CN1536935A - Reflection type color development assembly containing electrochromic material - Google Patents

Abstract

The present invention relates to a reflective color display component including an electrochromic material. The electrochromic material contained in the reflective color display component can shift its absorption spectrum or radiation spectrum by applying an external electric current, thereby changing its color. The present invention improves the structure of the reflective color display component, so that the shortcomings of the prior art packaging components for encapsulating organic electrochromic materials, such as easy leakage or short product life, are overcome, and the application range of the product is further expanded, such as: optical filters, window display color-changing materials, conductivity indicator devices, mirrors, engine-driven vehicle rearview mirrors, building or vehicle glass and sunroofs, etc.

Description

A reflective color rendering component comprising electrochromic material

field of invention

The present invention relates to improved chromogenic components containing electrochromic materials.

Background technique

Electrochromic material is a concept put forward by Platt in 1961. It is pointed out by theoretical calculation that the application of external electricity will cause the shift of the absorption spectrum or emission spectrum of some organic dyes, resulting in a change in the color of the dye. In 1969, after Deb discovered the conductive color-changing properties of tungsten trioxide, electrochromic materials began to be widely used. Its material range includes organic materials and inorganic materials. At present, the organic model is based on the color-changing material of alogen-based (any derivative of aerologen-based in this article, which is commonly known as a derivative of viologenes in English, referred to as VSEM for short). The most widely used, inorganic type is based on tungsten oxide (WO ₃ ).

The currently commonly used electrochromic materials are solution-type or gel-type organic electrochromic materials, and the color components made by the complete sealing and packaging technology are most widely used. Generally, the packaging components used to encapsulate organic electrochromic materials are mostly made of double-layer conductive glass as the packaging medium, or supplemented by other adhesive substances. The disadvantages are that it is prone to liquid leakage and the product life cannot last. Furthermore, the discoloration rate of general organic electrochromic materials is greatly affected by the peripheral temperature and environment, thus greatly reducing its applicable range.

Known electrochromic materials, the structure of the reflective color components that are applicable to them can be roughly divided into two types, and their cross-sectional structures are shown in Figure 1 and Figure 2, of which Figure 1 and Figure 2 are shown The numbers and their functions and functions are described as follows:

11 is the metal protection film back paint, and main function is to protect the metal coating at the rear from being scratched or coming off.

12 is a metal coating, and its main function is to reflect light from the front to form a reflective color development component of an electrochromic material.

13 and 18 are glass substrates, the main function of which is to serve as the skeleton structure of the overall color rendering component without deformation, and can be transparent glass for general optical use or architectural use.

14 and 16 are transparent conductive films whose main function is to conduct electricity.

15 and 19 are the sealing ends of the colloid space, and their main function is to establish and maintain the required storage space for the solution-type/gel-type electrochromic materials.

17 is the storage space for the solution type/gel type electrochromic material. as well as,

21 and 25 are glass substrates, whose main function is to serve as the skeleton structure of the overall color rendering component without deformation, and are transparent glasses for general optical use or architectural use.

22 is a conductive metal coating, and its main function can also be used as a conductive film in addition to reflecting the front light.

23 and 27 are the sealing ends of the colloid space, and their main function is to establish and maintain the required storage space for the solution-type/gel-type electrochromic materials.

24 is a transparent conductive film whose main function is to conduct electricity.

26 is the storage space for the solution-type/colloid-type electrochromic material.

Figures 1 and 2 show reflective color components of known electrochromic materials, which have the following disadvantages in use:

1. The cavity for storing electrochromic materials is built up with general resin sheet, general two-component epoxy glue or conductive copper film, which is prone to problems such as liquid leakage and poor packaging.

2. If the transparent conductive film used in the color development component is directly in contact with the glass or directly coated on it without any protection during production, the effect of the conductive film will be reduced due to the acidic nature of the glass itself.

3. The performance characteristics of any organic electrochromic material used in the market are seriously affected by temperature, which greatly limits the application range of the material.

In view of the shortcomings and limitations in the application of the aforementioned structures, the present inventors specially developed the present invention, which uses the reflective color display component proposed by the present invention to improve the known shortcomings.

Contents of the invention

The present invention relates to a reflective color-developing component containing electrochromic materials. Its purpose is to solve the problems of easy liquid leakage and unsustainable product life in the old structure, and to break through the color change rate of the old electrochromic materials. It is easily affected by the peripheral temperature environment, which leads to the disadvantage of limited application range; and then it is made into components with tight seal and no leakage, long product life and wide application range.

The reflective color-developing component comprising the electrochromic material of the present invention can be divided into three implementations according to the structural section of its composition, and its structural section is shown in Fig. 3, Fig. 4 and Fig. 5, wherein Fig. 3 is Improvements proposed for the known structure of FIG. 1; FIG. 4 and FIG. 5 are improvements proposed for the known structure of FIG. 2.

Description of drawings

Fig. 1 and Fig. 2 are reflective color components containing electrochromic materials in the prior art.

FIG. 3 is an improved component of the present invention for the prior art shown in FIG. 1 .

Fig. 4 and Fig. 5 are components of the present invention after improvements to the prior art shown in Fig. 2 .

Fig. 6 is a functional schematic diagram of the storage space for the electrochromic material.

Figure 7 shows the applicable electrochromic working electrode materials and auxiliary electrode materials.

Figure 8 shows materials suitable for use in the ion-conducting electrolytic layer.

Figure 9 is a suitable structural substrate material.

Fig. 10 is a schematic diagram of the gap support structure.

Description of numbers in the figure:

11 Metal protective film back paint 12 Metal coating

13 Glass substrate 14 Transparent conductive film

15 colloidal space sealing end 16 transparent conductive film

17 Storage space for electrochromic materials 18 Glass substrate

19 Colloid space sealing end 21 Glass substrate

22 Conductive metal coating 23 Colloidal space sealing end

24 transparent conductive film 25 glass substrate

26 Electrochromic material storage space 27 Colloidal space sealing end

31 Uniform heating heating sheet 32 Metal reflective film protective paint

33 Reflective layer 34 Structural substrate of color rendering components

35 Isolation protection layer                                                                                                                                                                                                                           36 clearance support structure

37 Conductive layer 38 Storage space for electrochromic materials

39 Structural base material of color rendering component 310 Isolation protective layer

311 gap support structure 312 conductive layer

313 metal fixture                             314 metal fixture

41 Uniform heating heating sheet 42 Structural base material of color rendering components

43 Isolation protection layer 44 Conductive layer

45 Gap Support Structure 46 Structural Substrate of Color Display Components

47 Storage space for electrochromic materials 48 Isolation protective layer

49 Conductive layer 410 Gap support structure

411 reflective layer 412 metal fixture

413 Metal Fixture 51 Uniform Heating Heater

52 Structural base material of color rendering component 53 Isolation protective layer

54 Conductive layer 55 Clearance support structure

56 Conductive layer 57 Isolation protection layer

58 Storage space for electrochromic materials 59 Structural base material of color rendering components

510 Clearance Support Structure 511 Metal Fixtures

512 Metal fixture 61 Electrochromic working electrode or auxiliary electrode

62 Leading electrolytic layer 63 Electrochromic working electrode or auxiliary electrode

Detailed ways

The details of each structure in Fig. 3, Fig. 4 and Fig. 5 are as follows:

3 , 4 , and 38 , 47 and 58 in FIG. 5 are storage spaces for electrochromic materials, and their functions can be illustrated by the schematic diagram in FIG. 6 .

In Fig. 6, 61 and 63 are the working electrode and the auxiliary electrode of the electrochromic change, both of which can be in solid or solution state, or one in solid state and the other in solution state. One layer is an electrochromic working electrode, and the other layer is an auxiliary electrode, and the relative position therebetween is not limited. The electrochromic working electrode is the main material for providing color change. The auxiliary electrode can increase the optical density change of the component or provide a colorful color change. It can be the same or a different material. The material can be a metal, a metal oxide, or another complementary color-changing material (i.e., reduced color Materials that are mixed with color-changing materials and oxidation-state color-changing materials).

For example, suitable electrochromic working electrode materials and auxiliary electrode materials are shown in FIG. 7 . 62 is then the electrolytic layer of conduction, and its form can be solid or liquid state or be gel state. It has the function of storing ions, and the ions needed in the color changing process are provided by the ion-conducting electrolytic layer. The ion-conducting electrolytic layer can participate in the color change reaction, or simply be a place for ion storage. Its composition can be a single material, or a mixture of many different materials. Materials that may be suitable for the ion-conducting electrolytic layer are shown in FIG. 8 .

In schematic diagram 6, the structures 61, 62 and 63 representing the functions of 38, 47 and 58, the material properties represented in 38, 47 and 58 do not necessarily have corresponding and visual effects on the complete structure of the finished product. Recognizable and obvious delamination, which can be different physical properties such as interlacing, mutual dissolution or delamination, and its determinant factors are different depending on the materials used.

The 34 , 39 , 42 , 46 , 52 and 59 are all the structural substrates of the color development component (see additional description 1 below for details). In the color developing component, 34, 39, 46 and 59 are transparent or see-through structural substrates, while 42 and 52 may be transparent or see-through or non-see-through structural substrates. For example: 34 is transparent or colored see-through glass; 39 is transparent or colored see-through glass; or 46 is transparent or colored see-through polymer resin; or 42 is opaque silver metal. Applicable structural substrate materials through experiments are shown in FIG. 9 , but not limited thereto.

35 , 310 , 43 , 48 , 53 and 57 are isolation protective layers, whose main function is to isolate and protect the base material from being damaged by the conductive layer, or/and protect the conductive layer from being damaged by the structural base material. For example, a silicon dioxide protective film or an inert metal protective film (such as platinum, rhodium, gold, iridium and other inert metals) made by vacuum sputtering or vacuum evaporation, or a polymer made by gel deposition Protective film, or a protective film made by electrolysis/plating. But wherein: 35, 310, 48 and 57 need to be transparent or light-permeable isolating protective layers, and 43, 53 can be transparent or light-permeable or the isolating protective layers made of any material that is opaque. Regardless of whether it is a transparent or light-transmitting, or opaque isolation protective film, in any case, or when the environmental conditions change, it must meet the requirements that it will not produce any electrochemical reaction with the structural substrate or the conductive layer, or have an This condition occurs in the case of surface oxidation.

312, 37, 44, 49, 54 and 56 are conductive layers, which can be general metal conductive layers or transparent conductive layers, but they need not interact with the color-changing working electrodes (61 and 63 indicated in Fig. 6) Or lead the electrolytic electrode (ie 62 in FIG. 6 ) to generate an electrochemical reaction or a surface chemical reaction. For example, tin oxide amorphous structure conductive film made by vacuum sputtering method or vacuum evaporation method, indium-doped tin oxide metal embedded structure conductive film, fluorine-doped tin oxide amorphous structure conductive film; SnO2 conductive film, ZnO conductive film, CdO conductive film, CdIn2O4 conductive film, Cd2SnO4 conductive film, Zn2SnO4 conductive film and In2O3-ZnO conductive film, ZnO: Al conductive film or metal surface passivation conductive film (such as platinum, rhodium, gold, iridium, chromium and other metals) or polyaniline made by gel deposition method, polythiophene polymer conductive film, or metal conductive film made by electrolysis/electroplating method (such as platinum, rhodium, gold, iridium, chromium other metals). Or metal oxides (such as vanadium trioxide, nickel oxide, manganese dioxide, iridium trioxide, rhodium oxide) but 37, 312, 49 and 56 need to be transparent or see-through conductive films, while 44 and 54 are It is a transparent or transparent or opaque conductive film. Applicable collocation combinations are shown in Table 3, but the applicable materials are not limited to those shown in Table 3 if they meet the above requirements. Among them, indium-doped tin oxide metal intercalation conductive film and ZnO:Al conductive film, ZnO conductive film are most suitable for the transparent electrode.

Table three: Icons 37, 312, 49, 56 Applicable Materials Icon 44, 54 Applicable Materials Tin oxide amorphous structure conductive film. Indium-doped tin oxide metal embedded conductive film. Fluorine-doped tin oxide amorphous conductive film. SnO2 conductive film. ZnO conductive film. CdO conductive film. CdIn2O4 conductive film. Cd2SnO4 conductive film. Zn2SnO4 conductive film. In2O3-ZnO conductive film. ZnO: Al conductive film. Tin oxide amorphous structure conductive film. Indium-doped tin oxide metal embedded conductive film. Fluorine-doped tin oxide amorphous conductive film. SnO2 conductive film. ZnO conductive film. CdO conductive film. CdIn2O4 conductive film. Cd2SnO4 conductive film. Zn2SnO4 conductive film. In2O3-ZnO conductive film. ZnO: Al conductive film or metal surface passivation conductive film (such as platinum, rhodium, gold, iridium, chromium and other metals). Polyaniline and polythiophene polymer conductive film made by gel deposition method. Metal conductive film (such as platinum, rhodium, gold, iridium, chromium and other metals) made by electrolysis/electroplating. Metal oxides (such as vanadium trioxide, nickel oxide, manganese dioxide, iridium trioxide, rhodium oxide, ruthenium oxide.

311, 36, 410, 45, 55 and 510 are clearance support structures. Its main function is to maintain the relative parallel position of the structural substrates on both sides without changing the distance, and to form a closed inner room space to prevent the color-changing material from directly contacting with the outside air and causing product failure. According to experimental tests, it can be conductive film, metal film, or glass fine ball sand, PU ball sand, PP ball sand mixed with single-liquid epoxy resin or single-liquid UV glue. According to the experiment, it is most suitable to use glass fine ball sand mixed with epoxy resin glue. The supported range is from 5μ to 250μ. Its structure is shown in Figure 10.

PP ball sand is spherical fine sand made of polypropylene.

PU ball sand is spherical fine sand made of polyurethane.

UV glue is the abbreviation of ultraviolet light curing glue

313, 314, 412, 413, 511 and 512 are metal clamps, whose main function is to provide the conductive layer and the external power supply line as close as possible to achieve the best effect of conduction. The material selection is generally copper alloy plus surface treatment. Such as phosphor bronze, phosphor bronze, or brass, and nickel metal plating on the surface.

31, 41, and 51 are heaters that generate heat evenly, and their main function is to maintain the color rendering unit at a set fixed temperature during operation, so as to prevent the color rendering unit from affecting the overall product performance due to changes in external temperature conditions. Because the discoloration speed of most of the above-mentioned organic electrochromic materials is deeply affected by temperature.

For comparison with specific experimental data, it is assumed that at 25°C the time required for complete discoloration and complete fading of the color development component is 6-9 seconds, and at 60°C the time required for complete discoloration and complete fading of the color development component is 4-6 seconds , and the time required for complete color change and complete fading of color components at minus 5°C is 20 to 35 seconds. Therefore, with the establishment of the uniform heating plate, the reflective color components can have better performance.

The general heating sheet can be set at any temperature within the range of 25 to 95 degrees Celsius.

33 and 411 are the reflective layer of the electrochromic reflective color component, its main function is to reflect back the light penetrating through the transparent surface to form a reflective color component, and the reflective light can be visible light or invisible light Either one of infrared light or ultraviolet light or a mixture of multi-wavelength light. The reflective layer can be a reflective layer made by electroplating, vapor deposition or sputtering, or chemical gel deposition or chemical vapor deposition. For example, the reflective layer formed by the nickel film formed by the electroplating method, the aluminum metal reflective layer formed by the evaporation method, etc. The available materials are gold, silver, copper, nickel, platinum, palladium, aluminum, magnesium, rhodium, iridium, chromium, vanadium and the like. However, the material selected for 411 must meet the condition that it will not have any electrochemical reaction with the structural substrate or conductive layer, or surface oxidation will occur when any situation or external environmental conditions change.

32 is metal reflective film protective paint: its main function is to protect the reflective layer of the reflective color development component. To avoid scratches, oxidation, or any factors affecting the reflective layer. It can be general one-component paint or two-component paint or polymer coating or metal oxide or scratch-resistant metal film and other materials.

Additional information

(Explanation 1): The structural substrate referred to here refers to the material that can provide the physical structural support of the color-changing component system, and can provide a stable and balanced room space by itself rigid or with the help of a gap support structure, as a place to place the color Change the space of the material layer to form a color-changing component. It can be a rigid, non-deformable material, or a bendable material. Its material selection can be any smooth and flat surface, the average roughness from the highest to the lowest is less than 2 cm per square centimeter, and it is solid or supercooled at room temperature. and 1-g) or/and the isolation protective layer (i.e. 1-i and 1-j in the figure) have good adhesion to the substrate, or through the glued interface, the conductive thin layer or/and the isolation protective layer can be well fixed Conductive materials, or the structural substrate itself may also have conductive properties. The smooth surface can be a flat surface or a curved surface, and a surface deformed by stress is also acceptable. Here, the so-called gluing interface refers to the glue that can make two or more substances in the same state and different phases (for example, both are solid, but the two shapes and phases are different), such as UV glue, epoxy resin glue, etc. , acrylic glue, etc.

(Explanation 2): Here, "transparent or see-through" in the present invention means that there is a light transmittance of 15% to 95% in the spectral wavelength range of 4,000 angstroms to 7,000 angstroms.

(Explanation 3): The scope of application of the present invention: optical filters, window display color-changing materials, conductivity indicating devices, mirrors, vehicle rearview mirrors driven by engines, glass or skylights for buildings or vehicles.

To sum up, the reflective color component of the present invention, which includes electrochromic materials, has not been published or disclosed in domestic and foreign literatures and markets. It can indeed improve the known shortcomings, and fully complies with the elements of the invention patent.

Claims (16)

1. reflection-type color-developing component that comprises electrochromic material, comprise by what the form substrate of even heating heating plate, metallic reflective coating protective paint, reflector, color-developing component, isolated protective layer, conductive layer etc. formed successively and repeatedly organize structure, the one end is provided with metal fixture; Other has another that formed successively by conductive layer, isolated protective layer and color-developing component form substrate etc. repeatedly to organize structure, and the one end also is provided with metal fixture; Wherein, form the storage space of electrochromic material between these two conductive layers of repeatedly organizing structure, and the two ends of this electrochromic material storage space, the gap supporting construction is set respectively.

2. reflection-type color-developing component that comprises electrochromic material comprises by what even heating heating plate, color-developing component form substrate, isolated protective layer, conductive layer, reflector etc. formed successively and repeatedly organizes structure that the one end is provided with metal fixture; Other has another that formed successively by conductive layer, isolated protective layer, color-developing component form substrate etc. repeatedly to organize structure, and the one end also is provided with metal fixture; Wherein, the storage space that forms electrochromic material between the conductive layer of structure is repeatedly organized in the last reflector of repeatedly organizing structure and back one, and the two ends of this electrochromic material storage space, and the gap supporting construction is set respectively.

3. reflection-type color-developing component that comprises electrochromic material comprises by what even heating heating plate, color-developing component form substrate, isolated protective layer, conductive layer etc. formed successively and repeatedly organizes structure that the one end is provided with metal fixture; Other has another that formed successively by conductive layer, isolated protective layer, color-developing component form substrate etc. repeatedly to organize structure; Wherein, this two repeatedly organizes the storage space that forms electrochromic material between the conductive layer of structure, and the two ends of this electrochromic material storage space, and the gap supporting construction is set respectively.

4. as comprising the reflection-type color-developing component of electrochromic material as described in claim 1 or 2 or 3, wherein this electrochromic material storage space comprises electrochromism work electrode and auxiliary electrode, therebetween and be provided with the diversion electrolyte layers; This electrochromism work electrode and auxiliary electrode the two, can all be solid-state or all be solution state, or one be solid-state that another person is a solution state.

5. as comprising the reflection-type color-developing component of electrochromic material as described in the claim 4, wherein this electrochromism work electrode and auxiliary electrode the two, can be identical or different material, this material can be metal, metal oxide or is another complementary look change material.

6. as comprising the reflection-type color-developing component of electrochromic material as described in the claim 4, this diversion electrolyte layers wherein can be solid-state or liquid or is gel state, and it has the effect of storage of ions.

7. as comprising the reflection-type color-developing component of electrochromic material as described in claim 1 or 2 or 3, wherein the form substrate of this color-developing component can optionally be transparent form substrate that maybe can have an X-rayed, that maybe can not have an X-rayed.

8. as comprising the reflection-type color-developing component of electrochromic material as described in claim 1 or 2 or 3; wherein this isolated protective layer is for utilizing formed silicon dioxide protective film of vacuum splashing and plating method or vacuum vapour deposition or inert metal diaphragm; or utilize the formed polymer protective film of gel deposition method, or utilize the formed diaphragm of electrolysis/galvanoplastic.

9. as comprising the reflection-type color-developing component of electrochromic material as described in claim 1 or 2 or 3, wherein this conductive layer can be the common metal conductive layer or is transparency conducting layer.

10. as comprising the reflection-type color-developing component of electrochromic material as described in claim 1 or 2 or 3, the wherein effect of this each gap supporting construction, be to keep the opposing parallel position of both sides form substrate, make it not because of distance changes, and form airtight electrochromic material storage space.

11. as comprising the reflection-type color-developing component of electrochromic material as described in the claim 10, wherein this gap supporting construction can be conductive glue slice, metallic film or mix and form with single-liquid type epoxy or single liquid UV glue for the thin ball sand of glass, PU ball sand, PP ball sand.

12. as comprising the reflection-type color-developing component of electrochromic material as described in the claim 11, wherein the scope that supported of this gap supporting construction is between 5 μ～250 μ.

13. as comprising the reflection-type color-developing component of electrochromic material as described in claim 1 or 2 or 3, this each metal fixture wherein is material and through surface treatment with the copper alloy.

14. as comprising the reflection-type assembly of electrochromic material as described in the claim 13, wherein this copper alloy is phosphor-copper, phosphor bronze or brass.

15. as comprising the reflection-type color-developing component of electrochromic material as described in the claim 13, wherein this copper alloy surface is electroplate with the nickel metal.

16. as comprising the reflection-type color-developing component of electrochromic material as described in claim 1 or 2 or 3, wherein evenly heating plate heating setpoint temperature of heating in 25～95 degrees centigrade of scopes.

Images