medium is an electrochromic solution containing a liquid solvent, the cathodic component and the anodic component and the dispersed phase is finely dispersed polymer, carry out deaeration initial electrochromic composition for the removal of dissolved oxygen and air, made with finely dispersed polymer, fill the enclosed space between the electrodes deaerated initial electrochromic composition, carry out the sealing of the closed space between the electrodes. It also describes the electrochromic device containing, for men what about between the electrodes hermetically closed and filled with the electrochromic composition, obtained in the above way. The technical result is to obtain electrochromic devices operating in conditions of prolonged maintenance of the painted condition, and also in terms of the effects of high operating voltage and polarity of the electrodes shown in the increase of the time preserving the uniformity of staining and discoloration, especially for electrochromic device with a large area of the working surface. 2 S. and 19 C.p. f-crystals, 2 Il.

The invention relates to the field of devices that change color under the influence of electric current, namely, electrochromic devices and their manufacturing techniques. Electrochromic devices are electrically controlled variable absorption or reflect. These devices include glare automotive rearview mirrors, Windows, svetoslava panels, curtain air box, group display, etc.

A known method of manufacturing electrochromic devices (US 4902108, 20.02.1990), in which the conductive coating of one of the two optically transparent electrodes applied thickened solution of polymermetal is glued both optically transparent electrode on the perimeter at a given distance from one another, fill formed between them an enclosed space electrochromic solution containing the cathode and anode components and indifferent electrolyte in a high-boiling solvent, through the opening (s) in the adhesive seam and seal this space. The above-mentioned layer of polymethylmethacrylate dissolved and saguday electrochromic solution that significantly reduces the negative effect of gravitational "stratification" electroacoustic forms of composition. Thus, the actual electrochromic composition only get after completing the Assembly of the above-described electrochromic device, which limits the adaptability of the device as a whole, while the electrochromic composition is a liquid phase varying degrees of viscosity, determined by the number of polymer-thickener. Indifferent electrolyte, is put into the electrochromic solution, provides the electrical conductivity in the last case, if the cathode and anode components do not dissolve to the ionic state. Also the indifferent electrolyte is injected and compositions based on Quaternary salts piperidine.

A known method of manufacturing electrochromic devices (US 5471337, 28.11.1995), in which a closed space is the solvent, thickened, preferably, polymethyl methacrylate, or plasticized with a solvent of the polymer and the dispersed phase in the form of polyoxometallate as the cathodic component and the anodic component.

A known method of manufacturing electrochromic devices (EN 2144937 C1, 27.01.2000), in which a closed space between the electrodes is filled electrochromic disperse system, which is a suspension consisting of the dispersion medium in the form of an electrochromic solution containing the cathode and anode components and the solvent of the dispersed phase in the form of fine polymer seal this space and maintain electrochromic disperse system to dissolve the polymer. This method makes it easy to get the electrochromic device with a wide range of viscosity of the electrochromic composition up to obtain electrochromic composition in the form of totopotomoy film that prevents the "delamination" electroacoustic forms of components of the above composition and reduces the risk of contact with the electrochromic composition of the accidental destruction of such devices. However, prolonged exposure to stress and especially when changing the polarity of the POM composition known electrochromic devices (EN 2144937 C1, 27.01.2000) any "spots", i.e. areas that differ in color and/or intensity of the color from the background. This negative effect is mostly characteristic for electrochromic devices with large work surface optically transparent SnO2:F-electrodes. In addition, in the manufacture of electrochromic devices after dissolution of the polymer and enlightenment electrochromic composition over the entire area of the working surface of the device, the formation of air bubbles, making the device unsuitable for practical use.

Known methods of manufacturing electrochromic devices, including obtaining totopotomoy film electrochromic composition directly into the device by polymerization and/or polymerization with crosslinking of chains of Monomeric compositions using the initiators of different types (EP 0612826 A1, 31.08.1994,; WO 97/34186, 18.09.1997; WO 98/42796, 01.10.1998). However, such polymerization reactions are accompanied by volume shrinkage, negatively affecting the quality of the electrochromic device. This negative effect can be demonstrated in electrochromic devices with significant interelectrode gaps (1-2 mm), usually provided in the electrochromic device is giving electrochromic device with an electrochromic composition in the form of a polymer layer, including tverdofaznogo, not showing any volumetric shrinkage in the process of structuring in a wide temperature range, which is homogeneous after structuring, with increased speed discoloration and providing increased stability of the electrochromic device, working in conditions of prolonged maintenance of the painted condition, and also in terms of the effects of high operating voltage and polarity of the electrodes shown in the increase of the time preserving the uniformity of staining and discoloration, especially for electrochromic device with a large area of the working surface.

The problem is solved by a method of manufacturing electrochromic devices containing at least two electrodes, at least one of which is optically transparent, thus hermetically closed space between the electrodes is filled electrochromic composition, namely, that: - receive the initial electrochromic composition in the form of electrochromic dispersed system containing at least a suspension and/or colloid, in this system the dispersion medium is an electrochromic solution containing liquid is R; - carry out deaeration initial electrochromic composition for the removal of dissolved oxygen and air, made with finely dispersed polymer; - fill the closed space between the electrodes deaerated initial electrochromic composition; - carry out the sealing of the closed space between the electrodes.

The electrochromic solution may optionally contain an indifferent electrolyte. The electrolyte concentration is 0.005 M-0.5 M

Deaeration of the initial electrochromic composition for the removal of dissolved oxygen and air, made with finely dispersed polymer, can be done by vacuum.

Superfine polymer preferably taken in an amount to provide education tverdofaznogo layer of electrochromic compound, which is characterized by the absence of volumetric shrinkage in the process of dissolution of the polymer in the above-described electrochromic solution in a wide range of temperatures.

This highly dispersed polymer is a linear polymer, in particular high molecular weight linear polymer, for example a copolymer of methyl methacrylate and methacrylic acid and/or a copolymer of methyl methacrylate, methacrylic acid and its with the ical connections.

Cathodic component is an individual organic electrochromic compound having at polarogram at least one reversible wave recovery, or a mixture of such organic electrochromic compounds, and the anodic component is the individual electrochromic organic compound having at polarogram at least one reversible wave oxidation, or a mixture of such organic electrochromic compounds.

The concentration of the cathodic and anodic components of 0.001 M To 0.2 M, more preferably 0.01 M And 0.1 M

In addition, preferably the cathode component is a Quaternary salt by dipyridine or its derivative or a mixture of salts.

The anode component is metallocen. Preferably the anode component is a ferrocene, its derivative, or a mixture thereof. Also, the anode component can be a 5,10-dihydro-5,10-dimethylpentyl, its derivative, or a mixture thereof.

To increase the duration of the existence of a disperse system in the form of a suspension and/or colloid dispersion medium is cooled before introduction of the dispersed phase, while the dispersion medium can be cooled to lower or higher who we are to improve the quality of manufacturing electrochromic devices carry out deaeration closed space between the electrodes before completing his initial electrochromic composition, for example, by purging it with an inert gas or vacuum.

The solution of the problem is also the electrochromic device containing at least two electrodes, at least one of which is optically transparent, and the space between the electrodes hermetically closed and filled with the electrochromic composition, and obtained in the above way.

Thus the electrochromic composition mentioned electrochromic device may further comprise a UV stabilizing additive.

UV stabilizing additives are widely used in electrochromic devices - see, for example, patent US 6433913 (column 15, lines 11-13).

In Fig.1 shows an example implementation of the electrochromic device with two optically transparent electrodes in the context of Fig.2 is an example implementation of the electrochromic device with two optically transparent electrodes in the context of shift electrodes.

For manufacturing electrochromic devices using optically transparent electrodes, which is a glass or polymer (in particular is of doped indium oxide In2O3or doped tin oxide SnO2. The electrodes are clamped on the perimeter preferably glued connection so that between them there was provided a set distance, while the electrically conductive coating is located inside a closed space bounded by the electrodes and adhesive connection. Adhesive may be a glue seam, which usually contains spacers (spacers) for fixing a given distance between the electrodes. To obtain the adhesive bonding can also use double-sided adhesive tape, if the thickness of this tape matches the given distance between the electrodes. The outer perimeter of the adhesive joints or along the longest sides of the electrodes have the feed bars. Pets tires inside the adhesive connection with the output conductors to the outside. In the adhesive connection leave one or more holes to fill the closed space between the electrodes of the initial electrochromic composition. After filling hole is closed with an inert sealant.

The initial electrochromic composition is an electrochromic dispersed system containing at least suspendered electrochromic dispersed system is electrochromic solution, which consists of a liquid solvent, the cathode component, the anode component and, if necessary, indifferent electrolyte. The liquid solvent can be as individual chemical compound, for example,-butyrolactone or propylene carbonate and a mixture of chemical compounds, for example, a mixture of the above substances.

The choice of liquid solvent is determined by the choice of anode and cathode components based on the selected superfine polymer and provide the desired technical result.

As cathode and anode components use organic electrochromic compounds having, as a rule, high extinction coefficients, electroactivated forms. The use of organic electrochromic systems also can significantly reduce the transmittance in the UV range at electronelectron colouring, which greatly improves consumer properties svetoslava electrochromic devices.

In the General case as a cathode component used individual organic electrochromic compound or mixture of organic electrochromic compounds capable of reversible reset the formation. The preferred cathodic component is a Quaternary salt dipyridine or its derivatives, or a mixture of salts. As a Quaternary salt dipyridine or its derivatives can be used perchlorate, tetrafluoroborate or hexaphosphate 4,4'-dipyridine, 2,2'-dipyridine, bis-1,1'-dipyridine with the linking nitrogen atoms alkalinous group with 1-10 carbon atoms; bis-2,2'-pyridinium or bis 4,4'-pyridinium from connecting phenylenebis group or keto group. As quaternionic groups pyridine rings dipyridine can be independent from one another alkyl group with 1-10 carbon atoms, phenyl and benzyl groups, phenyl or benzyl groups with different position from any carbon atom in a benzene ring alkyl substituents with 1 to 4 carbon atoms, halides (CL, Br, I), alkoxygroup or cyano groups, and alkylene binder group with 2-4 carbon atoms for 2,2'-dipyridinium derivatives. In addition, the pyridine ring can contain atoms of carbon are very different from each other substituents, such as alkyl groups with 1-4 carbon atoms, phenyl, phenyl groups with different position of carbon atoms in a benzene ring alkyl say in General use individual organic electrochromic compound or mixture of such compounds, capable of reversible elektrookislenie in the anode region of potentials, i.e., having at least one reversible current-voltage wave oxidation.

The preferred anode component is metallocen. The preferred anode component, representing ferrocene, its derivatives or mixtures thereof.

As ferrocene derivatives can be used compounds containing cyclopentadienyls the ring or rings by one or two are independent of one another Deputy: alkyl groups with 1-10 carbon atoms, phenyl group, alkylphenyl group with 1-4 carbon atoms in the alkyl group, alkoxygroup with 1-10 carbon atoms, alkoxyphenyl group with 1-4 carbon atoms in alkoxygroup, benzyl group, alkylbenzene group with 1-4 carbon atoms in the alkyl group, halogenidesilver group, phenolcarboxylic, nitroaniline, carboxamido, acyl, arrayline or acyl(aryl)alkyl groups, and others. Also use a mixture of mono-, di - and tetrachloroferrate received by THE 38-103219-88.

The anode component can also be taken 5,10-dihydro-5,10-dimethylpentyl, its derivative, or a mixture thereof.

Nature electrochromic costwise on the electrodes, no impact on the achievement of specified in the description of the technical results. The use of mixed compositions will provide for each individual electrochromic solution of certain spectral characteristics or colors or tones electroactivated state electrochromic composition in the interelectrode space.

The presence of indifferent electrolyte, optionally introduced into the dispersion medium, accelerates discoloration electroactivated electrochromic device and prevent the disruption of the uniformity of staining and discoloration after work electrochromic device for continuous polarization under DC voltage and/or after exposure to elevated stresses. As indifferent electrolyte used is known salts such as perchlorates, tetrafluoroborates or hexaphosphate alkaline or alkaline earth metals, and also with tetraalkylammonium alkyl groups with 1-4 carbon atoms.

In a dispersive medium can be introduced if necessary, UV stabilizing additive. As stabilizing additives can be used compounds from the class of beysolow, benzophenone and acrylation, 2,2'-dihydroxy-4-methoxybenzophenone or mixtures thereof.

All components of the dispersion medium after dilution to form a true solution. The concentration of the cathodic and anodic components are determined by the type of electrochromic device and the specified electro-optical parameters, therefore, can vary in a wide range from 0.001 M to 0.2 M. the Preferred concentration of the cathodic and anodic components of 0.01 M To 0.1 M. the Amount of the electrolyte may range from 0.005 M To 0.5 M. the content of the UV stabilizing additives varies in the range of 0.02 M To 0.2 M

The dispersed phase electrochromic dispersed system is a highly dispersible polymer.

In addition, the dispersed system can contain both a suspension and a colloid. This is due to the fact that highly dispersed substances may contain particles of different sizes despite the fact that the technical conditions for such substances it is customary to specify the maximum size of the particles. For example, according to the passport data for copolymers brand Vitan maximum particle size of not more than 40 μm, and the specific surface area is not less than 1.4-1.5 m2/, Therefore, to disperse system according to the invention cannot be excluded microheterogeneity, causing the formation to which spencei, formed larger particles finely dispersed polymer and colloid formed his smaller particles (see C. A. Kireev. A short course of physical chemistry. - M.: Chemistry, 1969, S. 503-505).

As a highly dispersed polymers are able to form a suspension and/or colloid in the electrochromic solution, can be used Homo - and copolymers of vinyl chloride with alkylphenate and chlorinated hydrocarbons, cellulose acetates with diethylphthalate and glycols, cellulose nitrate with dibutyl phthalate, polyvinyl butyral glycol, etc.

It is preferable to use fine linear high molecular weight polymer. An example of such a polymer is of high molecular weight (molecular weight up to 10) copolymer of methyl methacrylate and methacrylic acid brand Vitan-2M manufactured by THE 6-01-1174-91, or a copolymer of methyl methacrylate, methacrylic acid and its calcium salts brand Vitan-OS made by THE 6-02-128-96. The particle size of both copolymers does not exceed 610-5m

The amount of the dispersed phase is determined by the desired viscosity of the electrochromic composition and therefore may vary in a wide range from 0.9 to 40 wt.% the initial electrochromic composition.

(I.e., not having fluidity) of the layer of electrochromic composition, resulting from the structuring of the initial electrochromic composition in the process of dissolution of the dispersed phase in the dispersion medium. The process of education tverdofaznogo layer in this case without any volumetric shrinkage. Such electrochromic layer significantly increases the strain irreversible electrode reactions involving gas evolution, which ensures the stability of the electrochromic device to the effects of high (more than 2) stresses.

The initial electrochromic composition in the form as described above, the suspension and/or colloid is subjected to deaeration to remove dissolved oxygen and air, made with finely dispersed polymer in the process of obtaining an electrochromic composition. The implementation of this deaeration (e.g., by vacuum) contributes to the homogeneity of the initial electrochromic composition and, consequently, the homogeneity of its staining and discoloration.

To improve the quality of manufacturing electrochromic products also contributes to the implementation of the deaeration closed space between the two electrodes, for example, by purging with an inert gas or VA and/or colloid, the initial electrochromic composition is cooled, which reduces the rate of dissolution of fine polymer electrochromic solution.

The closed space between the electrodes is filled initial electrochromic composition through left in the adhesive connection of the one or more holes. Because the initial electrochromic composition is opaque, then the electrochromic device immediately after filling it turns out Matt. However, after some time (from several minutes to several hours depending on temperature, concentration of polymer and solvent), needed to complete the process of dissolution of fine polymer electrochromic solution, the electrochromic layer becomes transparent. Filled in the closed space between the two electrodes can be sealed either directly after filling, or in the process of transition of the initial electrochromic composition in a clear end state, or upon the completion of this process. To accelerate transition of the initial electrochromic composition in a transparent state, the device is heated to a temperature not exceeding 90oC.

The electrochromic device (Fig.1 or Fig.2) contains two of the transparent optically who represent a glass plate or a polymer film, the area of which is determined by a specific area using electrochromic devices. In electrochromic mirrors or electrochromic devices for information display means only one optically transparent electrode.

Along the long sides of the substrate 3 and 4, or around their perimeter (not shown) on the surface of the optically transparent electrodes 1 and 2 are the feed bars 5 and 6. Substrate 3 and 4 are fastened together along the perimeter between a glued connection 7 with the formation of the closed space. Adhesive 7 can represent, for example, adhesive joint or double-sided adhesive tape type VHB (manufacturer Minnesota Mining & Manufacturing Company). For example, the embodiment of the invention shown in Fig.1, the feed bars 5 or 6 between the adhesive connection 7 and the electrode 1 or 2, respectively, can be made in the form of a single conductor or at least two parallel conductors (not shown) to ensure a reliable electrical contact. In the case of a glutinous seam inside place spacers (spacers) to provide a specified distance between the optically transparent electrodes 1 and 2. Dogstreet a given distance between the electrodes 1 and 2. The closed space between the electrodes 1 and 2 are filled with the electrochromic composition 8 containing, if necessary, UV stabilizing additive, and sealed. The feed bars 5 and 6 are connected to the control device 9.

Example 1 Was fabricated electrochromic device containing two optically transparent Sn2electrode with the surface electrical resistance of 18 Ω/Ω/and the thickness of the glass substrate 4 mm (glass manufacturer Pilkington). The size of the electrodes was 2030 cm2. The electrodes were shifted one relative to another to ensure the electrical power supply on the long side and glued around the perimeter adhesive based on epoxy resin containing spacers (Spencers) to form the interelectrode gap of 0.4 mm In the glue line width of 5 mm left the opening for filling the device initial electrochromic composition, representing a disperse system in the form of a suspension with the following content components: a dispersive medium (electrochromic solution) is a solution of 0.01 M 1,1'-dimethyl-4,4 dipyridine of diperchlorate and 0.01 M ferrocene in-butyrolactone; the dispersed phase (20,7 wt.%) the copolymer Vitan-2M. Pego volume device initial electrochromic composition was carried out by the method of injection. After filling the hole in the adhesive seam was sealed with an inert sealant.

Evenly matte initial electrochromic composition after about 1.5 hours at a temperature of 20oWith became transparent. Thus over the entire area of the optical window of the device observed the formation of numerous air bubbles with a diameter of 1-2 mm, which did not disappear after long-term storage devices and even at elevated storage temperatures up to 60-70oC.

Example 2 Produced the electrochromic device as in example 1, but the initial electrochromic composition before filling was evacuated for 12 minutes

Evenly matte initial electrochromic composition after about 1.5 hours at a temperature of 20oWith became transparent without the formation of any visible air bubbles and without manifestations of volumetric shrinkage. When the transmission device in the visible range of the spectrum was 78%. When applying the device voltage DC 1.5 In the electrochromic layer acquired by the area of the window evenly blue color, and when the circuit electrodes short transmission device is returned to the source. At the opening of the device, the electrochromic composition represented terdapat the 100 cm2containing two optically transparent SnO2electrode with the surface electrical resistance of 18 Ω/Ω/and the thickness of the glass substrate 4 mm (K-glass). The electrodes were glued around the perimeter of double-sided adhesive tape VHB 4910 thickness of 1 mm and a width of 6 mm with two holes to fill in the electrochromic devices of the dispersed system. Along the long sides of each of the electrodes under adhesive tape were laid conductive bus in the form of copper wires with a diameter of 0.2 mm, bred out. Thus formed the inner space of the device 1 is filled by the injection method the initial electrochromic composition, representing a disperse system in the form of a suspension with the following content components: a dispersive medium (electrochromic solution) is a solution of 0.01 M 1,1'-dimethyl-4,4'-dipyridine of diperchlorate and 0.01 M ferrocene in a mixture of 60 vol.%-butyrolactone and 40% vol. the propylene carbonate; a dispersed phase of 20.5 wt.%) the copolymer Vitan-2M. Similarly filled in the internal space of the device 2 of the initial electrochromic composition as in the device 1, but additionally containing in dispersion medium lithium perchlorate in a concentration of 0.02 M. the persistence of the initial electrochromic composition was evacuated for 15 min, and the internal space of the devices 1 and 2 was purged with argon for 20-25 minutes, using the holes in the glue line. After filling the holes in the adhesive seam was sealed with an inert sealant.

Evenly matte initial electrochromic composition in both devices after about 5 hours at a temperature of 20oTo become transparent without the formation of any visible air bubbles and without manifestations of volumetric shrinkage.

The feed bars of each of the electrodes shorted to implement polarization from two sides at once. The device has filed a DC voltage of 1.5 Century, While the transmittance in the visible range of the spectrum decreased for the device 1 from 73% to 9%, and for device 2 from 72% to 10%. Staining occurred on the current trunks to the middle. For both devices the full time intensive blue staining was approximately 8 minutes After reaching the stationary mode and incubation for 1 h off the voltage and the electrodes are shorted. Return time to the initial (transparent) state when it was 15 min for 1 and 10 min for the device 2.

When applied to a parallel connected devices 1 and 2 output the I color. After three hours of storage devices in such electroactivated condition on a significant part of the window area of the device 1 was observed by the appearance of spots in the form clots brownish color with enlightened periphery, the size of which ranged from fractions of a millimeter to several millimeters. The new inequality was more pronounced in the process of bleaching in short circuit of the electrodes. More significant violation of the uniformity of dyeing-bleaching device 1 was observed when changing the polarity of the electrodes after prolonged exposure to high voltage, as described above, in the next cycle coloring-bleaching. In similar conditions of polarization (3 In three hours) unit 2 retain their original properties, while the quality of the device 1 was not restored even after prolonged subsequent storage.

Example 4
It was made electrochromic device size 75100 cm2containing two optically transparent Sn2electrode with the surface electrical resistance of 18 Ω/Ω/and the thickness of the glass substrate 4 mm (K-glass). The electrodes were glued on PERIMET the electrochromic disperse system. Additionally on the outer perimeter of the device proclaime adhesive based on epoxy resin so that the total width of the glue line was 8 mm, the Feed bars were made as in example 3. The internal space of the device was filled by the injection method the initial electrochromic composition, representing a disperse system in the form of a suspension with the following content components: a dispersive medium (electrochromic solution) is a solution of 0.01 M 1,1'-dimethyl-4,4'-dipyridine of diperchlorate and 0.01 M ferrocene in a mixture of 60 vol.%-butyrolactone and 40% vol. the propylene carbonate; a dispersed phase of 20.5 wt.%) the copolymer Vitan-2M. Before filling a disperse system in the form of suspension was evacuated for 15 minutes After filling the hole in the adhesive seam was sealed with an inert sealant.

Evenly matte initial electrochromic composition after 30 min at a temperature of 60oWith became transparent without the formation of any visible air bubbles and without manifestations of volumetric shrinkage. When the transmission device in the visible range of the spectrum was 75%. When applying the device voltage DC 1.7V was intensely blue colouring with sides tochapter 8% 9 minutes When you disable voltage after reaching the stationary mode and short circuit of the electrodes and the device is returned to the source (transparent) state. The full bleaching was 15 minutes

When storing the device in a vertical position for 5 months at ambient temperature and 1 month at a temperature of 65oSince it was not detected any signs of fluidity of the layer of electrochromic composition. Control is possible deformations due to hydrostatic pressure, carried out by the sensor of linear expansion, the accuracy of the measurement which was 5 μm.

Example 5
It was made electrochromic device 2025 cm2containing two optically transparent Sn2electrode with the surface electrical resistance of 18 Ω/Ω/and the thickness of the glass substrate 4 mm (K-glass). On the edge of the long sides of each electrode caused strips of conductive adhesive NTC (OST 107.46007.004-91) with a width of 2 mm and a thickness of 0.25 mm For implementing sufficient conductivity current trunks inside layer of glue NTC paved copper conductor with a diameter of 0.2 mm, bred out. The electrodes were glued on per the standing device of 0.8 mm In a glutinous seam precluding contact of the inner active layer with pre-shaped current-carrying tires, left two holes for filling the device by the method of injection of the initial electrochromic composition, representing a disperse system in the form of a suspension with the following content components: a dispersive medium (electrochromic solution) is a solution of 0.015 M 1,1'-dimethyl-4,4'-dipyridine of diperchlorate, 0,015 M ferrocene and 0.02 M of tetraethylammonium perchlorate in a mixture of 50 vol.%-butyrolactone and about 50. % propylene carbonate; a dispersed phase of 20.5 wt.%) the copolymer Vitan-2M. Before completing the initial electrochromic composition was evacuated for 15 minutes After filling the hole in the adhesive seam was sealed with an inert sealant.

Evenly matte initial electrochromic composition in the device after about 20 minutes at a temperature of 60oWith became transparent and homogeneous without showing volumetric shrinkage. The transmission device in the visible range of the spectrum was 76%, in the wavelength range 300-400 nm - 55%. When applying the device voltage DC 1.5 V, the transmittance in the visible range of the spectrum decreased to 6%, and in the near UV range (200-300 is ilos to the original (transparent) state.

Example 6
It was built device, similar in design to the device in example 5. The internal space of the device is filled by the injection method the initial electrochromic composition, representing a disperse system in the form of a suspension with the following content components: the dispersion medium is a solution of 0.01 M 1,1'-dimethyl-4,4'-dipyridine of diperchlorate, 0.01 M 5,10-dihydro-5,10-dimethylbenzene and 0.02 M of tetraethylammonium perchlorate in a mixture of about 60. %-butyrolactone and 40% vol. the propylene carbonate; a dispersed phase of 20.5 wt.%) the copolymer Vitan-2M. Before completing the initial electrochromic composition was evacuated for 15 min, and the internal space of the device was purged with argon for 25 minutes After filling the hole in the adhesive seam was sealed with an inert sealant. Evenly matte initial electrochromic composition in the device after 20 min at a temperature of 60oWith became transparent and homogeneous without showing volumetric shrinkage. When this layer of electrochromic composition in the device had a yellow tint.

When applying the device voltage is DC 4.5 V for 30 with the electrochromic composition quickly became uniform square window intense the pursuit of a layer of electrochromic composition not violated, and his original yellow tint is gone.


Claims

1. A method of manufacturing electrochromic devices containing at least two electrodes, at least one of which is optically transparent, thus hermetically closed space between the electrodes is filled electrochromic composition, namely, that receive the initial electrochromic composition in the form of electrochromic dispersed system containing at least a suspension and/or colloid, in this system the dispersion medium is an electrochromic solution containing a liquid solvent, the cathodic component and the anodic component and the dispersed phase is finely dispersed polymer; carry out deaeration initial electrochromic composition for the removal of dissolved oxygen and air, made with finely dispersed polymer; fill the closed space between the electrodes deaerated initial electrochromic composition; carry out the sealing of the closed space between the electrodes.

2. The method according to p. 1, characterized in that the electrochromic solution additionally contains an indifferent electrolyte.

3. The method according to p. 2, otli, what deaeration initial electrochromic composition for the removal of dissolved oxygen and air, made with finely dispersed polymer is carried out by vacuum.

5. The method according to any of paragraphs.1-4, characterized in that the finely dispersed polymer charge in an amount to provide education tverdofaznogo electrochromic layer structure.

6. The method according to any of paragraphs.1-5, characterized in that the finely dispersed polymer is a linear polymer.

7. The method according to p. 6, wherein the fine linear polymer is a high molecular weight.

8. The method according to p. 7, characterized in that as a finely dispersed high molecular weight linear polymer take a copolymer of methyl methacrylate and methacrylic acid and/or a copolymer of methyl methacrylate, methacrylic acid and its calcium salt.

9. The method according to any of paragraphs.1-8, characterized in that the liquid solvent is an individual chemical compound or mixture of chemical compounds.

10. The method according to any of paragraphs.1-9, characterized in that the cathode component is an individual organic electrochromic compound having at polarogram at least one reversible wave recovery ancestim electrochromic compound, with polarogram at least one reversible wave oxidation, or a mixture of such organic electrochromic compounds.

11. The method according to p. 10, characterized in that the concentration of the cathodic and anodic components of 0.001-0.2 M

12. The method according to p. 11, characterized in that the concentration of the cathodic and anodic components preferably equal to 0.01 and 0.1 M

13. The method according to any of paragraphs.10-12, characterized in that the cathode component is a Quaternary salt by dipyridine or its derivative or a mixture of salts.

14. The method according to any of paragraphs.10-12, characterized in that the anodic component is metallocenes.

15. The method according to p. 14, characterized in that the anodic component is a ferrocene, its derivative, or a mixture thereof.

16. The method according to any of paragraphs.10-12, characterized in that the anodic component is a 5,10-dihydro-5,10-dimethylpentyl, its derivative, or a mixture thereof.

17. The method according to any of paragraphs.1-16, characterized in that the dispersion medium is cooled before introduction of the dispersed phase.

18. The method according to any of paragraphs.1-17, characterized in that the carry out deaeration closed space between the electrodes before completing his initial electrochromic composition.

19. The way Phnom electrochromic composition is carried out by purging it with an inert gas or vacuum.

20. The electrochromic device containing at least two electrodes, at least one of which is optically transparent, and the space between the electrodes hermetically closed and filled with the electrochromic composition, characterized in that it is obtained by the method according to any of paragraphs.1-19.

21. The electrochromic device according to p. 20, characterized in that the electrochromic composition further comprises a UV stabilizing additive.

 

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The invention relates to materials for the preparation of superfine,non-ferrous, thermostable polarizing coatings (PP), which can be used in optics for manufacturing a display device, the production of Polaroid film on a polymer basis, polarizing glass for construction and automotive industries

FIELD: color-forming compositions and recording material.

SUBSTANCE: claimed composition includes developer containing urea-urethane compound and colorless or light colored leuco dye. Recording material based on this composition also is proposed.

EFFECT: color-forming compositions with improved image conservation ability and increased image intensity.

21 cl, 14 tbl, 153 ex

FIELD: optical data carriers.

SUBSTANCE: device has cation dye or mixture of cation dyes with optical characteristics, changed by means of recording beam, an at least one substance with functions of damper and phenol or substituted phenol with one hydroxide group or more, while it additionally contains phenol or substituted phenol in form of phenolate ion, forming a portion of anions for dye cations, as a stabilizer. Data carrier can contain anionic metal-organic thyolene complex as damper, which forms other portion of anions for dye cations.

EFFECT: higher stability, higher durability, lower costs.

5 cl, 1 tbl, 3 ex

FIELD: optical materials.

SUBSTANCE: invention relates to radiation-sensitive compositions with variable refraction coefficients allowing novel model with refraction coefficient distribution to be obtained, in particular optical material used in optical electronics and information representation devices. Invention discloses emission-sensitive composition with variable dielectric permittivity containing decomposable compound (A), non-decomposable component (B) including inorganic oxide particles resistant to acid or base originated from acid or base source (C), and radiation-sensitive degradable substance (C), wherein refraction coefficient nA of decomposable compound A and refraction coefficient nB of non-decomposable compound B lie in one of following relationships: nB-nA ≥ 0.05 (1) and nA-nB ≥ 0.05 (2), amount of component B ranges from 10 to 90 wt parts based on 100 wt parts of summary amount of components A and B, and amount of component C ranges from 0.01 to 30 wt parts based on 100 wt parts of summary amount of components A and B. Model obtained from indicated composition allows one to vary in a simple way refraction coefficients thereby achieving sufficiently large difference between them and their stability irrespective of application conditions.

EFFECT: expanded possibilities in optical representation of information.

12 cl, 3 tbl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to novel oxazine compounds of the formula (I): wherein X means carbon atom; R1 and R2 mean hydrogen atom; n = 0; A and A' mean independently of one another: (a) linear or branched (C1-C12)-alkyl, (C3-C12)-cycloalkyl; (b) unsubstituted or monosubstituted aryl groups. Also, invention relates to a method for synthesis of photochrome oxazine compounds of the formula (I). Invention provides synthesis of novel compounds and a method for their synthesis used as photochrome compounds.

EFFECT: improved method of synthesis.

10 cl, 1 tbl, 9 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to technology of manufacturing transparent profiled articles, for example, containers and bottles. Transparent article comprises continuous polyester matrix containing at least one incompatible filler dispersed therein. Incompatible filler provides domains in polyester matrix, each of them having particular size thereby forming a size range for domains contained in an article. To create turbidity, domain sizes lie within the range between about 400 nm and about 700 nm. Once size range is determined, a light absorbing substance can be selected to absorb light within a wavelength range, which at least essentially overlaps the preliminarily found domain size range.

EFFECT: facilitated finding substance masking turbidity of a polymer article.

20 cl, 12 dwg, 3 tbl

FIELD: physics, photographic material.

SUBSTANCE: invention pertains to polymer cholesteric photoactive compounds, which can independently generate laser emission when irradiated with laser light. Such a compound can be used, for example, in photonics, optoelectronics and telecommunication systems. The cholesteric photoactive compound for generating laser emission consists of cholesteric liquid crystal, photoactive additive and laser dye. The liquid crystal used contains conjoint polymer n-(6-acrylyl oxycapril hydroxyphenyl)-n-methoxy benzoate with cholesterine-11-acrylyl undecanoate, containing molar quantities between 30% and 25% of the cholesterine-11-acrylyl undecanoate links. Photoactive additive used is 2.5-bis(4-methoxy cynnamoyl)-1.4;3.6-dianhydro-B-sorbitol, while the laser dye used is 4-(dicyano methylene)-2-methyl-6-(4-dimethyl amino styryl)-4H-pyran. The invention improves the temporal and thermal stability of the compound, and allows for its use at room temperatures and at lower temperatures as well. Sensitivity of the compound to external effects is also lowered.

EFFECT: increased thermal stability of photoactive compounds and lower sensitivity to external effects.

2 ex, 1 dwg

FIELD: technological processes.

SUBSTANCE: method of object protection against forgery includes application of information identifying mark to the surface of protected object by means of glue layer, in composition of which light-sensitive protein bacteriorhodopsin is introduced. Information identifying mark or its part is made transparent, and corresponding portion of protected object surface is made transparent or with mirror reflecting coating. During monitoring of object authenticity light-sensitive element that contains bacteriorhodopsin is illuminated, by means of two sources of light with lengths of waves, accordingly, in band of main and intermediate conditions of bacteriorhodopsin absorption.

EFFECT: invention allows to increase reliability of protection against forgery and monitoring of valuable documents and items.

3 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: present invention pertains to new photochromic monomers and new polymers based on such monomers, intended for use in making two-photon photochromic recording media for three dimensional optical memory and photoswitches of optical signals. Description is given of monomers

Q=; ; ;

Alk=CH3-C10H21 X=Cl, Br, I, F, NH2, CH2OH, CH2Cl, CH2Br, CHO, CO2H and X=CH2, O, S, NAlk; Y=O, S, NAlk; n=0-6; Q=; ; ; ; ;

Alk=CH3-C10H21, methods of obtaining them, photochromic polymers based on them, method of obtaining photochromic monomers and their application. The proposed materials exhibit thermal irreversibility of photochromic transformations and properties, making it possible to use photochromic polymers in two-photon random access optical memory.

EFFECT: obtaining materials with thermal irreversibility of photochromic transformations and properties, making it possible to use photochromic polymers in two-photon random access optical memory.

15 cl, 46 dwg, 31 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to new photochromic monomers

Alk=CH3-C10H21 X=Cl, Br, I, F, NH2, CH2OH, CH2Cl, CH2Br, CHO, CO2H, method of obtaining them, photochromic polymers- polyazomethines, which are reversibly photocontrolled due to introduction into their structure, of dihetarylenthane class photochromic fragments.

EFFECT: obtaining new photochromic photocontrolled polymers for designing new information technologies.

8 cl, 25 dwg, 15 ex

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