RU2449331C2 - Thermochromic device (versions) - Google Patents

Abstract

FIELD: physics.

SUBSTANCE: device has at least two light-transmitting substrates and at least one thermochromic layer which reversibly changes transmission of light and thermal flux when its temperature changes in the visible and/or near infrared regions. In one case, the thermochromic layer is made from thermochromic material which is an aqueous liquid with transition metal complexes and halides of alkali and alkali-earth metals. In another version, the thermochromic layer is made from thermochromic material which is a lightfast gel containing substances capable of gelling, including in an aqueous medium, and containing transition metal complexes. In the third version, the thermochromic layer is made from thermochromic material which is an aqueous polymer film made from a vinyl-based water-soluble polymer containing at least one plasticiser and transition metal complexes.

EFFECT: higher thermochromic efficiency.

20 cl, 39 dwg, 9 tbl, 7 ex

Description

The invention relates to devices or devices for controlling the intensity, color, phase, polarization or direction of light emanating from an independent source, namely, devices for regulating lighting and energy conservation, and is intended, in particular, for the glazing of buildings, which includes glazing of windows, exterior and internal wall panels, partitions, doors, interior elements.

By a thermochromic light control device is meant a device in which a thermochromic effect is observed and which includes a transparent film, or a plate, or a layer of liquid or gel, which can be enclosed between glass plates, or transparent plastic, either applied to them or used directly.

Under the thermochromic effect is meant a reversible change in the transmission of the device in the ultraviolet (UV) and / or visible and / or infrared (IR) spectral regions due to a change in the temperature of the device.

Thermochromic efficiency (TCE) of a material and / or device refers to the ratio of optical density at a given wavelength of optical radiation at high (60-85 ° C) temperature to optical density at the same wavelength at low (20-25 ° C) thermochromic temperature material.

The basic principles of operation of existing devices for controlling illumination by changing their light transmission include a change in transmittance due to an increase or decrease in scattering, reflection or absorption of light under the influence of an electric field, optical radiation, a change in the gas environment or temperature inside the device.

The prior art devices controlled by an electric field, which are two sheets of glass, between which a multilayer polymer composition (triplex) is placed, capable of changing the light transmission due to the absorption or scattering of light under the influence of an electric field. Common disadvantages of electrically controlled devices are the small number of operation cycles without compromising the operational parameters of the device, insufficient uniformity of coloring and high cost, which prevents their use for external glazing, the need to use an external power source and control systems, which complicates the design, reduces its reliability and is associated with power consumption. (Lee, ES et al. "Advancement of Electro-chromic Windows." Lawrence Berkeley National Laboratory. California Energy Commission, Public Interest Energy Research (PIER) Program 2006, Final Report 500-01-023. LBNL-59821 , 101 p. )

Photochromic glasses are known that contain copper or silver halides, which reduce transmission in the visible region of the spectrum under the influence of ultraviolet radiation. However, such glasses are expensive, and the technology for the production of large-format sheet glass for glazing buildings has not been developed. (Barachevsky V.A., Lashkov G.I., V.A. Tsekhomsky "Photochromism and its application" M .: Chemistry, 1977, 300 p.). Attempts to find new solutions using glasses containing titanium and tungsten oxides have not yet led to the advent of a new commercial product (Anneke Georg, Andreas Georg, "Photochromic Window System for Use in Building Envelopes", University of Freiburg Fraunhoffer Institute. Annual Report 2004. p. 18).

A change in the gaseous medium in a gas-chrome double-chamber double-glazed window due to the introduction of gaseous hydrogen into the space between the glasses leads to a change in light transmission, which is manifested in the appearance or disappearance of the color of the inner surface of the outer glass coated with a thin layer of tungsten oxide, the discoloration of the glass is achieved by introducing gaseous oxygen into the inter-glass space. The disadvantage of this solution is the design complexity and the need to use explosive and fire hazardous gas mixtures. (J.Carmodi et al. “Window Systems For High Performance Commercial Buildings.” Lawrence Berkeley National Laboratory California Energy Commission, Public Interest Energy Research (PIER) Program 2006, CEC-500-2006-052-AT14).

Temperature-controlled light-regulating devices are known from the prior art, which are two sheets of glass between which a layer of liquid or gel is placed, the light transmission of which varies with temperature due to a change in the temperature of light scattering in the layer.

In US patent No. 7306833, published December 11, 2007 under the headings of IPC E06B 3/00, E04C 2/54, G02F 1/15, G09G 3/19, describes a device consisting of two sheets of glass, the space between which is filled with a layer of hydrogel, consisting 30% from polyvinylcaprolactam and 70% from water. At temperatures exceeding 25-30 ° C, the light transmission of the device decreases from 80% to 10-15%, which is caused by an increase in light scattering in the hydrogel layer. Since the change in light transmission is not associated with a change in light absorption, the device does not have thermochromic properties.

Thermochromic materials based on transition metal oxides (V, Fe, Ni, W, Ti, Nb) are known in the prior art. They undergo a transition from a semiconducting to a conducting state (Mott transition) at a “critical” temperature T _c . Their main disadvantage is that for most of these materials T _c > 70 ° C, which makes them impossible to use for glazing buildings. To reduce T _c, transition metal oxides, in particular vanadium oxide, are modified by introducing impurities (F, W, Mo, Nb and Re, Sn and SiO ₂ ) into them.

In US patent No. 4401690, published 30.08.1983 under the headings of the IPC B05D 5/12; B05D 3/02; C03C 17/245, describes a method for manufacturing a thermochromic device comprising a glass substrate and a coating containing vanadium oxide having a reduced T _c , which is achieved by introducing metal compounds having a larger ionic radius than the vanadium ionic radius into the film of vanadium oxide, such as tungsten , niobium, tantalum, iridium or molybdenum. However, a decrease in T _c leads to a decrease in the thermochromic efficiency of the material, since a change in light transmission in the operating temperature range occurs at an unacceptably low level of the initial light transmission of the layer (40-50%).

The disadvantages of the method for producing thermochromic glass with a layer of vanadium oxide are the need to use high (350-650 ° C) temperatures, vacuum and antioxidants to achieve the necessary V: O stoichiometry, as well as the difficulty of obtaining a layer over a large area. [Moon-Hee Lee. "Thermochromic Glazing of Windows with Better Luminous Solar Transmittance" Solar Energy Materials & Solar Cells. 2002, v. 71, p. 537-540].

In US patent No. 4741859, published 03.05.1988 under the headings of IPC G02F 1/13, C09K 19/30, 19/12, describes a method of manufacturing a liquid crystal material showing thermochromic properties in the entire visible spectral range. The thermochromic properties of this material are manifested in the selective reflection of incident white light, creating bright rainbow colors that change with temperature. The material is intended, in particular, for use as ink. Disadvantage: insufficiently large temperature range of operation (-5 ÷ + 50 ° C) of the material prevents its use as a thermochromic layer when glazing buildings.

Thermochromic polymer gels are known, including those containing transition metal complexes. These gels, in particular, based on the polyester - ethylene oxide - carboxyvinyl system, turned out to be non-lightfast and short-lived in operation due to fatigue phenomena. It turned out to be impossible to use the best samples of thermochromic organic compounds and their compositions for adaptive glazing due to high working temperatures (about 80 ° C) and insufficient temperature resistance. [S. M. Lampert "Chromogenic Switchable Glazing: Towards the Development of the Smart Window", Proceedings of Window Innovations, 1995. Toronto, Canada, June 5-6, 1995].

In US patent No. 3192101, published June 29, 1965 under the heading of IPC B32B 17/10, a method for manufacturing safe thermochromic glass based on the use of plasticized polyvinyl butyral containing cobalt amino complexes is described. Disadvantages: firstly, the thermochromic effect of the material is insufficient for the material to be heated by sunlight, and the inventors have to use an additional source of electric heating, which complicates the design, secondly, the light transmission ceases to decrease when the temperature reaches 50 ° C, while how the glazing temperature when exposed to sunlight in summer can reach 70-80 ° C at the latitude of Paris.

US Pat. No. 6,446,402, published September 10, 2002 under the headings of IPC G02F 1/01 and G02F 1/23, describes a thermochromic device that can be used to transmit sunlight into a building at low ambient temperature and absorb solar radiation at high temperature the environment.

This thermochromic device includes a light-transmitting substrate, a thermochromic material that reversibly changes the light transmission from large to small with increasing temperature, and a material with constant light transmission. The thermochromic material is in the substrate or in a layer deposited on the substrate and comprising from 0.1 to 20 wt.% Of the substrate or layer, and the material with constant light absorption can be in the same layer or in a layer different from the layer of thermochromic material. In particular, the thermochromic device may include a low emissivity layer. We described such a design earlier, where it was shown that it provides energy saving due to the fact that in the cold season (winter) a thermochromic layer optimized for “response” in the temperature range above the “comfortable” (20-25 ° C) remains highly transmissive (See: 1. OVYanush, VAMilovidov, IU Halopenen "Variable transmission window for automatic regulation of lighting". Abstracts of International Symposia "Optical Thin Films on Glass", USA, Wheeling, West Virginia, October 18-21, 1998. P .37 .; 2. I. Halopenen, O. Yanush, V. Milovidov "Smart laminated glasses for regulation of lighting". // Proceedings of the 6 ^th International Conference on Architectural and Automotive Glass - Glass Processing Days. - 1999. - P.324-326 .; 3. OVYanush, IUHal openen, T. Markova, VAMilovidov, SSKholchansky, REArutjunjan, IKMaksimov, H. Kawahara "Laminated glass with variable transmission for daylight regulation" // Proceedings of the 7 ^th International Conference on Architectural and Automotive Glass - Glass Processing Days. - 2001 .-- P.324-326).

The disadvantage of the device according to US patent No. 6446402 is the complexity of the multilayer structure, each of the layers of which provides a change in light transmission in a narrow temperature range, as well as the need to use protective coatings to increase light resistance, the use of additional absorbing materials that provide heating of the glazing with sunlight, but lead to a decrease in the initial light transmission level.

In US patent No. 7525717, published on 04/28/2009 under the headings of the IPC G02F 1/01, G02F 1/00, G09G 3/34, C07F 15/04, in US patent No. 7538931, published on 05/26/2009 under the headings of the IPC G02F 1/01 , in US patent No. 7542196, published 02.06.2009 under the headings of the IPC G02F 1/01, G02F 1/15, G09G 3/34; in US applications: WO 2008/028099 published March 6, 2008 under the heading of IPC G02B 21/02; No. 2008/0105851, published on 05/08/2008 under the heading of IPC G01K 11/16 and No. 2009/0283728, published on 11/19/2009 under the heading of IPC G02B 5/23, thermochromic devices are described that are characterized by a reversible change in the transmission of optical radiation with temperature, which is achieved by using layers of thermochromic materials with ligand exchange.

Materials include ions of at least one transition metal, which experience thermally induced changes in chemical bonds in the complex and / or coordination of ligands around the transition metal ion, which changes the ability of ions to absorb optical energy when temperature changes.

These patents have identical contents in the description and examples. Essentially, they present a well-known mechanism of one of the common types of thermochromic effect [Sone K., Fukuda Y. Inorganic Thermochromism. Berlin: Springer-Verlag, 1987. 184 p.], Which consists in a reversible change with temperature of the composition and / or structure of transition metal complexes (s) in a thermochromic material.

For the prototype of the present invention adopted US patent No. 7525717 for the invention of "Multilayer thermochromic system with exchange of ligands", published 04/28/2009 according to the IPC indices G02F 1/01, G02F 1/00, G09G 3/34, C07F 15/04. The patent proposes a thermochromic device that changes the transmission in the visible and / or near infrared range under the influence of temperature, including two thermochromic layers made of polymers, in particular polyvinyl butyral, containing Co (II) and / or Ni (II) complexes with concentrations from 0 , 02 to 0.4 mol / kg of polymer, as well as halides, phosphines, phosphinates, diols, triols and polyols as ligands. A thermochromic device is characterized by an optical density in the visible and near infrared wavelength range of optical radiation of less than 0.3 at a temperature of 25 ° C and more than 0.8 at a temperature of 85 ° C. The highest thermochromic efficiency (the ratio of optical densities at 60 and 25 ° C (D ⁶⁵ / D ²⁵ )) is achieved mainly only with thermochromic layer thicknesses greater than 0.8 mm.

In the prototype and other patents of the same applicant (US patents 7542196, 7538931, US application No. 2009/0283728), some metal halides are used as a source of ligands, which, when the temperature rises, should become part of the transition metal complex, leading to a thermochromic effect.

The disadvantage of the prototype and other patents of the same applicant (US patent 7542196, 7538931, 6446402, 6084702, US application No. 2009/0283728) consists, firstly, in the use of solvents, plasticizers and polymers, which in most cases are toxic substances (for example, the most commonly used: concentrated acids (sulfuric, hydrochloric, hydrobromic, hydroiodic, formic), alkalis (sodium and potassium hydroxides), hydrogen peroxide (30%), sodium hydride, benzyl chloride, 2,2-dimethoxypropane, diethylene glycol, dimethyl phthalate , hexachloroacetone, 2, 2'-dipyridyl ketone, 2-mercapto-5-methylbenzimidazole, urethanes, poly-2-vinylpyridine, polystyrenes, polyacrylamide, polyvinyl methyl ether and others. Secondly, in the process of manufacturing thermochromic layers, toxic transition metal halides are used as a source of ligands (Zn (II), Mn (II), Cd (II)), as well as phosphines, phosphinates, cyanates, thiocyanates, etc. Thirdly, there is a need for a high degree of dehydration of polymer thermochromic layers based on polyvinyl butyral, due to the fact that during the interaction of polyvinyl butyral with water about razuetsya toxic product - butyraldehyde (str.33-34 prototype).

The properties of substances by their toxicity used in the manufacture of thermochromic layers are widely known to specialists in this field of technology. The sources of information used by us that most fully reflect such information: 1 / GOST 12.1.007-76 “Classification and general safety requirements”; 2 / “Harmful substances in industry.” Handbook for chemists, engineers and doctors. Ed. 7th, per. and add. In three volumes. Ed. N.V. Lazareva and E.N. Levina. L., "Chemistry", 1976; 3 / Chemical and Other Safety Information: http://msds.chem.ox.ac.uk, published by The Physical and Theoretical Chemistry Laboratory, Oxford University .; 4 / Material Safety Data Sheet for various substances. 2010 catalog of ChemExper Inc .; 5 / Aldrich catalog. http://www.sigmaaldrich.com/catalog/.

Table 1 provides information on the toxicity of the most widely used substances in our application and in the prototype.

Table 1 Toxicity Information one 2 3 four Substance Maximum allowable concentration (MPC) in the air of the working area, mg / m ³ The average lethal dose (LD ₅₀ ) for rats when introduced into the stomach, mg / kg Hazard class (determined according to columns 2 and 3 in accordance with [1]), toxicity Substances used in our application water not dangerous glycerol not dangerous polyvinyl alcohol (PVA) not dangerous dimethyl sulfoxide twenty 4 (low hazard) ethanol 1000 (pairs) 4 (low hazard) CoI ₂ · 2H ₂ O 6157 4 (low hazard) Cu (NO ₃ ) ₂ 794 3 (moderately dangerous) CuBr ₂ · 2H ₂ O 536 3 (moderately dangerous) isopropanol 10 (pairs) 3 (moderately dangerous) 1-propanol 10 (pairs) 3 (moderately dangerous) CoCl ₂ · 6H ₂ O 766 3 (moderately dangerous) KBr 3070 3 (moderately dangerous) LiBr 1800 3 (moderately dangerous) LiCl 526 3 (moderately dangerous) Co (NO ₃ ) ₂ · 6H ₂ O 691 3 (moderately dangerous)

Continuation of Table 1 one 2 3 four Substance Maximum allowable concentration (MPC) in the air of the working area, mg / m ³ The average lethal dose (LD ₅₀ ) for rats when introduced into the stomach, mg / kg Hazard class (determined according to columns 2 and 3 in accordance with [1]), toxicity Substances used in the prototype and other Pleotint patents, but not used in our application tribenzylphosphine 5 1 (extremely dangerous) isocyanate 0.05-1 1-2 (extremely or highly hazardous) highly toxic benzyl chloride 0.5 (pairs) 2 (highly hazardous) hexachloroacetone 0.5 2 (highly hazardous), herbicide sodium hydride one toxic, 2 (highly hazardous) potassium hydroxide 0.5 (aerosol) 2 (highly hazardous) sodium hydroxide 0.5 (aerosol) 2 (highly hazardous) dimethyl phthalate 0.3 (vapors, spray) 2 (highly hazardous) diethylene glycol 0.2 (vapors and spray) 2 (highly hazardous) formic acid one 2 (highly hazardous) hydrogen peroxide (30%) 2 (highly hazardous) poly 2-vinylpyridine 0.5 (by monomer) 2 (highly hazardous), moderately toxic sulphuric acid 1 (aerosol) 2 (highly hazardous), potent chem. substance concentrated hydrochloric acid 5 (pairs) 2 (highly hazardous), potent chem. substance thiocyanate 0.8-0.9 2 (highly hazardous)

Unlike the prototype, more than half (53%) of the substances used belong to extremely and highly hazardous toxic substances (hazard classes 1 and 2, respectively), most of the substances used in our application are non-hazardous, low-hazard, and moderately hazardous (substances 4 and 3 hazard classes respectively).

The disadvantage of the manufacturing technology of the thermochromic layer for the devices described in the prototype is that it requires thorough cleaning of the starting reagents, as well as intermediate products of long multi-component multi-stage synthesis (from 1 to 72 hours at 45-90 ° C) and the final product is a film - from impurities, in particular from water impurities, the removal of which is carried out in an inert gas atmosphere without oxygen impurities, or in vacuum (prototype, example No. 290), and the intermediate products are dried after solvent removal I'm on a "silica gel chromatograph" (prototype, p.129 pos. 50, 65; p. 130 pos. 15, 30, 45, 60).

Another disadvantage of the technology is that in the prototype (claim 5 of the formula, as well as the description on page 35 - "Substrates"), to enhance the adhesion of the thermochromic layer to the surfaces of the substrates and separation layers, they have to be treated with plasma, corona discharge, or ozone, which greatly complicates the technology of manufacturing a thermochromic device.

The objective of the invention is to provide a thermochromic light control and / or energy-saving device, which achieves improved properties through the use of materials characterized by high thermochromic efficiency, ease of synthesis, low toxicity in production, operation and disposal, availability and low cost of raw materials.

The general approach used in the new technical solution in the selection of high-performance thermochromic materials consists in choosing materials in which the ligands, as a rule, are molecules of the components of the solvent and / or plasticizer and / or solvate complexes (molecular adducts). In some cases, the same ligands with the same transition metal ion can form both low absorbing and highly absorbing complexes depending on the number of ligands and the symmetry of their arrangement around the transition element ion.

In contrast to the prototype, the solvents used in the synthesis of thermochromic materials participate in complex formation as strong field ligands that form transition metal complexes with low oscillator strengths and relatively short-wavelength absorption bands due to electronic transitions inside the d shell (d-d transitions). In our case, such ligands are water molecules, monobasic alcohols, products of the interaction of molecules of various solvents and plasticizers (molecular adducts), which are non-toxic and / or low-toxic substances.

The use of such ligands makes it possible to achieve the highest possible transmission of light and heat fluxes at low temperatures (below the “threshold” temperature of 20-25 ° C, at which the “triggering” of the thermochromic device begins, that is, a decrease in the transmittance with a further increase in temperature above 25 ° C) and effectively reducing the transmittance with increasing temperature above the "threshold".

Unlike the prototype, the thermochromic layer of the developed thermochromic device uses charge-transfer transition metal complexes, the absorption bands of which are characterized by record high oscillator strengths, which ensures high thermochromic efficiency of the layer material in the visible and ultraviolet regions of the spectrum of optical radiation. [Sone K., Fukuda Y. Inorganic Thermochromism. Berlin: Springer-Verlag, 1987, 184 p.; Liver E. Electronic spectroscopy of inorganic compounds, M .: Mir, 1987. T.1-2.].

The simplification of the manufacturing process of a thermochromic device in comparison with the prototype is achieved by the following means:

1. The use of ready-made and readily available reagents, as well as combining all stages of the synthesis into one, which reduces to mixing all the components and heating at temperatures of 60-100 ° C for a relatively short time (maximum - for 1 hour in the case of liquid, gel and film thermochromic layers, which significantly reduces the contact time of personnel with reagents), followed by the application (in the case of a thermochromic film) of the film-forming composition on the substrate and drying to achieve optimal solution concentrations the retailer.

2. The exception stages of obtaining intermediate products of long multi-component multi-stage synthesis, as well as procedures for cleaning the starting reagents and end products (thermochromic layers formed by polymer films, liquids or gels) from impurities of water, which in the inventive device, as a rule, is an integral component of thermochromic materials , and from other impurities, since they do not affect the thermochromic and other properties of materials.

3. The simplification of the technological process in the claimed device is also achieved due to the high adhesion to the substrate of the thermochromic films based on vinyl developed by us (tear-off force exceeds 10 N / cm. The method of measuring adhesion consisted in cutting a strip of 1 cm wide tape glued to the substrate, to the end of which was attached tear-off force along the film plane in the direction of the glued part of the film).

4. The use of thin layers of photo- or thermo- or chemically curable compositions to create interlayers between different thermochromic layers of the claimed device without additional processing of the surfaces of the layers to be connected by plasma, corona discharge, or ozone, as is done in the prototype (see prototype: 5 formulas, as well as the description on page 35 - "Substrates").

5. Reducing the temperature of lamination (triplexing) to 120 ° C when using the developed thermoplastic thermochromic polymer materials with a lower glass transition temperature, which ensures energy saving during triplexing and prevents damage to transition metal complexes with high thermochromic efficiency that would be unstable at higher temperatures.

The object of the invention is solved by three variants of a thermochromic device, united by a common inventive concept, in which the original compositions of the thermochromic material are used: in the form of a polymer film or liquid, or gel. In this case, the thermochromic layers are made by irrigation or extrusion methods, followed by drying, mainly using substrates made of glass, as well as substrates made of polyethylene terephthalate, polypropylene, polyethylene, or cellulose acetate, or a lacquer layer deposited from a solution of polyvinyl butyral or polyvinyl acetate , or polyvinyl ethyl in organic solvents.

Option 1 thermochromic device includes at least two light-transmitting substrates and at least one thermochromic layer, reversibly changing the transmission of light and heat flux when its temperature changes in the visible and / or near infrared spectral regions, in which, unlike the prototype the thermochromic layer is made of a thermochromic material, which is an aqueous liquid with complexes of transition metals and with halides of alkali and alkaline earth metals.

These materials have high thermochromic efficiency, as a rule, exceeding the thermochromic efficiency of prototype materials. (see Table 2 (examples 1-32, figures 1-28)).

In particular, in the case of liquid (Table 2, examples 2, 3, 17, 28, figures 3, 4, 16, 27) and gel-like (made on the basis of the same liquids) thermochromic layers, a decrease in the initial level of light transmission T (70-80 % at 20-25 ° C, which corresponds to an optical density of D = log (100 / T) = ~ 0.15-0.10) when the temperature rises to 65-70 ° C by ~ 7-8 or more (the optical density changes by ~ 7-10 and more times and is ~ 1) is achieved with a thermochromic layer thickness of 0.04-0.1 mm, while in the prototype examples (all examples of liquids from the description of the prototype, as well as Examples 189-214) are term great characteristics are achieved only with layer thicknesses of 0.8 mm or more, which is close to the upper limit of the thickness of polyvinyl butyral films commonly used for automotive triplexes (0.4-1 mm).

This means that the thermochromic layer of the prototype will contain extremely high concentrations of transition metal complexes and ligands, which, in principle, can lead to chemical instability and increased light scattering in the prototype, while in the inventive device it is possible to reduce the concentration of transition compounds tens of times metals while maintaining the thickness of the thermochromic layer, which optimally regulates the transmission of light and heat fluxes, at a level of less than 1 mm.

The thermochromic material may contain pyridine or morpholine. The use of these components leads to a short-wavelength shift of the absorption bands of the heated thermochromic layers towards the maximum sensitivity of the human eye (500-550 nm region), which increases the efficiency of light control. For example, in the case of thermochromic layers containing cobalt (II) complexes, the absorption band from the range of 650-750 nm is shifted to the region of 600-650 nm (Table 2, examples 24-31, figures 24-27).

The thermochromic material further comprises nitrophenols.

This makes it possible to expand the color gamut of thermochromic transitions while maintaining the lightfastness of the material and provide additional protection for the room from ultraviolet (UV) radiation (Table 2, example 32, figure 28).

Thermochromic material can be a non-toxic or low toxic liquid (Table 2. Examples 1, 2, 4, figures 1, 2, 3, 5). This condition is necessary due to the use of thermochromic devices for residential premises and for other purposes involving contact between a person and the device.

The thermochromic device can be made with at least one layer of thermochromic material with a non-uniform area of color. This embodiment of the device is suitable for use in environmental design elements.

The thermochromic layer is made of a thermochromic material containing metal complexes with charge transfer.

Such compositions contribute to increasing the thermochromic efficiency of the inventive thermochromic device due to the known high value of the molar extinction coefficient of the absorption bands, which makes it possible to effectively cut off UV radiation in the region of 200-400 nm (Table 2, examples 17-19, 21, figures 16-18, 20 ) without the use of UV absorbers and UV stabilizers, without which most of the examples of thermochromic layers specified in the prototype do not do (p. 37, 38 of the prototype, Examples 245, 254-280, 282, 286-294).

In addition, the use of complexes of transition metals with charge transfer allows you to achieve high thermochromic efficiency in the center of the visible range of 500-550 nm (Table 2, examples 1, 3, 4, figures 1, 4, 5), which simplifies the creation of highly efficient thermochromic layers of bronze and gray colors, and also allows you to enhance the energy-saving effect, since this spectral region accounts for the maximum energy emitted by the sun.

Option 2 of the thermochromic device includes at least two light-transmitting substrates and at least one thermochromic layer reversibly changing the transmission of light and heat fluxes when its temperature changes in the visible and / or near infrared spectral regions. Unlike the prototype, in the inventive device, the thermochromic layer is made of a thermochromic material, which is a light-resistant gel containing at least one copolymer based on unsaturated acid and pentaerythritol esters, or at least one peptide-based polymer, or at least one vinyl-based polymer and containing transition metal complexes. These substances share a common property to form gels, including in the aquatic environment.

The thermochromic device according to Option 2 is convenient for use due to the fact that the gel does not leak from the space between the substrates in the event of cracks during the destruction of the thermochromic device (glass packet) and does not exert hydrostatic pressure on the substrates.

In contrast to the prototype, the use of a thermochromic layer in the form of a gel makes it possible to simplify the manufacturing technology of a thermochromic device due to the absence of polymer film manufacturing steps, as well as triplexing in an autoclave at elevated temperatures and pressures.

Examples of thermochromic gel formulations are presented in Table 3 (examples 33-35). The test results showed that the thermochromic properties of the gels are very close to the thermochromic properties of the corresponding liquids (Table 2, example 22 (figures 21, 22), example 5, example 1 (figures 1, 2)).

The thermochromic material may contain pyridine or morpholine.

The use of these components leads to a short-wavelength shift of the absorption bands of the heated thermochromic layers towards the maximum sensitivity of the human eye (500-550 nm region), which increases the efficiency of light control. For example, in the case of thermochromic layers containing cobalt (II) complexes, the absorption band from the range of 650-750 nm is shifted to the region of 600-650 nm (see examples from Option 1: Table 2, examples 24-31, figures 24-27) .

The thermochromic material further comprises nitrophenols. This makes it possible to expand the color gamut of thermochromic transitions while maintaining the lightfastness of the material and provide additional protection for the room from UV radiation (see the example from Option 1: Table 2, example 32, figure 28).

The thermochromic material is a non-toxic or low-toxic gel (Table 3, example 35 (figures 1, 2); examples from Option 1: table 2, examples 1, 2, 4, figures 1, 2, 3, 5). This condition is necessary due to the use of thermochromic devices for residential premises and for other purposes involving contact between a person and the device.

A thermochromic device comprises at least one thermochromic layer of a thermochromic material with a non-uniform area color. This embodiment of the device is suitable for use in environmental design elements.

The thermochromic layer contains metal complexes with charge transfer.

Such compositions contribute to increasing the thermochromic efficiency of the claimed thermochromic device due to the known high value of the molar extinction coefficient of the absorption bands, which makes it possible to effectively cut off UV in the region of 200-400 nm (see examples from Option 1: Table 2, examples 17-19, 21 , figures 16-18, 20).

In addition, the use of complexes of transition metals with charge transfer allows to achieve high thermochromic efficiency in the center of the visible range of 500-550 nm (Table 3, example 35, figure 1, and also see examples from Option 1: Table 2, examples 1, 3, 4, figures 3, 4, 5), which simplifies the creation of highly efficient thermochromic layers of bronze and gray colors, and also allows you to enhance the energy-saving effect, since the maximum spectral energy emitted by the Sun falls on the same spectral region.

Option 3 of the thermochromic device includes or does not include at least one light transmitting substrate and at least one thermochromic layer that reversibly changes the transmission of light and heat fluxes when its temperature changes in the visible and / or near infrared regions of the spectrum, in which, unlike the prototype, the thermochromic layer is made of thermochromic material, which is a water-containing polymer film made of a water-soluble vinyl-based polymer containing at least one plasticizer op and transition metal complexes comprising a solvent component or a plasticizer, or halides, or mixtures thereof.

Such compositions have high thermochromic efficiency (see Table 4.1-4.6, examples 36-74, figures 30-39), as a rule, superior to the thermochromic efficiency of the compositions used in the manufacture of thermochromic prototype devices. For example, in the case of thermochromic layers described in examples 36-45, 49, 50, 53, 56-58 (Table 4.1-4.4), the decrease in the initial level of light transmission is ~ 70-80% (optical density 0.1-0.15 at 20-25 ° C) by ~ 12 or more times (in this case, the transmission decreases to 6.7–4.5%, and the optical density increases to 1.2–1.35) when the temperature is increased to 65–70 ° C, it is achieved at thermochromic layer thicknesses of 0.1–0.2 mm , while in the examples of the prototype (Examples 189-214), the best results (a change in optical density of 7-8 times) are achieved, mainly, with a thickness of 0.8 mm or more, which corresponds to the top the limit of thickness of polyvinyl butyral films commonly used for automotive triplexes (0.4-1 mm).

The advantage of performing a thermochromic layer in the form of a polymer film in the inventive device is the possibility of using standard industrial equipment and standard or simplified, compared to standard, technologies used both in the manufacture of film and in the manufacture of glass triplexes (for example, automobile triplex).

In contrast to the prototype, the simplification of the technological process of manufacturing a thermochromic device is achieved through the exclusive use of ready-made and readily available reagents, as well as combining all stages of the synthesis into one, which reduces to mixing all components and heating at temperatures of 60-100 ° C for a relatively short time (maximum - within 1 hour) followed by applying a film-forming composition to a substrate and drying (if necessary) until optimal solvent concentrations are achieved.

The thermochromic material may contain pyridine or morpholine. The use of these components leads to a short-wavelength shift of the absorption bands of the heated thermochromic layers towards the maximum sensitivity of the human eye (500-550 nm region), which increases the efficiency of light control. For example, in the case of thermochromic layers containing cobalt (II) complexes, the absorption band from the range of 650-750 nm is shifted to the region of 600-650 nm (Table 4.6, examples 66-68, figures 30, 31).

The thermochromic material further comprises nitrophenols. This allows you to expand the color gamut of thermochromic transitions while maintaining the lightfastness of the material and provide additional protection for the room from UV radiation (Table 4.6, example 73, figure 38).

Thermochromic material is a non-toxic or low-toxic polymer composition (Table 4.6, example 71, figures 35, 36). This condition is necessary due to the use of thermochromic devices for residential premises and for other purposes involving contact between a person and the device.

A thermochromic device comprises at least one thermochromic layer of thermochromic material with a non-uniform color area. This embodiment of the device is suitable for use in environmental design elements.

The thermochromic layer contains metal complexes with charge transfer. Such compositions contribute to increasing the thermochromic efficiency of the claimed thermochromic device due to the known high value of the molar extinction coefficient of the absorption bands, which makes it possible to effectively cut off the UV (200-400 nm, Table 4.6, examples 70-72, figures 34, 35, 37) without using UV absorbers and UV stabilizers, without which most of the examples of thermochromic layers specified in the prototype do not do (p. 37, 38 of the prototype, Examples 245, 254-280, 282, 286-294).

In addition, the use of transition metal complexes with charge transfer allows one to achieve high thermochromic efficiency in the center of the visible range (500-550 nm), which simplifies the creation of highly effective thermochromic layers of bronze (Table 4.6, example 71 (figure 35)) and gray (Table. 4.6, example 72 (figure 37)) of colors, and also allows you to enhance the energy-saving effect, since the same spectral region accounts for the maximum energy emitted by the Sun.

A thermochromic device may include at least one layer between the thermochromic layer and the substrate and / or thermochromic layers made of a photo- or thermo- or chemically curable composition based on mixtures of monomers and oligomers of unsaturated acid derivatives.

The use of such a layer allows us to reduce the process of triplexing the thermochromic layer to applying a curable composition with a thickness of 0.01 to 1 mm (between the layer and the substrate, or between different thermochromic layers) and subsequent polymerization for 15-20 minutes, which greatly simplifies and reduces the cost of manufacturing the claimed thermochromic devices compared to the prototype. In addition, the use of such layers between thermochromic layers makes it possible to expand the range of color transitions and create a thermochromic device of neutral (gray) color.

Thermochromic layer (thermochromic layers) according to option No. 3 are materials having glass transition temperatures not exceeding 120 ° C.

Our developed thermoplastic thermochromic polymer layers with a lower glass transition temperature (Table 4.6, examples 69, 70, 74 (Figures 32-34, 39)) allow lamination (triplexing) at low temperatures (not exceeding 120 ° C), which allows to protect from destruction, highly efficient transition metal complexes that would be unstable at higher temperatures and also provide energy saving during triplexing.

As described above, the presented options for thermochromic devices are united by the task and ways to achieve it.

The inventive thermochromic device is characterized by the maximum ease of manufacturing thermochromic material. The manufacturing procedure for all options is reduced to the simultaneous mixing of the components and short-term heating of the mixture. Moreover, unlike the prototype, there are no triplexing stages in the autoclave at elevated temperatures and pressure.

The use of a thermochromic device according to Options No. 1 and No. 2 is expedient and only possible when performing a thermochromic layer in the spaces between non-planar substrate substrates.

The higher efficiency of the thermochromic layers we have developed makes it possible to reduce the concentrations of transition metal compounds or the thickness of the thermochromic layer, which simplifies the manufacturing process of thermochromic devices, especially in options 1 and 2, and further reduces the harmfulness of production.

Table 2 shows the formulations of the compositions and the optical properties of the material of the thermochromic layer made in the form of a liquid.

table 2 No.
ra Components The average concentration of the components, mol / l The optical density D, measured at a wavelength of λ at different temperatures Layer thickness mm Figure number wavelength λ, nm 20 ° C 70 ° C 85 ° C Examples to paragraph 1 of the formula one water 520 0.16 0.70 0.86 0.25 one CuBr ₂ · 2H ₂ O one KBr one 1375 0.56 1.44 1.70 2 2 ethanol 640 0.17 0.36 0.42 0.050 3 CuBr ₂ · 2H ₂ O 0.3 LiBr 0.9 3 methanol 575 0.18 0.39 0.45 0.045 four Cu (NO ₃ ) ₂ · 3H ₂ O 0.3 LiBr 0.9 four dimethyl sulfoxide 520 0.18 0.48 0.57 0.25 5 Cu (NO ₃ ) ₂ · 3H ₂ O 0.3 LiBr 0.45

Continuation of table 2 No.
ra Components Average concentrations of components
tov, mol / l The optical density D, measured at a wavelength λ, at different temperatures Layer thickness mm Figure number wavelength λ, nm 20 ° C 70 ° C 85 ° C 5 water 690 0.06 0.59 0.75 one - CoCl ₂ · 6H ₂ O 0.05 LiCl 8.8 6 water 700 0.09 0.66 0.83 0.5 - CoCl ₂ · 6H ₂ O 0.5 LiCl 5.3 7 acetone 700 0.19 0.94 1.17 1.5 6 water 32 vol.% (Over 100) CoBr ₂ · 6H ₂ O 0.42 8 methanol 677 0.08 0.8 1.02 5 7 CoCl ₂ · 6H ₂ O 0.025 LiCl 0.203 9 methanol 707 0.08 0.76 1.0 four 8 CoI ₂ · 2H ₂ O 0.5 10 methanol 700 0.16 1.42 1.80 four 9 water 14 vol.% (Over 100) CoBr ₂ · 6H ₂ O 0.43 LiBr 0.90 eleven ethanol 668 0.05 1.02 1.31 one 10 water 40 vol.% Over 100 CoCl ₂ · 6H ₂ O 0.5 LiCl one 12 glycerol 700 0.17 0.41 0.48 one eleven CoCl ₂ · 6H ₂ O 0.025 LiCl 2.6 13 ethylene glycol 700 0.18 0.50 0.60 one 12 CoCl ₂ · 6H ₂ O 0.025 LiCl 2.6

Continuation of table 2 fourteen ethanol 677 0.15 0.77 0.96 3 13 Co (NO ₃ ) ₂ · 6H ₂ O 0.5 LiBr 0.25 fifteen ethanol 700 0.15 0.8 1.0 2 fourteen water 5 vol.% (Over 100) Co (NO ₃ ) ₂ · 6H ₂ O 0.5 LiBr 0.5 16 dimethyl sulfoxide 680 0.16 0.76 0.95 0.2 fifteen Co (NO ₃ ) ₂ · 6H ₂ O 0.5 LiBr 0.75 17 dimethyl sulfoxide 340 0.02 0.97 1.94 0.04 16 water 20 vol.% (Over 100) Co (NO ₃ ) ₂ · 6H ₂ O 0.5 670 0.01 2.5 5.0 LiBr 4.0 eighteen methanol 310 0.69 3.25 4.0 3 17 NiCl ₂ · 6H ₂ O 0.27 600 0.17 0.81 1.0 LiCl 5.3 19 methanol 310 2.92 13.6 16.8 0.2 eighteen NiBr ₂ · 3H ₂ O 0.77 647 0.19 0.76 0.93 LiBr 7.87 twenty dimethyl sulfoxide 620 0.11 1.18 1.54 0.6 19 NiCl ₂ · 6H ₂ O 0.5 21 dimethyl sulfoxide 356 0.63 8.3 15.6 0.7 twenty Ni (NO ₃ ) ₂ · 6H ₂ O 0.51 680 0.17 0.87 1.10 LiBr 6.1 22 dimethyl sulfoxide 61.1 mol % 620 0.09 0.85 1.10 0.65 21 water 38.9 mol % NiCl ₂ 0.5 1320 0.11 0.37 0.45 22 LiCl 4.4 23 dimethyl sulfoxide 61.3 mol. % 680 0.18 1.20 1.54 0.3 23 water 38.7 mol % Ni (NO ₃ ) ₂ 0.51 LiBr 12.1

The end of table 2 Examples to paragraph 2 of the formula 24 pyridine 690 0.05 0.53 0.67 10 - CoCl ₂ · 6H ₂ O 0.003 LiCl 0.009 pyridine 690 0.15 0.53 0.67 one - CoCl ₂ · 6H ₂ O 0.03 LiCl 0.06 pyridine 690 0.2 0.71 0.89 one - CoCl ₂ · 6H ₂ O 0.04 LiCl 0.08 25 pyridine 621 0.09 0.84 1.1 1.5 24 CoCl ₂ · 6H ₂ O 0.052 26 pyridine 670 0.06 0.77 0.97 1.3 25 CoBr ₂ · 6H ₂ O 0.024 LiBr 0.093 27 pyridine 80 mol. % 650 0.03 0.85 1.1 1.5 26 water 20 mol. % Co (NO ₃ ) ₂ · 6H ₂ O 0.02 LiBr 0.29 28 pyridine 80 mol. % 650 0.02 0.72 0.94 0.1 27 water 20 mol. % CoBr ₂ · 6H ₂ O 0.448 29th morpholine 550 0.15 0.28 0.32 10 - Co (NO ₃ ) ₂ · 6H ₂ O 0.005 600 0.10 0.24 0.27 thirty morpholine 610 0.33 0.87 1.12 10 - CoCl ₂ · 6H ₂ O 0.0032 LiCl 0.1 31 morpholine 610 0.2 0.52 0.67 one - CoCl ₂ · 6H ₂ O 0.019 LiCl 0.6 Examples to paragraph 3 of the formula. 32 pyridine 80 mol. % 650 0.03 0.85 1.1 1.5 28 water 20 mol. % Co (NO ₃ ) ₂ · 6H ₂ O 0.02 LiBr 0.29 picric acid 0.01

Similar examples of the addition of nitrophenols in order to expand the color gamut of thermochromic transitions while maintaining the light fastness of the material and provide additional protection of the room from UV radiation in accordance with paragraph 3 of the formula can be obtained by adding the spectrum of nitrophenol (Fig. 29 (picric acid concentration - 0.01 mol / l, layer thickness - 1 mm)) with spectra of solutions (examples 1-31) according to paragraphs 1-2 of the formula.

Examples to paragraph 4 of the formula - 1, 2, 4. Examples to paragraph 5 of the formula can be obtained by combinations of thermochromic layers described in examples 1-31 (to paragraphs 1-4, 6 of the formula) in accordance with Example 7 of the manufacture of a thermochromic device. Examples to paragraph 6 of the formula relating to thermochromic layers containing metal complexes with charge transfer are 1-4, 9, 17-19, 21.

Table 3 shows the formulations of the compositions and the optical properties of the material of the thermochromic layer made in the form of a gel.

Table 3 No.
ra Components Medium concentration
tions
components The optical density D, measured at a wavelength of λ at different temperatures Layer thickness mm Figure number wavelength λ, nm 20 ° C 70 ° C 85 ° C Examples to paragraph 7 of the formula 33 copolymer of acrylic acid and pentaerythritol polyallyl ethers (SAKAP) 24 g / l 620 0.09 0.85 1.10 0.65 21 dimethyl sulfoxide 61.1 mol % water 38.9 mol % 1320 0.11 0.37 0.45 22 NiCl ₂ 0.5 mol / l LiCl 4.4 mol / l 34 PVA 377 g / l 690 0.06 0.59 0.75 one - water 581 g / l glycerol 58 g / l CoCl ₂ · 6H ₂ O 0.05 mol / l LiCl 8.8 mol / l

Continuation of table 3 No.
ra Components Average component concentrations The optical density D, measured at a wavelength of λ at various temperatures. Layer thickness mm Figure number wavelength λ, nm 20 ° C 70 ° C 85 ° C 35 gelatin 15 g / l 520 0.16 0.70 0.86 0.25 one water 600 g / l CuBr ₂ · 2H ₂ O 1 mol / l 1375 0.56 1.44 1.70 2 KBr 1 mol / l

The use of SAKAP, PVA and gelatin to obtain thermochromic gels (in accordance with paragraphs 7-12 of the formula) in relation to the remaining examples (1-31) is similar.

Tables 4.1–4.6 give formulations of the compositions of the material of the thermochromic layer made in the form of an aqueous polymer film, including a water-soluble vinyl-based polymer.

Table 4.1 Example No. The components of the solution to obtain a layer The average concentration of the components of the solution, wt.% The optical density D, measured at a wavelength λ at various temperatures and a layer thickness of 0.2 mm The maximum change in the integral * light transmission (%) at an initial level of light transmission of 80% and when the temperature changes from 20 to 60 ° C with a layer thickness of 0.1 mm Layer transparency,% Wavelength λ, nm 20 ° C 70 ° C 85 ° C Example to paragraph 13 of the formula 36 PVA 7.7 680 0.1 1.2 1.6 35 80 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 isopropanol 35.6 water 53.4 glycerol 1.0

Here and in Tables 4.1-4.4, the integral (over the spectrum) light transmission of the material T _integr is determined by the total (over the spectrum) decrease in the eye response to the light flux, after its attenuation by passage through the material. In the calculation, it is necessary to take into account the spectral sensitivity function of the eye (the visibility function φ (λ)) and the spectral distribution function of the energy of the light source (Sun) E (λ), which are tabulated, for example, in (D. Kay, T. Laby. Physicist-experimenter . - M., 1949, p. 187). The calculation is carried out according to the formula:

,

,

where T (λ) is the experimental material transmission curve as a function of wavelength; dλ is the wavelength differential.

Table 4.2 No.
ra The components of the solution to obtain a layer The average concentration of the components of the solution, wt.% The maximum change in integrated light transmission at an initial light transmission level of 80% and when the temperature changes from 20 to 60 ° C Layer transparency,% Layer thickness mm Examples to paragraph 13 of the formula 37 PVA 7.4 38 85 0.094 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 isopropanol 12.8 water 72.9 glycerol 1.0 formalin 3.6

Continuation of table 4.2 No.
ra The components of the solution to obtain a layer The average concentration of the components of the solution, wt.% The maximum change in integrated light transmission at an initial light transmission level of 80% and when the temperature changes from 20 to 60 ° C Layer transparency,% Layer thickness mm 38 PVA 7.7 35 82 0.098 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 n-propanol 35.6 water 53.4 dibutyl phthalate 1.0 39 PVA 7.7 37 82 0.094 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 n-propanol 13.4 water 75.6 ethylene glycol 1.0 40 PVA 7.7 32 80 0.1 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 ethanol 35.6 water 53.4 formamide 1.0 41 PVA 7.7 31 80 0.1 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 ethanol 13.4 water 75.6 urea 1.0 42 PVA 7.7 35 80 0.178 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 isopropanol 35.6 water 53.1 glycerol 1.0

Continuation of table 4.2 No. at measure The components of the solution to obtain a layer The average concentration of the components of the solution, wt.% The maximum change in integrated light transmission at an initial light transmission level of 80% and when the temperature changes from 20 to 60 ° C Layer transparency,% Layer thickness mm 43 * PVA 7.7 35 78 0.178 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 isopropanol 35.6 water 53.1 glycerol 1.0 44 * PVA 7.7 37 78 0.178 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 isopropanol 35.6 water 53.4 glycerol 1.0 45 * PVA 7.7 35 80 0.178 CoCl ₂ · 6H ₂ O 1.7 LiCl 0.6 isopropanol 35.6 water 53.4 glycerol 1.0 * cooking time was 1.5 hours

In example 42, PVA grade A is used with an acetate group content of 10-15%; in example 43 - PVA 16/1 with a content of acetate groups of 0.8-0.2%; in example 44 - PVA 40/2 with a content of acetate groups of 2%; in example 45 - PVA 9/3 with a content of acetate groups of 3%.

Table 4.3 Example No. The components of the solution to obtain a layer The average concentration of the components in the layer, wt.% Type of basis / transparency,% Type of coating / transparency,% The maximum change in integrated light transmission at an initial light transmission level of 80% and when the temperature changes from 20 to 60 ° C. Layer Thickness 0.1 mm The transparency of the device,% Examples to paragraph 13 of the formula 46 PVA 67.8 PET / 92 PET / 92 eighteen 68 CoCl ₂ 8.7 LiCl 3.5 ethanol 2.1 water eleven glycerol 6.1 47 PVA 57.1 PE / 90 PET / 92 eighteen 62 CoCl ₂ 15.8 LiCl 5.4 n-propanol 4.0 water 6.1 glycerol 11.6 48 PVA 62.5 PP / 90 PET / 92 28 79 COCl ₂ 12.2 LiCl 4.4 isopropanol 4.8 water 7.2 glycerol 8.9 49 PVA 62.5 Cellulose acetate
over / 91 Cellulose Acetyl / 91 35 83 CoCl ₂ 12.2 LiCl 4.4 isopropanol 4.8 water 7.2 dibutyl phthalate 8.9 fifty PVA 62.5 Cellulose acetate
over / 91 PVB / 91 36 80 CoCl ₂ 12.2 LiCl 4.4 isopropanol 4.8 water 7.2 ethylene glycol 8.9

Continuation of table 4.3 Example No. The components of the solution to obtain a layer The average concentration of the components in the layer, wt.% Type of basis / transparency,% Type of coating / transparency,% The maximum change in integrated light transmission at an initial light transmission level of 80% and when the temperature changes from 20 to 60 ° C. Layer Thickness 0.1 mm The transparency of the device,% 51 PVA 62.5 Cellulose acetate
over / 91 PVA / 91 thirty 79 CoCl ₂ 12.2 LiCl 4.4 isopropanol 4.8 water 7.2 formamide 8.9 52 PVA 62.5 Cellulose acetate
over / 91 PVE / 91 29th 78 CoCl ₂ 12.2 LiCl 4.4 isopropanol 4.8 water 7.2 urea 8.9 53 PVA 58.9 PET / 92 PET / 92 36 83 CoCl ₂ 11.5 LiCl 4.1 isopropanol 4.5 water 6.8 glycerol 8.4 formalin 5.8

Table 4.4 Example No. The components of the solution to obtain a layer The average concentration of the components in the layer, wt.% The presence of 2 layers made of glass The maximum change in integrated light transmission at an initial light transmission level of 80% and when the temperature changes from 20 to 60 ° C. Layer Thickness 0.1 mm The transparency of the device,% Examples to paragraph 13 of the formula 54 PVA 63.0 + 19 80 CoCl ₂ 11.5 LiCl 3.7 ethanol 1.7 water 9.5 glycerol 10.6 55 PVA 58.1 + 19 67 COCl ₂ 19.0 LiCl 6.3 n-propanol 4.0 water 6.1 glycerol 6.5 56 PVA 60.6 + 36 75 CoCl ₂ 15.2 LiCl 5.0 isopropanol 2.7 water 7.9 glycerol 8.6 57 PVA 60.6 + 37 75 CoCl ₂ 15.2 LiCl 5.0 isopropanol 2.7 water 7.9 dibutyl phthalate 8.6 58 PVA 60.6 + 37 74 COCl ₂ 15.2 LiCl 5.8 isopropanol 2.7 water 7.9 ethylene glycol 8.6

Continuation of table 4.4 Example No. The components of the solution to obtain a layer The average concentration of the components in the layer, wt.% The presence of 2 layers made of glass The maximum change in integrated light transmission at an initial light transmission level of 80% and when the temperature changes from 20 to 60 ° C. Layer Thickness 0.1 mm The transparency of the device,% 59 PVA 60.6 + thirty 75 CoCl ₂ 15.2 LiCl 5.0 isopropanol 2.7 water 7.9 formamide 8.6 60 PVA 60.6 + 28 75 CoCl ₂ 15.2 LiCl 5.0 isopropanol 2.7 water 7.9 urea 8.6 61 PVA 57.1 + 33 77 CoCl ₂ 8.7 LiCl 3.7 isopropanol 1.0 water 9.1 glycerol 6.1 formalin 14.3

Table 4.5 Example No. Layer Components The average concentration of the components in the layer Optical density D measured at a wavelength λ at various layer temperatures Layer thickness mm Wavelength λ, nm 20 ° C 70 ° C 85 ° C Examples to paragraph 13 of the formula 62 PVA 67.8 wt.% 668 0.12 0.72 0.9 0.2 CoCl ₂ · 6H ₂ O 0.94 mol / l LiCl 1.41 mol / l water 9 wt.% glycerol 6.1 wt.% 63 PVA 67.8 wt.% 668 0.12 0.72 0.9 0.2 CoCl ₂ · 6H ₂ O 0.94 mol / l LiCl 1.88 mol / l water 14 wt.% glycerol 6.1 wt.% 64 PVA 67.8 wt.% 705 0.20 0.62 0.74 0.29 CoBr ₂ · 6H ₂ O 0.5 mol / l LiBr 4 mol / l water 4 wt.% glycerol 6.1 wt.% DMSO 7.2 wt.% 65 PVA 67.8 wt.% 668 0.20 0.59 0.71 one Co (NO ₃ ) ₂ · 6H ₂ O 0.5 mol / l LiBr 3 mol / l water 9 wt.% glycerol 6.1 wt.% trimethyl phosphate 0.92 wt.%

Table 4.6 Example No. Layer Components The average concentration of the components in the layer Optical density D measured at a wavelength λ at various layer temperatures Layer thickness mm Figure number Wavelength λ, nm 20 ° C 70 ° C 85 ° C Examples to paragraph 13 of the formula 66 PVA 67.8 wt.% 663 0.15 0.80 1.0 0.4 thirty CoCl ₂ · 6H ₂ O 0.92 mol / l LiCl 3 mol / l water 24 wt.% glycerol 6.1 wt.% pyridine 1.9 wt.% 67 PVA 67.8 wt.% 650 0.10 0.71 0.9 1.2 31 CoBr ₂ · 6H ₂ O 0.018 mol / l water 5 wt.% glycerol 6.1 wt.% pyridine 16 wt.% 68 PVA 67.8 wt.% 610 0.2 0.52 0.67 one - CoCl ₂ · 6H ₂ O 0.019 mol / l LiCl 0.6 mol / l water 5 wt.% glycerol 6.1 wt.% morpholine 16 wt.% 69 PVA 846 g / l 620 0.24 0.96 1.17 one 32 NiCl ₂ · 6H ₂ O 0.73 mol / l LiCl 6.96 mol / l water 0-5 vol.% 1420 0.26 0.41 0.45 33 glycerol 75.05 g / l DMSO 54.05 vol.% 70 PVA 846 g / l 680 0.18 1.20 1.54 0.3 34 Ni (NO ₃ ) ₂ · 6H ₂ O 0.73 mol / l LiBr 10 mol / l water 0-3 vol.% glycerol 75.05 g / l DMSO 54.05 vol.% 71 PVA 67.8 wt.% 600 0.25 0.68 0.81 0.5 35 CuBr ₂ 0.3 mol / l LiBr 2.3 mol / l water 20 wt.% 1370 0.29 0.69 0.80 36 glycerol 6.1 wt.%

Continuation of table 4.6 Example No. Layer Components The average concentration of the components in the layer Optical density D measured at a wavelength λ at various layer temperatures Layer thickness mm Figure number Wavelength λ, nm 20 ° C 70 ° C 85 ° C 72 from PVA 67.8 wt.% 520 0.13 0.39 0.44 0.128 37 l CuBr ₂ 0.3 mol / l about LiBr 200 g / l th water 20 wt.% one glycerol 6.1 wt.% from PVA 67.8 wt.% 667 0.08 0.39 0.47 l CoCl ₂ · 6H ₂ O 0.94 mol / l about LiCl 59.2 mol / l th water 3 wt.% 2 glycerol 6.1 wt.%

Examples to paragraph 14 of the formula are examples 66-68 (table 4.6).

Continuation of table 4.6 Example No. Layer Components The average concentration of the components in the layer The optical density D, measured at a wavelength λ, at different temperatures of the layer Layer thickness mm Figure number Wavelength λ, nm 20 ° C 70 ° C 85 ° C Examples to paragraph 15 of the formula 73 PVA 67.8 wt.% 630 0.18 0.99 1.23 0.2 38 CoCl ₂ · 6H ₂ O 0.94 mol / l LiCl 3.9 mol / l water 31 wt.% glycerol 47 wt.% ethanol 2.1 wt.% picric acid 0.35 g / m ² Layer

The use of nitrophenols (concentration of 0.2-0.5 g / m ² film) to obtain thermochromic films (in accordance with paragraph 15 of the formula) in relation to other examples (36-68, 74) is similar.

An example to paragraph 16 of the formula is example 71.

The examples to paragraph 17 of the formula can be obtained by combinations of thermochromic layers described in examples 36-74 (to paragraphs 13-16, 18-20 of the formula) in accordance with Examples 6 and 7 of the manufacture of a thermochromic device.

Examples to paragraph 18 of the formula relating to thermochromic layers containing metal complexes with charge transfer, 70-72.

Examples to paragraph 19 of the formula are set forth in Example 5 of the manufacture of a thermochromic device.

Examples to paragraph 20 of the formula are examples 69, 70 and 74.

End of table 4.6 Example No. Layer Components The average concentration of the components in the layer The optical density D, measured at a wavelength λ at various layer temperatures. Layer thickness mm Figure number Wavelength λ, nm 20 ° C 70 ° C 85 ° C Example to paragraph 20 of the formula 74 PVA 67.8 wt.% 630 0.18 0.99 1.23 0.2 39 CoCl ₂ · 6H ₂ O 0.94 mol / l LiCl 3.9 mol / l water 31 wt.% glycerol 47 wt.% ethanol 2.1 wt.%

As can be seen from tables 2, 3, 4.1-4.6, a thermochromic material made from the presented examples of compositions has high thermochromic efficiency (D ⁷⁰ / D ²⁰ ), which is understood as the ratio of optical densities at a given wavelength achieved at high (60- 85 ° C) and low (20-25 ° C) temperatures, which is explained by the fact that the developed new thermochromic material contains water as an integral component, which is a strong field ligand, which is necessary to optimize the thermodynamic parameters of the thermochromic reaction transition in order to achieve high thermochromic efficiency. The use of water is also preferable from the point of view of environmental and fire safety of the production and operation of a thermochromic device.

The production technology of the inventive thermochromic device differs from the prototype production technology in simplicity and low cost by combining all stages of the synthesis of the thermochromic layer into one (mixing all components (solvents, transition and alkali and alkaline earth metal compounds, polymers and plasticizers)), followed by filling the gap between the substrates in the case of liquids and gels, and the manufacture and triplexing of the film in the case of a thermochromic device according to Option 3.

As can be seen from the examples, the ratio of D ⁷⁰ / D ²⁰ in most cases exceeds the highest results achieved in the prototype. For example, in the case of liquid (Table 2, examples 2, 3, 17, 28, figures 3, 4, 16, 27) and gel-like (made on the basis of the same liquids) thermochromic layers, a decrease in the initial level of light transmission T (~ 70-80 % at 20-25 ° C, which corresponds to an optical density of D = log (100 / T) = ~ 0.15-0.10) when the temperature rises to 65-70 ° C by ~ 7-8 or more (the optical density changes by ~ 7-10 or more times and is ~ 1) is achieved with a thermochromic layer thickness of 0.04-0.1 mm, while in the examples of the prototype (all examples of liquids from the description of the prototype, as well as Examples 189-214), such results tats are achieved only at thicknesses of 0.8 mm and more, which corresponds to the upper limit of the thickness of polyvinyl butyral films commonly used for automobile triplexes (0.4-1 mm).

This means that the thermochromic layer of the prototype device will contain extremely high concentrations of transition metal complexes and ligands, which, in principle, can lead to chemical instability of such systems and increase the light scattering of the device. Or, to increase the stability in the prototype devices, it will be necessary to use even thicker thermochromic layers, and in the device we declare, we have the opportunity to lower the concentration of transition metal compounds by a factor of ten. At the same time, the thickness of the thermochromic layer that optimally regulates the transmission of light and heat fluxes will still remain less than 1 mm.

In the case of thermochromic layers, claimed according to Option 3 and described in examples 36-45, 49, 50, 53, 56-58 (Table 4.1-4.4), the decrease in the initial level of light transmission is ~ 70-80% (optical density 0.1-0.15 at 20–25 ° C) by a factor of ~ 12 or more (in this case, the transmission decreases to 6.7–4.5%, and the optical density increases to 1.2–1.35) with increasing temperature to 65–70 ° C, it is reached at thermochromic layer thicknesses of 0.1–0.2 mm , while in the examples of the prototype (Examples 189-214), the best results (change in optical density by 7-8 times) are achieved, mainly, with a thickness of 0.8 mm or more, which Meets the upper limit of the thickness of polyvinyl butyral films commonly used for automotive triplexes (0.4-1 mm). The higher efficiency of the thermochromic layers we have developed makes it possible to reduce the concentrations of transition metal compounds or the thickness of the thermochromic layer, which simplifies the process of manufacturing thermochromic devices, and also helps to reduce their light scattering and increase their chemical stability.

The advantage of performing a thermochromic layer in the form of a polymer film in the device we declare is the possibility of using standard industrial equipment and standard or simplified, compared with standard, technologies used both in the manufacture of film and in the manufacture of glass triplexes (for example, automobile triplex). In contrast to the thermochromic devices of the prototype, the simplification of the manufacturing process of the thermochromic device developed by us is achieved through the exclusive use of ready-made and readily available reagents, as well as combining all stages of the synthesis into one, which reduces to mixing all components and heating at temperatures of 60-100 ° C for relatively a short time (maximum - within 1 hour), followed by applying a film-forming composition to a substrate and drying to achieve optimal concentration s solvent.

The drawings show graphs of the optical density spectra of the thermochromic layer at two temperatures. The horizontal axis (abscissa axis) shows wavelengths in nanometers λ (nm), and the vertical axis (ordinate axis) shows the optical density of the thermochromic layer D = log (100 / T), where T is the transmission of the thermochromic layer. The spectra are reduced to an absorbing layer thickness of 1 mm. In all figures, spectra with lower optical densities (at the wavelength indicated in Tables 2, 3, 4.6) correspond to a temperature of 20 ° C, and spectra with large optical densities correspond to a temperature of 60 ° C, with the exception of Figures 19-23, 32 -34, for which the heating temperature was 50 ° C.

Figure 1 presents the absorption spectra in the visible range of the thermochromic material described in example 1 (Table 2) and example 35 (Table 3).

Figure 2 presents the absorption spectra in the near infrared (IR) range of the thermochromic material described in example 1 (Table 2) and example 35 (Table 3).

Figure 3 presents the absorption spectra in the thermochromic material described in example 2 (Table 2).

Figure 4 presents the absorption spectra of the thermochromic material described in example 3 (Table 2).

Figure 5 presents the absorption spectra of the thermochromic material described in example 4 (Table 2).

Figure 6 presents the absorption spectra of the thermochromic material described in example 7 (Table 2).

Figure 7 presents the absorption spectra of the thermochromic material described in example 8 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 9 (Table 2).

Figure 9 presents the absorption spectra of the thermochromic material described in example 10 (Table 2).

Figure 10 presents the absorption spectra of the thermochromic material described in example 11 (Table 2).

Figure 11 presents the absorption spectra of the thermochromic material described in example 12 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 13 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 14 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 15 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 16 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 17 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 18 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 19 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 20 (Table 2).

Figure 20 presents the absorption spectra of the thermochromic material described in example 21 (Table 2).

On Fig presents absorption spectra in the visible range of the thermochromic material described in example 22 (Table 2) and in example 33 (Table 3).

On Fig presents absorption spectra in the near infrared range of the thermochromic material described in example 22 (Table 2) and in example 33 (Table 3).

On Fig presents the absorption spectra of the thermochromic material described in example 23 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 25 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 26 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 27 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 28 (Table 2).

On Fig presents the absorption spectra of the thermochromic material described in example 32 (Table 2).

On Fig presents the absorption spectrum of a solution of picric acid (Table 2). The spectrum is reduced to a picric acid concentration of 0.01 mol / L and an absorbing layer thickness of 1 mm. The spectrum was measured at 20 ° C.

On Fig presents the absorption spectra of the thermochromic material described in example 66 (Table 4.6).

On Fig presents the absorption spectra of the thermochromic material described in example 67 (Table 4.6).

On Fig presents absorption spectra in the visible range of the thermochromic material described in example 69 (Table 4.6).

On Fig presents absorption spectra in the near infrared range of the thermochromic material described in example 69 (Table 4.6).

On Fig presents the absorption spectra of the thermochromic material described in example 70 (Table 4.6).

On Fig presents absorption spectra in the visible range of the thermochromic material described in example 71 (Table 4.6).

On Fig presents absorption spectra in the near infrared range of the thermochromic material described in example 71 (Table 4.6).

On Fig presents the absorption spectra of the thermochromic material described in example 72 (Table 4.6).

On Fig presents the absorption spectra of the thermochromic material described in example 73 (Table 4.6).

On Fig presents the absorption spectra of the thermochromic material described in example 74 (Table 4.6).

The manufacture of a thermochromic device is as follows:

Example 1. The manufacture of a thermochromic device according to option 1 in accordance with paragraphs 1-4 and 6 of the formula

The composition of the thermochromic layer is prepared (the formulations are shown in Table 2 (examples 1-32), for which all components are simultaneously mixed and the mixture is heated with stirring at 60-100 ° C for 15-30 minutes until the components are completely dissolved (until the precipitate disappears). The pre-fabricated single-chamber or multi-chamber double-glazed unit, the chambers of which are formed by glass sheets or polymer sheets with a transparency, preferably not less than 90%, and which can be strengthened by the gaps of the thickness of the gap, are filled with liquids when otovlennymi according to Embodiment 1, picking up the component concentration and layer thickness by calculation from the absorbance spectrum, to achieve the desired color and the degree of darkening when triggered, and sealed.

Based on the described single-chamber or multi-chamber sealed double-glazed window filled with thermochromic liquids, a window double-glazed window is assembled according to well-known technology, containing a gap filled with air or inert gas, as well as a low-emission coating (Low E), applied to protect one of the internal surfaces of the glass from damage . This design provides automatic control of the illumination of the room, as well as energy-saving effect when using the claimed thermochromic device as a window glass or structural glazing of walls.

Example 2. The manufacture of a thermochromic device according to option 2 in accordance with paragraphs 7-10, 12 of the formula

The composition of the thermochromic layer is prepared (the formulations are shown in Table 3 (Example 33)), for which all components, except for the copolymer of acrylic acid and polyallyl pentaerythritol esters (SAKAP), are simultaneously mixed and the mixture is heated with stirring at 100 ° C for 15-30 min until the components are completely dissolved (until the precipitate disappears). The resulting composition is cooled, SAKAP is added (in the amount indicated in Table 3 (Example 33)), mixed and poured at room temperature into a prefabricated single-chamber or multi-chamber double-glazed unit, the chambers of which are formed by glass sheets or polymer sheets with a transparency, preferably not less than 90 % and which can be hardened by clamps of the thickness of the gap, and seal. The concentrations of the components and the thickness of the layers are selected based on the need to achieve the desired color gamut and the degree of darkening when triggered.

Based on the described single-chamber or multi-chamber sealed double-glazed window filled with thermochromic gels, a window double-glazed window is assembled according to well-known technology, containing a gap filled with air or inert gas, as well as a low-emission coating (Low E), applied to protect one of the internal surfaces of the glass from damage . This design provides automatic control of the illumination of the room, as well as energy-saving effect when using the claimed thermochromic device as a window glass or structural glazing of walls.

Example 3. The manufacture of a thermochromic device according to option 2 in accordance with paragraphs 7-10, 12 of the formula.

All components in the original quantities (the formulation of the composition are shown in Table 3 (example 34)) are simultaneously mixed, then the mixture is refluxed for 1 hour until the components are completely dissolved (until the precipitate disappears). The resulting composition is cooled to a temperature corresponding to an acceptable viscosity (for example, 60 ° C), and poured into a prefabricated single-chamber or multi-chamber double-glazed unit, the chambers of which are formed by glass sheets or polymer sheets, preferably with a transparency of at least 90-92% and which can be reinforced with clamps of the thickness of the gap, and seal. The concentrations of the components and the thickness of the layers are selected based on the need to achieve the desired color gamut and the degree of darkening when triggered.

Based on the described single-chamber or multi-chamber sealed double-glazed window filled with thermochromic gels, a window double-glazed window is assembled according to well-known technology, containing a gap filled with air or inert gas, as well as a low emission coating (Low E).

Example 4. The manufacture of a thermochromic device according to option 2 in accordance with paragraphs 7-10, 12 of the formula

10-30 g of gelatin is added to 250 g of cold water and left to swell for 30-40 minutes, then the remaining components are added (the composition of the composition is shown in Table 3 (example 35)), mixed, still water is added or not added to the mixture until its content equal to 1000-1250 g (depending on the desired viscosity), then the resulting mixture is refluxed until the components are completely dissolved (until the precipitate disappears), then it is filtered, cooled to a temperature corresponding to an acceptable viscosity, and poured into a prefabricated single chamber minutes or multichamber glazing, which chamber are formed by sheets of glass or polymer sheets, preferably with transparency of not less than 90-92% and which can be hardened locks the gap thickness, and sealed. The concentration of the components and the thickness of the layers are selected based on the need to achieve the desired color gamut and the degree of darkening when triggered.

On the basis of the described single-chamber or multi-chamber sealed double-glazed window filled with thermochromic gels, a window double-glazed window is assembled using well-known technology similar to that described in Example 3.

Example 5. The manufacture of a thermochromic device according to option 3 in accordance with paragraphs 13-16, 18-20 of the formula.

All components in the original quantities (the formulation is shown in Tables 4.1-4.6 (examples 36-74)) are simultaneously mixed. Polyvinyl alcohol according to TU-6-05-041-548-74 is used as a water-soluble vinyl-based polymer. Then, the resulting mixture was refluxed for ~ 1 h until the components were completely dissolved (until the precipitate disappeared). After cooling, the resulting composition is either applied hot (depending on viscosity) using an extruder or by pouring through a die onto the surface of a glass sheet or a polymer sheet, preferably with a transparency of at least 90-92%. Drying is carried out at 60-90 ° C for 4 or more minutes until the desired shade of the material (magenta - in the case of examples 36-68, 72 (layer 2), 73, 74 (Table 4.1-4.6)). Drying is controlled spectrophotometrically by optical densities in the absorption bands of octahedral (400-550 nm) and tetrahedral (600-800 nm) cobalt (II) complexes (in the case of examples 36-68, 72 (layer 2), 73, 74 (Table .4.1-4.6)) and nickel (II) (in the case of examples 69, 70 (Table 4.6)), as well as in the charge transfer band of copper (II) complexes in the region of 500-650 nm (in the case of examples 71, 72 ( layer 1) (Table 4.6)). Then, lamination is performed using a second glass or polymer substrate with a transparency, preferably at least 90-92%, using a standard autoclave technology (Examples 36-68, 71-73 (Table 4.1-4.6)).

If necessary, reduce the triplexing temperature to values not exceeding 120 ° C, in order to prevent the destruction of highly efficient transition metal complexes that would be unstable at higher temperatures, and also in order to ensure energy savings, use the compositions of thermochromic layers shown in examples 69, 70, 74 (Table 4.6).

In order to obtain an additional color gamut with respect to the examples 36-71, 73, 74 (Table 4.1-4.6), the thermochromic layers can be combined into a multilayer triplex (Example 72 (Table 4.6)), in which the thermochromic layers can be separated layers of glass or polymer, or photo-, or thermo-, or chemically curable compositions based on mixtures of monomers and oligomers of unsaturated acid derivatives (according to paragraph 19 of the formula). If it is necessary to separately store the thermochromic layer (film) up to its subsequent triplexation (lamination), the thermochromic composition is applied to the surface with low adhesion, dried as described above, and then removed from the surface and stored, after having transferred the obtained layers with a material with low adhesion for the purpose protection of thermochromic layers from sticking.

On the basis of the described single-layer or multilayer thermochromic triplex, a window pane is assembled according to well-known technology, containing a gap filled with air or inert gas, and also including a low emissivity coating (Low E), applied to protect it from damage on one of the inner surfaces of the glass pane. This design provides automatic control of the illumination of the room, as well as energy-saving effect when using the claimed thermochromic device as a window glass or structural glazing of walls.

The energy-saving effect according to Option 3, as well as to Options 1 and 2 is achieved due to the fact that in the cold season (winter) a thermochromic layer optimized for “response” in the temperature range above the “comfortable” (20-25 ° C), remains highly transparent. Therefore, sunlight and heat freely penetrate through the window into the room, or when using the structure as a "structural" glazing (instead of plaster), they fall on the wall of the building and heat it. Since the heated wall and room emit heat in the far infrared range (10 μm), the low-emission coating does not let it out, providing energy saving. In the warm season (summer) when using this design as a window glazing, the thermochromic layer “works”, its transmission of light and heat decreases. In this case, automatic control of the illumination in the room is achieved, and all the solar energy absorbed by the thermochromic layer leads to its heating and is emitted in the far infrared range and, therefore, is reflected outward by a low-emission coating applied to one of the surfaces of the structure internal to the room. When using this design as a "structural" glazing in the summer, all solar energy absorbed by the thermochromic layer is reflected outside in the far infrared range, without creating a glare effect, in contrast to the well-known constant-reflection sunscreens.

Example 6. The manufacture of a thermochromic device according to option 3 (paragraph 17 of the formula).

Prepare a single-layer or multi-layer thermochromic triplex according to option 3, according to Example 5 of the manufacture of a thermochromic device. At the same time, at least one of the thermochromic layers is composed (made) in the form of a mosaic picture (or stained glass) of pieces of a thermochromic layer of different thermochromic efficiency and / or color, which provides a heterogeneous color of the thermochromic device and a change in the plot of the stained glass window depending on light and weather conditions.

Example 7. The manufacture of a thermochromic device according to option 1 (paragraph 5 of the formula), according to option 2 (paragraph 11 of the formula) and according to option 3 (paragraph 17 of the formula)

Prepare a single-layer or multi-layer thermochromic double-glazed window according to option 1 or 2, or a single-layer or multi-layer triplex according to option No. 3, according to Examples 1, 2-4 and 5, respectively, manufacturing a thermochromic device. At the same time, at least one of the substrates of the double-glazed unit (triplex) contains a transparent conductive coating providing heating of the thermochromic layer or thermochromic layers that is uneven in area, leading to a non-uniform in color coloring of the thermochromic device, which changes or does not change over time.

The presented examples of manufacturing the claimed product show that the technological process for manufacturing thermochromic devices is simplified in comparison with the known solutions in this field, and also show the special availability of creating finished products, including glass and polymer surfaces (substrates) of complex configuration (in liquid and "gel" options ), which is especially important in the manufacture of glass or polymer caps, lamps, etc. In the proposed variants of the new invention, as a rule, non-toxic or low-toxic substances are used. In particular, a reduction in the toxicity of production and operation is achieved, the process is simplified by reducing the number of stages of the synthesis of thermochromic layers, as well as reducing the duration and complexity of the drying process. The use of selected water-containing materials helps to reduce the synthesis temperature, providing the creation of strong field complexes, and allows you to create thermochromic layers with increased thermochromic efficiency D ⁷⁰ / D ²⁰ (the ratio of optical densities at temperatures of 70 ° C and 20 ° C) at thicknesses less than 0.1 mm.

The most profitable way of using the energy-saving light-regulating thermochromic glazing (ESTO) developed by us for energy saving purposes is its use as an external glazing as a part of a double-glazed window coated with Low E.

ESTO compositions are optimized in such a way that, at temperatures lower than 20 ° C (for example, in winter), the maximum influx of light and heat into the room is achieved, helping to reduce heating costs. In summer, at temperatures higher than 20 ° C, on the contrary, ESTO will reduce the flow of light and heat into the room, thereby reducing air conditioning costs and eliminating excessive lighting.

In general, the advantages of ESTO are: automatic autonomous mode for regulating solar radiation without energy consumption and regulation systems, power sources; lack of light reflection in the visible range (no glare effect); relative simplicity of production technology, low cost, non-toxicity and availability of raw materials.

The durability of ESTO is more than 10 years, and its cost is much lower in comparison with analogues that are closest in properties.

Claims (20)

1. Thermochromic device, comprising at least two light-transmitting substrates and at least one thermochromic layer, reversibly changing the transmission of light and heat flux when its temperature changes in the visible and / or near infrared regions of the spectrum, characterized in that thermochromic the layer is made of a thermochromic material, which is an aqueous liquid with transition metal complexes and with alkali and alkaline earth metal halides. 2. The thermochromic device according to claim 1, characterized in that the thermochromic material contains pyridine or morpholine. 3. The thermochromic device according to claim 1, characterized in that the thermochromic material further comprises nitrophenols. 4. The thermochromic device according to claim 1, characterized in that the thermochromic material is a non-toxic or low toxic liquid. 5. The thermochromic device according to claim 1, characterized in that it contains at least one layer of thermochromic material with a non-uniform color area. 6. The thermochromic device according to claim 1, characterized in that the thermochromic layer contains metal complexes with charge transfer. 7. Thermochromic device, comprising at least two light-transmitting substrates and at least one thermochromic layer, reversibly changing the transmission of light and heat flux when its temperature changes in the visible and / or near infrared spectral regions, characterized in that the thermochromic the layer is made of a thermochromic material, which is a light-resistant gel containing substances capable of forming gels, including in an aqueous medium, in particular at least one copolymer based on unsaturated acid and ether s pentaerythritol, or at least one polymer on a peptide basis, or at least one vinyl-based polymer and containing transition metal complexes. 8. The thermochromic device according to claim 7, characterized in that the thermochromic material contains pyridine or morpholine. 9. The thermochromic device according to claim 7, characterized in that the thermochromic material further comprises nitrophenols. 10. The thermochromic device according to claim 7, characterized in that the thermochromic material is a non-toxic or low toxic gel. 11. The thermochromic device according to claim 7, characterized in that it contains at least one thermochromic layer of thermochromic material with a non-uniform in color area. 12. The thermochromic device according to claim 7, characterized in that the thermochromic material contains metal complexes with charge transfer. 13. Thermochromic device, including or not including at least one light-transmitting substrate and at least one thermochromic layer, reversibly changing the transmission of light and heat flux when its temperature changes in the visible and / or near infrared spectral range, characterized in that the thermochromic layer is made of a thermochromic material, which is a water-containing polymer film made of a water-soluble vinyl-based polymer containing at least one plasticizer and complexes transition metals, including components of a solvent or plasticizer or halides, or a mixture thereof. 14. The thermochromic device according to item 13, wherein the thermochromic material contains pyridine or morpholine. 15. The thermochromic device according to item 13, wherein the thermochromic material further comprises nitrophenols. 16. The thermochromic device according to item 13, wherein the thermochromic material is a non-toxic or low toxic polymer composition. 17. The thermochromic device according to item 13, characterized in that it contains at least one thermochromic layer of thermochromic material with a non-uniform in color area. 18. Thermochromic device according to item 13, wherein the thermochromic material contains metal complexes with charge transfer. 19. The thermochromic device according to item 13, characterized in that it includes at least one layer between the thermochromic layer and the substrate and / or thermochromic layers made of a photo, or thermo, or chemically cured composition based on mixtures of monomers and oligomers of unsaturated acid derivatives. 20. The thermochromic device according to item 13, wherein the thermochromic layers are materials having glass transition temperatures not exceeding 120 ° C.

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