TW201920596A - Article for production of or use in an electrochromic device - Google Patents

Abstract

The present invention relates to compositions (also referred to as inks) comprising electrochromic nanoobjects, to an article for production of or use in an electrochromic device, to a process for producing said article and to a process for preconditioning a multilayer structure for production of or use in an electrochromic device.

Description

Manufacturing of electrochromic devices or articles used in them

The present invention relates to a composition (also referred to as an ink) containing an electrochromic nano-object, the manufacture or use of an electrochromic device, a method of manufacturing the same, and a pretreatment of the electrochromic device. The method of multilayer structure among them.

An electronic device such as an optoelectronic device or an electrochromic device usually contains a functional layer, which includes nano-objects, such as nano-objects including electrochromic materials. US 8,593,714 B2 discloses an electrochromic device comprising a pair of electrodes separated by an electrolyte layer, wherein one of the electrodes includes an electrochromic material, an ion conductive adhesive, and a conductive nanowire. More specifically, the electrode contains particles that are electrochromic and bound to an ion-conductive binder. This electrode also has a network of electronically conductive nanowires.

US 8,593,714 B2 does not provide detailed information on the manufacture of electrodes containing electrochromic materials, ion conductive adhesives and conductive nanowires, although this is not a significant issue, at least due to the large number of interactions that must be made in such electrodes Different components (electrochromic materials, nanowires, ionic conductors, adhesives) in order to meet different functions (electrochromic, electronic conduction, ion conduction, matrix construction). A large number of different ingredients can cause problems with regard to their chemical compatibility. In addition, in order to allow such electrodes to be manufactured favorably by printing or other wet processing techniques, a composition (also known as an ink) is needed in which, in addition to their constituents in a dissolved state, the insoluble constituents of the electrodes (electrolytic The particles of the discoloration material and the electronically conductive nanowires) are suspended. It is well known that suspensions of nano-objects have limited stability because suspended nano-objects tend to coalesce.

Ionic conductors commonly used in electrochromic composite electrodes, as disclosed in US 8,593,714 B2, are electrolytes containing cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ . Unfortunately, high concentrations of such electrolytes have an adverse effect on the stability of suspended nano-objects against coalescence and sedimentation. Therefore, the inks used to prepare electrochromic devices containing such electrolytes must be used shortly after preparation, and only low-concentration suspended nano-objects are possible to avoid coalescence and sedimentation. In order to promote the preparation of electrochromic composite electrodes by wet processing technology, it is desirable to increase the storage stability and concentration of suspended nano-objects in such inks.

The previous technology is also JP 2008 287001 A NAJAFI-ASHTIANI NAMED et al .: `` A dual electrochromic film based on nanocomposite of copolymer and WO ₃ nanoparticles: Enhanced electrochromic coloration efficiency and switching response '', JOURNAL OF ELECTROANALYTICAL CHEMISTRY, ELSEVIER, AMSTERDAM, NL, Volume 774, April 30, 2016 (2016-04-30), pages 14-21, XP029593937, ISSN: 1572-6657, DOI: 10.1016 / J.JELECHEM.2016.04.046 US 6,175,441 B1.

According to a first aspect of the present invention, there is provided a composition (A-0) comprising: (a) a nano-object comprising one or more electrochromic oxides selected from the group consisting of: a transition metal , Rare earth elements and Groups 12, 13 and 14 other than carbon (c) Carrier liquid with a boiling point below 120 ° C (d) One or more types of polymerizable part (e) One or more kinds of Agent for initiating free-radical polymerization of the one or more types of polymerizable moiety (f) optionally one or more organic polymers suspended or dissolved in the carrier liquid (g) having a boiling point of 120 ° C or more High aprotic organic liquid wherein the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ in the composition (A-0) is 2 ppm or less, preferably 0.02 ppm Or lower, preferably 0.002 ppm or lower.

As used herein, "ppm" means "parts per million" relative to the total weight of the composition.

The composition according to the invention is in the form of a suspension, also known as a slurry. In the case of certain technical applications, such compositions are also referred to as inks. The preparation of suspensions is known in the art. The term "suspension" means a dispersion, which contains a liquid continuous phase (sometimes referred to as the external phase ep in the literature) and at least one solid dispersed phase (sometimes referred to as the internal phase in the literature) ip). In forming a suspension of the composition according to the invention, the nano-object (a) forms a dispersed phase which is dispersed in the liquid external phase. The external liquid phase consists of the liquid components (c) and (g) as defined above and any components dissolved in these liquid components.

Surprisingly, it has been found that an electrochromic electrode obtained from an ink as described above (which contains almost no cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ ) can be subsequently used in a power-chromic device. Sufficient ionic conductivity in the multilayer structure manufactured or used therein. This is done by allowing the ions of the electrolyte comprising a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ as defined above to migrate or diffuse from the multilayer structure or other layers to the composite To achieve in the middle.

The ingredients of the composition according to the present invention will now be described in detail.

According to ISO / TS 27687: 2008 (as published in 2008), the term "nano-object" refers to one, two or three nano-scale external dimensions, that is, dimensions in the range of approximately 1 nm to 100 nm Objects.

According to ISO / TS 27687: 2008, nanometer objects with one nanometer-level external size, while the other two significantly larger external dimensions are generally called nanoplates. The external dimension of one nanometer corresponds to the thickness of the nanoplate. The two significantly larger sizes differ more than three times from the nanoscale size. The two larger external dimensions are not necessarily nanoscale. Another commonly used term for a nano-sized object with one nano-level external dimension and two other significantly larger external dimensions is "nano flakes."

According to ISO / TS 27687: 2008, nanometer objects with two nanometer-like external dimensions and a significantly larger third external dimension are generally referred to as nanofibers. The third significantly larger size is more than three times larger than the nano-sized size. The maximum external dimensions are not necessarily nanoscale. This maximum external dimension corresponds to the length of the nanofibers. Nanofibers usually have a nearly circular cross section. The section extends perpendicular to the length. The two external dimensions in the nanometer range are defined by the diameter of the circular cross section.

Conductive nanofibers are also called nanowires. Hollow nanofibers (irrespective of their electrical conductivity) are also called nanotubes. Nanometer objects with two nanometer-like external dimensions, while the third external dimension (length) is significantly larger (which is rigid (ie, non-flexible)) are often referred to as nanorods. Nano objects with two similar nano-level external dimensions, while the third external dimension (length) is significantly larger, and has a nearly rectangular cross section extending perpendicular to the length are commonly referred to as nanobelts.

According to ISO / TS 27687: 2008, all three external dimensions are of the nanometer class. The length of the longest axis and the shortest axis of a nanometer object are not significantly different. Nanometer objects are generally called nanoparticle. The difference between the length of the longest axis and the length of the shortest axis does not exceed three times.

Nanoparticles of approximately equal length (that is, the aspect ratio (longest: shortest direction) of all three orthogonal external dimensions close to 1) are commonly referred to as nanospheres.

Preferably, the nano-object of the component (a) of the present invention is a nano-particle. It is preferred that the nano particles are approximately equal in length, that is, the aspect ratio (longest: shortest direction) of all three orthogonal external dimensions is in the range of 1 to 2. Particularly preferred nano particles are nano spheres.

Particularly preferred nano particles are primary particles having an initial particle diameter of 1 nm to 100 nm, preferably 3 nm to 50 nm (measured by nitrogen absorption, X-ray diffraction or transmission electron microscopy). Nanoparticles having an initial particle diameter of less than 20 nm, more preferably less than 15 nm, more preferably 12 nm or less are preferred. According to DIN 53206-1: 1972-08, the term "primary particle" refers to an entity that can be discerned by an individual by means of light microscopy or transmission electron microscopy.

Advantageously, the nano-objects are nano-particles with a hydrodynamic size D ₉₀ in suspension of less than 100 nm (measured by dynamic light scattering or centrifugal deposition techniques).

The nano-objects (a) include one or more electrochromic oxides of an element selected from the group consisting of transition metals, rare earth elements, and Group 12, 13 and 14 elements other than carbon. More preferably, the nano-objects (a) are composed of one or more electrochromic oxides selected from the group consisting of transition metals, rare earth elements and Groups 12, 13 and 14 other than carbon element. As used herein, "group 12, 13, and 14 elements" refers to groups 12, 13, and 14 of the periodic table of elements according to the IUPAC notation.

When a voltage is applied to an electrochromic material, the electrochromic material is characterized by its ability to reversibly and continuously change its optical properties (see Claes G. Granqvist, Solar Energy Materials & Solar Cells 99 (2012) 1-13). This ability is also referred to herein as the "electrochromic effect". When electrons are transferred to or away from the electrochromic material, a change in the light absorption of the electrochromic material occurs. Some electrochromic materials have the property of exhibiting a change in color (within the visible range of the electromagnetic spectrum), reproduction, or bleaching, such as by electron transfer (redox) methods or by sufficient electrochemical potential (see Mortimer, RJ : "Electrochromic materials", Annu. Rev. Mater. Res. 2011, 41: 241-68). However, as used herein, the term "electrochromic material" is not limited to materials that exhibit a change in color (ie, within the visible range of the electromagnetic spectrum), reproduce, or bleach. Therefore, materials that change light absorption without visible color changes, for example, in the UV or IR range of the electromagnetic spectrum are also referred to herein as "electrochromic."

Electrochromic metal oxides are known in the art, see, for example, Mortimer, RJ: "Electrochromic materials", Annu. Rev. Mater. Res. 2011, 41: 241-68 and Granqvist, CG: "Oxide electrochromics: An introduction to devices and materials ", Solar Energy Materials & Solar Cells 99 (2012) 1-13.

Preferably, the nano-objects (a) include or consist of Ti, Ni, Zn, Y, Zr, Nb, Mo, Cd, Ce, Hf, Ta, W, Ag, La, Pr, Nd, Sm, Eu , Si, Sn, Pb, In, V and Ir, one or more types of electrochromic oxide composition. More preferably, the nano-objects (a) are nano-particles (as defined above), including, preferably, Ti, Ni, Zn, Y, Zr, Nb, Mo, Cd, Ce, Hf, Ta , W, Ag, La, Pr, Nd, Sm, Eu, Si, Sn, Pb, In, V, and Ir, one or more types of electrochromic oxide composition.

More preferably, the nano-objects (a) comprise one or more nickel oxides, preferably consist of one or more nickel oxides, or comprise one or more tungsten oxides, preferably consist of one or more tungsten oxides .

Particularly preferably, the nano-objects (a) are nano-particles containing one or more nickel oxides, preferably consisting of one or more nickel oxides, or containing one or more tungsten oxides, preferably consisting of one Nanoparticles composed of one or more tungsten oxides.

The preparation of nano-objects (a) comprising one or more electrochromic metal oxides is known in the art. For example, the nano-objects (a) are nano-particles synthesized by a gas phase pyrolysis method, preferably flame spray synthesis. Such nano particles are commercially available.

In some cases, it is preferred that the composition further comprises (b) one or more metal salts of formula (I) (M ^{a +} ) _z (Z ^b- ) _y (I), where M ^{a +} represents a metal cation, Z ^{b -} represents the corresponding salt anion, a is 2, 3, 4 or 5, b is 1, 2 or 3, z is the least common multiple of a and b, divided by ay is the least common multiple of a and b, divided by b.

Therefore, when a is 2 and b is 1, z is 1 and y is 2.

Therefore, when a is 2 and b is 2, z is 1 and y is 1.

Therefore, when a is 2 and b is 3, z is 3 and y is 2.

Therefore, when a is 3 and b is 1, z is 1 and y is 3.

Therefore, when a is 3 and b is 2, z is 2 and y is 3.

Therefore, when a is 3 and b is 3, z is 1 and y is 1.

Therefore, when a is 4 and b is 1, z is 1 and y is 4.

Therefore, when a is 4 and b is 2, z is 1 and y is 2.

Therefore, when a is 4 and b is 3, z is 3 and y is 4.

Therefore, when a is 5 and b is 1, z is 1 and y is 5.

Therefore, when a is 5 and b is 2, z is 2 and y is 5.

Therefore, when a is 5 and b is 3, z is 3 and y is 5.

Preferred are metal salts of formula (I), where M represents a metal selected from the group consisting of transition metals, rare earth metals, Mg, Ca, Sr, Ba, Al, In, Ga, Sn, Pb, Bi, Zn , Cd and Hg, preferably selected from the group consisting of Ni, Cu, Zn, Al, In, Sc, La, Ce and Y or Z ^{b -} represents an anion selected from the group consisting of acetate, formate, lemon The acidity of acid, oxalate, nitrate, difluorophosphate and weakly coordinated anions is higher than that of 100% sulfuric acid.

More specifically, metal salts of formula (I) are preferred, where M represents a metal selected from the group consisting of transition metals, rare earth metals, Mg, Ca, Sr, Ba, Al, In, Ga, Sn, Pb, Bi, Zn, Cd, and Hg are preferably selected from the group consisting of Ni, Cu, Zn, Al, In, Sc, La, Ce, and Y and Z ^{b -} represents an anion selected from the group consisting of: acetate , Formate, citrate, oxalate, nitrate, difluorophosphate and weakly coordinated anions, the acidity of the corresponding acid is higher than that of 100% sulfuric acid.

In the metal salt of the preferred formula (I), Z ^{b -} is a weakly coordinated anion whose acidity of the corresponding acid is higher than that of 100% sulfuric acid, b = 1, z = 1 and y = a.

The term "weakly coordinated anion" is known in the art, see for example I. Krossing and I. Raabe, Angew. Chem. Int. Ed. 2004, 43, 2066-2090. Weakly coordinated anions (sometimes referred to as non-coordinating anions) are independently stable and do not have a tendency to donate electrons to an electron acceptor. These anions are prone to release their respective cations because their negative charge is delocalized on a large area of non-nucleophilic and chemically stable portions. The coordination capacity of each anion is limited by its most basic site; it will always assign a site to its most nucleophilic, spatially accessible part. Therefore, the acidity of the corresponding acid is a measure of the coordination capacity of the anion.

Acids with an acidity higher than that of pure sulfuric acid (100% sulfuric acid) are known in the art and are also referred to as "superacids".

As used herein, the term acidity refers to the equilibrium super strong acidity scale in the solvent 1,2-dichloromethane according to the equilibrium super acidic scale proposed by A. Kütt et al., J. Org. Chem. Vol. 76, Issue 2, 2011. Acidity, and can be determined by the method described herein.

A composition comprising a nano-object (a) and a metal salt (b) of formula (I) is described in a patent application filed on the same day by the same applicant as the present application. The anion Z ^- of a group of weakly coordinated anions having an acidity higher than that of 100% sulfuric acid.

Preferably, in the salt of formula (I), the anion Z ^-is selected from the group consisting of: (Z-1) [BX ₄ ] ^- , wherein X is selected from F, -OTeF ₅ , -CN And R (Z-2) [X ₃ BE-BX ₃ ] ^- , where X is selected from F, -OTeF ₅ , -CN and R and E is selected from F and CN (Z-3) [CB ₁₁ H _{12 ^- m} X _{m] -,} wherein X is selected from F, Cl, Br, I, and R; and in is an integer of m (Z-4) in the range of from 1 to 12 selected from the _{[CB 9 H 10 - m X} m] - , wherein X is selected from F, Cl, Br, I, and R; and in m is an integer selected from _{(Z-5) [AlX 4} ] within the range of 1 to 10 ^-, wherein X is selected from F, Cl, Br, I, -OR, R, and -OC {X ' _m R _{3 - m} }, where m is an integer selected from the range of 0 to 3, and X' is selected from F, Cl, Br, I, and -OR (Z -6) [X ₃ Al-E-AlX ₃ ] ^- , wherein X is selected from the group consisting of F, Cl, Br, I, -OR, R, and -OC {X ' _m R _{3 - m} }, where m is selected from An integer in the range of 0 to 3, and X 'is selected from F, Cl, Br, I, and -OR and E is selected from CN and F (Z-7) [EX ₆ ] ^- , where E is selected from P, As and Sb X are selected from F, CN, -OTeF ₅ and R (Z-8) [X ₅ E -A-EX ₅ ] ^- , wherein E is selected from P, As and Sb X are selected from F, CN , -OTeF ₅ and R; A is selected from F and CN (Z-9) [E (SO ₂ X ) _m ] ^- , where X is selected from F and R; E is selected from O, N and C; m is an integer selected from the range of 1 to 3; for E = O, m = 1; for E = N, m = 2; for E = C, m = 3; (Z-10) [N (OPR ₂ ) ₂ ] ^- (Z-11) [RSO ₄ ] ^- (Z-12) [ClO ₄ ] ^- (Z-13 ) N (CN) ₂ ^- wherein the anion selected from the group consisting of (Z-1) to (Z-13) consisting of the group of, R (if present) selected from the group consisting of the following group consisting _{of: - C n H 2n + 1} - _p F _p , where n is an integer selected from the range of 1 to 16 and p is an integer selected from the range of 0 to (2n + 1)-C _n H _{( 2n - 1 ) -p} F _p , where n is an optional An integer from 2 to 16 and p is an integer selected from the range of 0 to (2n-1)-C _n H _{( 2n - 3 ) -p} F _p , where n is an integer selected from the range of 2 to 16 And p is an integer selected from the range of 0 to (2n-3)-C ₆ H _{( 5 - n ) -p} F _p (CH _{3 - q} F _q ) _n , where n is selected from the range of 0 to 5 Integer, p is an integer selected from the range of 0 to 5 and q is an integer selected from the range of 0 to 3.

Preferably, in the salt of the formula (I), the cation M ^{a +} is selected from the preferred cations M ^{a +} as defined above, and the anion Z ^{b −} is selected from the preferred ones as defined above anion Z ^-.

Preferred anions are the anions (Z-9) as defined above, where X is F or C _n H _{2n + 1 - p} F _p , where n is an integer selected from the range of 1 to 16 and p is selected from 0 Integer in the range of (2n + 1).

Particularly preferred metal salts of the formula (I) are zinc diacetate, aluminum triacetate, yttrium triacetate, zinc dinitrate, aluminum trinitrate, yttrium trinitrate, bis (trifluoromethane) sulfoiminofluorene, and Fluoromethane) yttrium sulfonimide, aluminum bis (trifluoromethane) sulfonimide, lanthanum bis (trifluoromethane) sulfonimide, cerium bis (trifluoromethane) sulfonimide, bis (fluorosulfonium Sulfonium) imide nickel, bis (fluorosulfonyl) fluorenimide copper, bis (fluorosulfonyl) fluorenimide zinc, yttrium trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, trifluoromethane Lanthanum sulfonate, cerium trifluoromethanesulfonate and yttrium fluorosulfonate.

Metal salts of formula (I) as defined above are commercially available.

Preferably, the metal M of the metal salt of the formula (I) is different from the metal of the metal oxide in the metal oxide nano-object dispersed in the first suspension.

Without being bound by theory, the metal salt of formula (I), as defined above, acts as a dispersing aid for the nano-object (a), and is at least partially physically adsorbed on the surface of the nano-object (a), and can be Partially dissolved in the carrier liquid (c) of the suspension. The term "dispersion aid" as used herein means a substance that promotes the separation of suspended particles and is used to prevent or inhibit the agglomeration or sedimentation of such particles. In the context of the present invention, the term "dispersion aid" is used for a metal salt of formula (I) as defined herein, which stabilizes these suspended nano-objects (a). The use of certain metal salts of formula (I) as dispersants for nano-objects is described in WO 2016/128133 A1.

In the composition according to the invention, the surface of the nano-object (a) is at least partially coated with a physically adsorbed metal salt of the formula (I). As used herein, the term physical adsorption defines adsorption, where the force involved is an intermolecular force (van der Waals or electrostatic force) and it does not include significant changes in the electronic orbital pattern of the species involved. In the context of this application, "physical adsorption" means the adsorption of molecules or ions on a surface by electrostatic attraction or Van der Waals forces. Compared with chemical adsorption, physical adsorption molecules or ions do not change their chemical properties after adsorption. Therefore, by physical adsorption, neither covalent bonds are formed nor destroyed, nor are the atoms ionized or ionized nor deionized or undergo changes in their charge.

Coating the nano-object (a) with the one or more metal salts of formula (I) can be achieved by procedures known in the art, see for example WO 2016/128133 A1, which is incorporated herein by reference. . For example, the carrier liquid (c) and the nano-objects (a) are combined, for example, by mixing, ultrasonic processing, or ball milling. To the obtained initial suspension is added one or more metal salts (b) of formula (I) as defined above. Coating the nano-object (a) with one or more metal salts (b) of the formula (I) as defined above is performed at room temperature or during mixing after heating. Alternatively, the carrier liquid (c) and the one or more metal salts (b) of the formula (I) are combined, for example, by mixing. To obtain one or more initial solutions of the metal salt (b) of formula (I) in the carrier liquid (c), a nano-object (a) is added. Coating the nano-object (a) with one or more metal salts of the formula (I) as defined above is performed at room temperature or during mixing after heating.

Preferably, in the composition according to the present invention, the molar percentage of the metal ion M ^{a +} of the metal salt (b) of the formula (I) is in the range of 0.02 to 6 mol%, which is the total amount of each of the following Total:-Molar number of metal in metal ion M ^{a +} of metal salt (b) of formula (I)-and Molar number of metal in metal oxide of nanometer object (a).

If the Mohr percentage as defined above is less than 0.02%, the amount of the metal salt of formula (I) may not be sufficient to achieve the aforementioned effect of inhibiting the aggregation and sedimentation of the nano-object (a). If the Mohr percentage as defined above is greater than 6%, then in the electrochromic composite layer (see below) prepared from the composition according to the invention, one or more electrochromic compounds as defined above The amount of nano-object (a) may not be sufficient to achieve a proper electrochromic effect.

Especially if the nano-object (a) contains or consists of one or more nickel oxides, it is preferred that the metal salt (b) according to formula (I) is present in the composition according to the first aspect of the invention.

The carrier liquid (c) is only a vehicle for wet processing and is usually not held in a layer formed from the composition defined above.

Based on the polarity index of water, the polarity index of the carrier liquid (c) is> 4 according to the polarity scale (VJ Barwick, Trends in Analytical Chemistry, Vol. 16, No. 6, 1997, p. 293ff, Table 5) .

Preferably, the boiling point of the carrier liquid is lower than 120 ° C. The boiling point refers to a standard pressure of 101.325 kPa.

This carrier liquid is not polymerizable.

Preferably, the carrier liquid is selected from the group consisting of water, alcohol, amine, carbonic acid, ester, ketone, organic carbonate, polyether, sulfide, nitrile, and mixtures thereof. More preferably, the carrier liquid is selected from the group consisting of water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, third butanol, 2-butanone, 2-pentanone, methyl isobutyl ketone, dimethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxy-ethane, acetonitrile, pyridine, propionitrile, dimethylamine, Formic acid, acetic acid, ethyl acetate, dimethoxyethane, acetone, dimethyl carbonate, dioxane, trifluoromethyl methyl carbonate, ethyl methyl carbonate, 2-methyltetrahydrofuran, chloroform, and mixtures thereof.

The preferred carrier liquid is selected from the group consisting of water, ethanol, methanol, 2-propanol, 2-methyltetrahydrofuran, and mixtures thereof.

Especially if the nano-object (a) contains or consists of one or more tungsten oxides, preferably, the carrier liquid (c) is an organic liquid containing water and one or more of the above-mentioned boiling points below 120 ° C. mixture. In this case, it is more preferable that the above-mentioned component (b) is not present in the composition according to the first aspect of the present invention. Preferably, in this case, the carrier liquid is a mixture comprising water and one or more organic liquids selected from the group consisting of ethanol, methanol, 2-propanol, 2-methyl-tetrahydrofuran, and mixtures thereof.

The composition according to the invention further comprises (d) one or more types of polymerizable moieties.

The term "polymerizable moiety" as used herein includes polymerizable monomers and polymerizable oligomers.

The polymerizable portions (d) are dissolved in the liquid phase of the composition.

The polymerizable moieties (d) are polymer matrix precursors. In the method of preparing a layer from the composition defined above, the polymerizable portions form a polymer matrix by polymerizing on the surface of a solid substrate that has been coated with the composition defined above. In the layer obtained from the preferred composition according to the invention as defined above, the matrix binds and contains the nano-object (a) and optionally other ingredients (see below), filling the The voids between nano-objects (a), provide mechanical integrity and stability to the layers, and bond the layers to the surface of a solid substrate.

Preferably, the polymerizable moieties are selected from the group consisting of alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, vinyl chloride, vinyl fluoride, and propylene. Nitrile, vinylidene fluoride, vinylidene chloride, hexafluoropropylene, trifluoroethylene, tetrafluoroethylene, tetrahydrofuran, vinylpyrrolidone, polyisocyanate, combined with a polyol and / or a diamine.

Most preferably, the polymerizable moieties are copolymerizable monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates and the group consisting of hydroxyalkyl acrylates and hydroxyalkyl methacrylates. Preferably herein, the total amount of monomers selected from the group consisting of alkyl acrylate and alkyl methacrylate and the monomers selected from the group consisting of hydroxyalkyl acrylate and hydroxyalkyl methacrylate The molar ratio between the total amounts is in the range of 0.0002 to 50,000, preferably 0.4 to 400. Preferably, the polymerizable monomers are butyl acrylate and hydroxybutyl acrylate.

In the case where the polymerizable moiety (d) is polymerizable by free radical polymerization, the composition preferably further comprises (e) one or more initiators for initiating the free radical of the one or more types of polymerizable moiety polymerization.

Suitable initiators are known in the art and are commercially available. Preferably, the initiators are selected from the group consisting of compounds that decompose into free radicals when exposed to electromagnetic radiation.

Optionally, the composition according to the present invention further comprises (f) one or more organic polymers which are suspended or dissolved in the liquid external phase of the composition.

In the method of preparing a layer from a composition, the polymers are incorporated into a matrix as defined above.

The polymer (f) is dissolved in the liquid external phase of the composition, or in the case where it is insoluble in the liquid phase, it exists in the form of particles suspended in the liquid phase.

Preferably, the polymers (f) are selected from the group consisting of polyalkyl acrylate, polyalkyl methacrylate, polyhydroxyalkyl acrylate, polyhydroxyalkyl methacrylate, poly Vinyl chloride, polyvinyl fluoride, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polyhexafluoropropylene, polytrifluoroethylene, polytetrafluoroethylene, polytetrahydrofuran, polyvinylpyrrolidone, polyamine Formates, polyethylene oxide.

The composition according to the present invention further comprises (g) an aprotic organic liquid having a boiling point of 120 ° C or higher.

The boiling point refers to a standard pressure of 101.325 kPa.

In the composition according to the invention, the aprotic organic liquid (g) is mixed with a carrier liquid such that a common liquid phase is present in the composition defined above. Therefore, the carrier liquid (c) having a boiling point lower than 120 ° C and the aprotic organic liquid (g) having a boiling point 120 ° C or higher are selected to be miscible.

The aprotic organic liquid is selected to have a boiling point of 120 ° C or higher to allow the aprotic organic liquid (g) to remain in the combination defined by the above when heat is applied during the steps of removing the carrier liquid and polymerizing the polymerizable portion物 制备 的 层。 In the preparation layer.

The aprotic organic liquid (g) is not polymerizable.

The aprotic organic liquid (g) is selected to allow an electrolyte containing a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ^{+ to} migrate or diffuse into a layer prepared from the composition according to the present invention Dissolves and dissociates (for further details, see below).

Preferably, the aprotic organic liquid (g) is selected from the group consisting of organic carbonates, alcohols, amidines, carboxylic acid esters, ethers, polyethers, ketones, lactones, lactams, phosphates, amidines, Derivatives of sulfenyl, sulfonate, urea, thiourea, individual urea and thiourea, and mixtures thereof. Derivatives of the respective urea and thiourea are compounds in which one or more hydrogen atoms of the respective urea and thiourea are substituted. Examples are ethylene urea (2-imidazolinone) N, N'-dimethylpropaneurea, N- (2-hydroxyethyl) ethylene urea and corresponding thiourea derivatives.

Most preferably, the aprotic organic liquid (g) is selected from the group consisting of ethyl carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butyl carbonate, 1,3-butyl carbonate, 1,4-butyl carbonate, 2,3-butyl carbonate, ethylene glycol, diethylene glycol, diethyl carbonate, γ-butyrolactone, γ-pentyl Lactone, cyclobutane, dimethylarsine, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU) and mixtures thereof.

Particularly preferred are ethylene carbonate, fluorinated ethylene carbonate, 1,2-propylene carbonate, fluorinated 1,2-propylene carbonate, 1,3-propylene carbonate, and fluorinated carbonate 1, 3-propenyl esters and mixtures thereof.

Optionally, the composition according to the present invention further comprises (h) an electronically conductive nano-object, which does not include any compound selected from the group consisting of elemental oxides, which are selected from the group consisting of transition metals, rare earth elements, and 12th, 13th And a group of 14 group elements.

The electronically conductive nano-objects (h) form a dispersed phase which is dispersed in the liquid external phase of the composition according to the invention.

In a layer made from the preferred composition defined above, the electronically conductive nano-objects can form a conductive network of adjacent and overlapping electronically conductive nano-objects capable of carrying current (see below).

Preferably, the conductive nano-objects (h) have two outer dimensions in the range of 1 nm to 100 nm, and their third outer dimensions are in the range of 1 µm to 100 µm. Transmission electron microscopy. Generally, the two external dimensions are similar in the range of 1 nm to 100 nm, that is, the difference in size is less than three times. The third dimension of these conductive nano-objects is significantly larger, that is, it differs from the other two external dimensions by more than three times. Preferably, the conductive nano-objects (h) are nano-wires as defined in ISO / TS 27687: 2008 (published in 2008) (for details, see above).

Preferably, the electronically conductive nano-object (h) has a length in the range of 1 µm to 100 µm, preferably 3 µm to 50 µm, more preferably 10 µm to 50 µm, and a diameter of 1 nm to 100 nm, preferably The nanowires in the range of 2 nm to 50 nm, more preferably 15 nm to 30 nm, the length and diameter were determined in each case by transmission electron microscopy.

Preferably, the electronically conductive nano-objects are nano-wires, which include materials selected from the group consisting of silver, copper, gold, platinum, tungsten, and nickel, and selected from the group consisting of silver, copper, gold, platinum, An alloy of two or more metals consisting of tungsten and nickel. More preferably, the electronically conductive nano-objects are nano-wires, which are composed of a material selected from the group consisting of: silver, copper, gold, platinum, tungsten, and nickel, and selected from silver, copper, gold, platinum An alloy of two or more metals consisting of tungsten, nickel and nickel.

Contains ingredients (a), (c), (d), and (g), as defined above, and one, more, or all of the ingredients (b), (e), (f), and (h) The composition according to the present invention contains a single continuous liquid phase, which contains components (c) and (g) which are liquid at a temperature below 120 ° C at a standard pressure of 101.325 kPa, and is dissolved in the liquid phase Component (d) and (if present) component (e) and component (f) (if present, in the form of a soluble polymer). Component (a) and (if present) component (h) and component (f) (if present, in the form of polymer particles) each form a dispersed phase, which is dispersed in the liquid external phase.

Contains ingredients (a), (c), (d), and (g), as defined above, and one, more, or all of the ingredients (b), (e), (f), and The composition according to the present invention (h) can be used to prepare a composite layer, which can function as an electrochromic electrode in an electrochromic device.

Available from a composition according to a first aspect of the present invention (which contains the ingredients (a), (c), (d), (g) as defined above, and optionally one, more or all of the above) The composite layer of the defined components (b), (e), (f) and (h)) comprises-a matrix formed of one or more organic polymers, the one or more organic polymers being composed of a polymerizable polymerizable moiety (d ) Formation-and (a) nano-objects dispersed in the matrix, comprising one or more electrochromic oxides of elements selected from the group consisting of transition metals, rare earth elements, and 12th excluding carbon Groups 13, 13 and 14 elements (b) As appropriate, one or more metal salts (g) according to formula (I), an aprotic organic liquid having a boiling point of 120 ° C. or higher, wherein in the composite layer, selected from the group consisting of H The total concentration of cations of the group consisting of ⁺ , Li ⁺ , Na ^+, and K ⁺ is 100 ppm or less, preferably 20 ppm or less, and most preferably 2 ppm or less.

As the case may be (in the case where the composition according to the first aspect of the present invention comprises the component (h) as defined above as appropriate), the composite layer as defined above further comprises (h) electronic conductivity Nano-objects, which do not contain any compounds selected from the group consisting of elemental oxides, which are selected from the group consisting of transition metals, rare earth elements and Groups 12, 13 and 14 elements dispersed in one or more organic polymers Matters are formed within the matrix.

The term composite layer refers to a layer comprising a discrete nano-object (a) containing one or more electrochromic oxides as defined above, and components dispersed in a continuous phase (matrix) extending throughout the layer (g) and (h) as appropriate. The additional ingredients can be dispersed in the matrix, each fulfilling a specific function and interacting with other ingredients.

Within the composite layer, the matrix provides mechanical integrity and stability and combines and contains the components of the composite layer dispersed within the matrix as defined above. Without being bound by theory, the letter believes that nano-objects (a) containing one or more electrochromic oxides as defined above and (if present) electronically conductive nano-objects (h) as defined above (which are dispersed in Intra-matrix) forms a network extending throughout the composite layer, allowing electrons to travel toward and away from the nano-object (a). Without being bound by theory, in the composite layer, the aprotic organic liquid (g), as defined above, is limited to the pores extending through the matrix. When an electrolyte (see below) containing cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ from an external source enters the composite layer by migration or diffusion, the aprotic organic liquid (g) makes the electrolyte Dissolves and dissociates, thus providing a network to transport ions to and away from the nano-object (a).

Therefore, the composition according to the invention which can be used to prepare a composite layer as defined above comprises an organic polymer matrix precursor of the composite layer (in the form of a polymerizable part (d) and optionally a dissolved or suspended polymer ( f) form), and-components (a), (g) and optionally (h) of the composite layer to be dispersed in the organic polymer matrix as defined above, and-boiling points below 120 ° C The carrier liquid (c) does not become a component of the composite layer, but serves only as a vehicle for wet processing, and is substantially free of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ . This is a significant advantage, as electrolytes containing cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ have been found to have an adverse effect on the stability of suspended nanoobjects against coalescence and sedimentation. Accordingly, the present invention provides an ink comprising suspended nano-objects (a), wherein these inks have improved storage stability and allow an increase in the concentration of suspended nano-objects (a). In turn, sufficient ionic conductivity of the layer prepared from the composition according to the invention can be achieved when the electrolyte subsequently migrates or diffuses into the layer prepared from the composition according to the invention.

Preferably, in the composition (A-0) according to the first aspect of the present invention, (a) the total amount of these nano-objects containing one or more electrochromic oxides is 0.1% by weight to 20% by weight. %, Preferably 0.5% to 10% by weight, (b) the total amount of the salt of formula (I) in the range of 0% to 2% by weight, preferably 0% to 1% by weight, ( c) the amount of the carrier liquid is in the range of 70% to 99.5% by weight, preferably 88% to 99% by weight, (d) the total amount of the polymerizable portion is 0.005 to 7.0% by weight, preferably 0.21% by weight % To 2.5% by weight, (e) the total amount of these initiators is in the range of 0.00001% to 0.06% by weight, preferably 0.0001% to 0.05% by weight, (f) the total amount of these polymers is in In the range of 0% to 7.0% by weight, preferably 0.21% to 2.5% by weight, (g) the amount of the aprotic organic liquid having a boiling point of 120 ° C. or higher is 0.00009% to 1% by weight, preferably 0.005% by weight (H) the total amount of these electronically conductive nano-objects is in the range of 0% to 0.9% by weight, preferably 0% to 0.4% by weight, in each case with the composition Total weight, where The composition (A-0) are selected from the group consisting of H ^+, Li ^+, Na ⁺ and K ⁺ cations of the total concentration of the group consisting of 2 ppm or less, preferably 0.02 ppm or less, the best 0.002 ppm Or lower.

The concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ can be determined by means of pH measurement (H ⁺ ) and inductively coupled plasma optical emission spectroscopy (Li ⁺ , Na ⁺ , K ⁺ ) . The detection limit of this method is 30 ppt. This method is known in the art.

Preferably, in the composition, the ratio between (a) the total weight of the nano-objects comprising one or more electrochromic oxides and (h) the total weight of the electronically conductive nano-objects is between The range is from 1 to 1000, preferably from 5 to 300.

At weight ratios above 1000, the amount of electronically conductive nano-objects (h) in a composite layer prepared from a composition according to the invention may not be sufficient to have a significant effect on the electronic conductivity. On the other hand, at a weight ratio of less than 1, in the composite layer prepared from the composition according to the present invention, the amount of the nano-object (a) containing one or more electrochromic oxides as defined above It may not be sufficient to achieve a proper electrochromic effect.

More preferably, (d) the total weight of the polymerizable portions and (a) the nano-objects containing one or more electrochromic oxides (g) the aprotic organic liquid having a boiling point of 120 ° C or higher ( h) The ratio between the total weight of these electronically conductive nano-objects is in the range of 0.00002 to 70, preferably 0.018 to 4.95.

At a weight ratio of less than 0.00002, when the composite layer is prepared from the composition according to the present invention, the amount of the polymerizable portion in the composition may not be sufficient to form an ingredient (a), ( g) and (h). On the other hand, at a weight ratio higher than 70, the amount of components (a), (g), and (h) that determine the electrochromic effect and other important characteristics of the composite layer prepared from the composition according to the present invention may be Not enough to achieve the required characteristics.

More preferably, the ratio between (c) the weight of the carrier liquid and (a) the total weight of the nano-object comprising one or more electrochromic oxides is in the range of 3.5 to 995, preferably 8.8 to 198.

At weight ratios below 3.5, the fraction of solids in the composition is quite high, which can prevent coating of the composition by means of wet processing techniques. On the other hand, at a weight ratio higher than 995, the fraction of the carrier liquid that must be removed in the process of forming the composite layer is relatively large, and the processing becomes inefficient.

The composite layer as defined above, which is arranged on the surface of a solid substrate, can be obtained by a method comprising the following steps-by applying the composition according to the first aspect of the present invention to the surface of the solid substrate on the solid substrate Formation of a wet film on the surface of the substrate-removal of the carrier liquid of the composition from the wet film formed on the surface of the solid substrate (c)-polymerization of a polymerizable portion on the surface of the solid substrate (d ).

Particularly preferably, the composition applied to the surface of the solid substrate comprises (d) one or more polymerizable moieties, and (e) one or more initiators for initiating free-radical polymerization of the copolymerizable moieties. .

The polymerization of the polymerizable portion is preferably initiated by irradiation, particularly irradiation having a wavelength in the range of 360 nm to 420 nm in the presence of an initiator, and when exposed to the irradiation, the initiator is decomposed into free radicals. Suitable initiators are known in the art and are commercially available.

In some cases, the method further includes the step of annealing the layer formed on the surface of the solid substrate after polymerizing the polymerizable monomer.

The solid substrate includes one or more materials selected from the group consisting of glass, metal, transparent conductive oxide, and organic polymer, and is preferably composed of it.

In some cases, the surface of the solid substrate coated with the composition according to the invention comprises an electronically conductive material, preferably an optically transparent electronically conductive material. The preferred optically transparent conductive material is a transparent conductive oxide (TCO), preferably selected from the group consisting of ITO (indium-doped tin oxide), AZO (aluminum-doped zinc oxide), IGZO (indium-gallium-doped zinc oxide), GZO (gallium-doped zinc oxide), FTO (fluorine-doped tin oxide), indium oxide, tin oxide, and zinc oxide. In some cases, the surface of the solid substrate layer on which the composite layer is disposed comprises one or more metal electronic conductive materials, wherein the metal is preferably selected from the group consisting of Cu, Ag, Au, Pt, and Pd. Preferably, the metal at the surface of the solid substrate is in the form of an optically transparent structure, such as a fine grid or nanowires.

However, it has been found that in the case where the composition comprises a conductive nano-object (h) as defined above, the in-plane electrical conductivity of the composite layer prepared from the composition according to the invention is sufficiently high so that it can be omitted to provide The surface of a solid substrate of an electronically conductive material.

The solid substrate is preferably in a form selected from the group consisting of a foil, a film, a mesh, a frame, and a plate.

In some cases, the solid substrate includes an organic polymer and has a thickness in a range of 10 μm to 200 μm, preferably 50 μm to 150 μm.

In other cases, the solid substrate comprises glass and has a thickness in the range of 3 to 7 mm, preferably 4 to 6 mm, or in the range of 0.5 to 2.5 mm, preferably 0.7 to 2 mm.

Preferred types of glass are, for example, float glass, low-iron float glass, heat strengthened glass, and chemically strengthened glass. Optionally, the glass has a low-emissivity / low-e coating, a solar protection coating, or any other coating on the surface facing away from the composite layer.

Preferred organic polymers are selected from the group consisting of polymethyl methacrylate (PMMA, such as commercially available as Plexiglas ^™ ), polycarbonate (PC), polyethylene (PE), and low density polyethylene (LDPE). , Linear low density polyethylene (LLDPE), polypropylene (PP), low density polypropylene (LDPP), polyethylene terephthalate (PET), glycol modified polyethylene terephthalate, Polyethylene naphthalate (PEN), cellulose acetate butyrate, polylactide (PL), polystyrene (PS), polyvinyl chloride (PVC), polyimide (PI), polyoxypropylene ( PPO) and mixtures thereof. PET and PEN are particularly preferred.

Preferably, the solid substrate has a light transmittance of 80% or more as measured according to ASTM D1003 (Procedure A) published in November 2013.

Preferably, the composition applied to the surface of the solid substrate in the method according to the present invention is selected from the preferred compositions defined above according to the first aspect of the present invention. Preferably, the composition according to the invention is applied to the surface of the solid substrate by coating or printing, preferably by a coating technique selected from the group consisting of: roll-to-roll ), Roll-to-sheet, sheet-to-sheet, slot die, spray coating, ultrasonic atomization, dip coating and doctor blade coating, or by a group selected from the group consisting of Printing technology: inkjet printing, pad printing, offset printing, gravure printing, screen printing, gravure printing and board-to-board printing.

Preferably, the thickness of the wet film formed by applying the composition according to the present invention to the surface of the solid substrate is in the range of 1 µm to 250 µm, preferably 20 µm to 150 µm. This thickness is also called "wet thickness".

In the method according to the present invention as defined above, by exposing the wet film on the surface of the solid substrate to a range of 20 ° C to 120 ° C, preferably 40 ° C to 120 ° C, and most preferably 80 ° C to 120 ° C The internal temperature allows the carrier liquid to evaporate or volatilize to remove the carrier liquid with a boiling point below 120 ° C from the wet film.

The step of polymerizing a polymerizable portion on the surface of the solid substrate is performed after the step of removing the carrier liquid having a boiling point lower than 120 ° C from a wet film formed on the surface of the solid substrate. In some cases, in the step of polymerizing the polymerizable portion, the degree of dialogue of the double bonds in the polymerizable portion is significantly lower than 96%, preferably 90% or less, more preferably 80% or less, more It is preferably 70% or less, particularly preferably 60% or less, or 50% or less, and the polymerization is completed at a later stage, for example, when the surface of the composite layer facing away from the solid substrate is bonded to another layer ( (See below).

In some cases, after polymerizing the polymerizable portions on the surface of the solid substrate, a process including the following steps is performed-by applying the composition according to the present invention as defined above to a layer (where polymerizable Partially polymerized) to form a wet film,-remove the carrier liquid (c) of the composition from the wet film,-the polymerizable portions in the polymerized layer,-optionally after polymerizing the polymerizable monomer This layer is annealed and repeated at least once as appropriate.

Preferably, in a method of preparing a composite layer as defined above, the following components of the composition according to the first aspect of the present invention are applied to the surface of the solid substrate at the following amount per cm² of the surface: ( a) Nano-objects containing one or more electrochromic oxides as defined above in an amount of 0.05 mg / cm² to 6 mg / cm² (d) may be in an amount of 0.0007 mg / cm² to 13.3 mg / cm² Polymeric part (f) Amount of polymer optionally present in the amount of 0.0007 mg / cm² to 13.3 mg / cm² (g) Aprotic having a boiling point of 120 ° C. or higher in the amount of 0.0001 mg / cm² to 2.05 mg / cm² Organic liquid (h) An electrically conductive nano-object in the amount of 0.0009 mg / cm² to 6 mg / cm², optionally containing no nickel oxide, in the presence of electrons.

When the polymerizable moiety is a copolymerizable monomer selected from the group consisting of an alkyl acrylate and an alkyl methacrylate, and a copolymerizable monomer selected from the group consisting of a hydroxyalkyl acrylate and a hydroxyalkyl methacrylate, These single systems consisting of a group of free alkyl acrylates and alkyl methacrylates are coated in an amount of 0.0006 mg / cm² to 10.9 mg / cm² and are selected from hydroxyalkyl acrylates and hydroxyalkyl methacrylates These single systems of ester groups are applied in amounts of 0.0001 mg cm² to 2.4 mg / cm².

In a second aspect, the present invention relates to the manufacture of an electrochromic device or an article used therein, and a method of preparing such an article. As used herein, the term "electrochromic device" refers to a device that utilizes an electrochromic effect as defined above. Such devices include at least one electrode containing an electrochromic material, a counter electrode, and a separation layer sandwiched between the electrodes and electrically separating the electrodes. Electrochromic devices are used in particular as front and top elements, internal structures and design elements for buildings and vehicles, displays, visualization optics and electrochromic mirrors. A well-known type of electrochromic device is a so-called smart window. The term "smart window" is known in the art.

The article according to the second aspect of the present invention includes each of the following or consists of (A-1) a substrate, (A-2) a composite layer disposed on the surface of the substrate (A-1), and the composite layer ( A-2) comprises-a matrix formed of one or more organic polymers, and-and dispersed in the matrix: (a) a nano-object comprising one or more elements selected from the group consisting of Color-changing oxides: transition metals, rare-earth elements, and Group 12, 13 and 14 elements other than carbon (b) One or more metal salts (g) according to formula (I), if present, with a boiling point of 120 ° C or more High aprotic organic liquid wherein the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ in the composite layer (A-2) is 100 ppm or less, preferably 20 ppm Or lower, preferably 2 ppm or lower, and (B-1) a separation layer disposed on the surface of the composite layer (A-2) facing the substrate (A-1), the separation layer (B- 1) Contains-a matrix formed of one or more organic polymers-and (g ") an aprotic organic liquid having a boiling point of 120 ° C or higher dispersed in the matrix.

As used herein, "ppm" means "parts per million" with respect to the total weight of the composite layer (A-2).

Preferably, the solid substrate (A-1) comprises one or more materials selected from the group consisting of glass, metal, transparent conductive oxide, and organic polymer. The solid substrate is preferably in a form selected from the group consisting of a foil, a film, a mesh, a frame, and a plate. Preferably, the solid substrate is optically transparent, that is, exhibits a light transmittance of 80% or more as measured according to DIN EN 410. For other specific and preferred features of the solid substrate, refer to the disclosure provided above.

The thickness of the composite layer (A-2) disposed on the surface of the solid substrate (A-1) is in a range of 0.05 μm to 500 μm, preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 30 μm.

This separation layer (B-1) is almost electronically insulated, but allows ion flow. Without being bound by theory, in the separation layer (B-1), the aprotic organic liquid (g ''), as defined above, is limited to the pores extending through the matrix, thus providing a network for transporting ions road.

In the separation layer (B-1), preferably, the matrix is formed of an aprotic organic liquid (g) having the same organic polymer as the matrix in the composite layer (A-2) and having a boiling point of 120 ° C or higher (g '') Is the same as the aprotic organic liquid (g) in the first composite layer.

The thickness of the separation layer is preferably in the range of 0.05 µm to 1500 µm, preferably 0.05 µm to 1000 µm, and most preferably 1 µm to 800 µm. Thickness can be determined by profilometry, atomic force microscopy, or electron microscopy.

The object as defined above can be obtained by a method including the following steps-by the method described above, the composite layer (A-2) as defined above is prepared on the surface of the solid substrate (A-1), and -Place the separation layer (B-1) as defined above on the surface of the composite layer (A-2) facing away from the solid substrate.

Placing a separation layer (B-1) on the surface of the composite layer (A-2) facing away from the first solid substrate (A-1) includes the following steps-by applying to the surface a composition containing the following ( B-0) and the formation of a wet film (c '') on the surface of the composite layer, and optionally a carrier liquid (d '') having a boiling point below 120 ° C, one or more types of polymerizable portions, (e '') Optionally, one or more initiators are present for initiating the radical polymerization of the one or more types of polymerizable moiety (g'') aprotic organic liquid (i''having a boiling point of 120 ° C or higher ) At least one electrolyte, as appropriate, having a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ ,-in the case where the composition contains a carrier liquid (c '') having a boiling point below 120 ° C Next, a carrier liquid having a boiling point lower than 120 ° C. is removed from a wet film formed on the surface of the composite layer-a polymerizable portion in a layer formed on the surface of the composite layer.

In some cases, the composition (B-0) used to prepare the separation layer contains a carrier liquid (c ''). However, in the composition for placing a separation layer as defined above, it is advantageous to omit a carrier liquid as a wet processing vehicle, as compared to the above-mentioned combination for preparing a composite layer or a precursor layer thereof. The composition does not contain insoluble matter. Therefore, the step of removing the carrier liquid from the wet membrane can be omitted in preparing the separation layer.

Preferably, in the composition (B-0), the total amount of the carrier liquid (c '') is 0% by weight (d '') The total amount of the polymerizable portion is in the range of 65% to 94% by weight, (e '') The total amount of these initiators is in the range of 0.1% to 5% by weight. (g '') The amount of the aprotic organic liquid having a boiling point of 120 ° C or higher is 5% to 20% by weight. The ranges are based on the total weight of the composition (B-0) in each case.

In some cases (see below), the composition (B-0) further comprises (i '') at least one electrolyte having a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ , Wherein in the composition (B-0), the total concentration of the electrolytes is in a range of 0.5% to 15% by weight based on the total weight of the composition.

Regarding the preferred and specific carrier liquid (c ''), polymerizable portion (d ''), initiator (e ''), and aprotic organic liquid (g '') having a boiling point of 120 ° C or higher, as above In the case of the first aspect of the present invention, the carrier liquid (c), the polymerizable portion (d), the initiator (e), and the boiling point of the composition according to the first aspect of the present invention are 120 ° C. or more, respectively. The situation revealed by the high aprotic organic liquid (g) is equally applicable.

In the composition for preparing a separation layer, preferably, the polymerizable portion (d '') is the same as the polymerizable portion (d) in the composition for preparing a composite layer, and has a boiling point of 120 ° C or higher. The aprotic organic liquid (g '') is the same as the aprotic organic liquid (g) in the composition for preparing the composite layer.

If the composition for preparing a separation layer contains a carrier liquid, the step of polymerizing the polymerizable portion is after the step of removing the carrier liquid having a boiling point lower than 120 ° C from a wet film formed on the surface of the solid substrate. get on.

In some cases, in the step of polymerizing the polymerizable portion, the degree of dialogue of the double bonds in the polymerizable portion is significantly lower than 96%, preferably 90% or less, more preferably 80% or less, more It is preferably 70% or less, particularly preferably 60% or less, or 50% or less, and the polymerization is performed during bonding the surface of the separation layer facing away from the composite layer to another layer.

In some cases, after polymerizing the polymerizable portions on the surface of the composite layer, a process including the following steps is performed-by applying a composition as defined above to the layer (where the polymerizable portion is polymerized) A wet film is formed on the surface,-in the case that the composition contains a carrier liquid (c "), the carrier liquid having a boiling point lower than 120 ° C is removed from the wet film,-the polymerizable portions in the polymerized layer , And repeat at least once as appropriate.

Preferably, the composition for preparing the separation layer is applied to the surface of the composite layer by coating or printing, preferably by a coating technique selected from the group consisting of: roll-to-roll -roll), roll-to-sheet, sheet-to-sheet, slot die, spray coating, ultrasonic atomization, dip coating and doctor blade coating, or by selecting from the group consisting of Group printing technology: inkjet printing, pad printing, offset printing, gravure printing, screen printing, gravure printing and board-to-board printing.

In the method for placing a separation layer defined above, by exposing the wet film on the surface of the solid substrate to 20 ° C to 120 ° C, preferably 40 ° C to 120 ° C, and most preferably 80 ° C to 120 ° Remove the carrier liquid (c '') from the wet film (if present) at a temperature in the range of ° C.

Preferably, the composition for preparing the separation layer does not contain a carrier liquid (c ''), and the thickness of the wet film formed by applying the composition for preparing the separation layer to the surface of the composite layer is 0.05. µm to 1500 µm, preferably 0.05 µm to 1000 µm. This thickness is also called "wet thickness".

For further details on the placement of a separation layer on the surface of the composite layer defined above facing the first solid substrate, see the unpublished patent application with application number PCT / EP2017 / 055320.

The object as defined above is suitable for the manufacture or use of a multilayer structure for producing a electrochromic device by combining the object with a counter electrode as described below. The counter electrode is a second composite layer (C-2) disposed on the surface of the substrate (C-1), and the second composite layer (C-2) includes-a matrix formed of one or more organic polymers- And dispersed in the matrix: (a ') a nano-object comprising one or more electrochromic oxides of an element selected from the group consisting of a transition metal, a rare earth element, and a twelfth, Groups 13 and 14 elements, the one or more electrochromic oxides are different from the electrochromic oxides (b ') contained in the nano-object (a) of the first composite layer (A-2) as appropriate Or more aprotic organic liquids having a boiling point of 120 ° C or higher according to the metal salt (g ') of formula (I).

The second composite layer (C-2) disposed on the surface of the second solid substrate (C-1) can be obtained by a method as described above in the case of the first aspect of the present invention. In order to prepare the second composite layer (C-2), a composition (C-0) is used, the composition (C-0) comprising (a ') a nano-object comprising one or more selected from the group consisting of Electrochromic oxides of elements: transition metals, rare earth elements, and Groups 12, 13, and 14 elements other than carbon, the one or more electrochromic oxides are different from those used to prepare the first composite layer (A-2 The electrochromic oxide (b ') contained in the nano-object (a) of the composition (A-0), as the case may be, as defined above, the metal salt (c') according to formula (I) boiling point Carrier liquid (d ') below 120 ° C One or more types of polymerizable moiety (e') Optionally one or more initiators, which are used to initiate the radical polymerization of the one or more types of polymerizable moiety (f ') Optionally, one or more organic polymers (g') suspended or dissolved in the carrier liquid (g ') Aprotic organic liquids (h') with a boiling point of 120 ° C or higher, as appropriate Rice objects, which do not contain any compounds selected from the group consisting of elemental oxides, which are selected from Metals, rare earth elements and the second group 12, 13 and 14 elements of the group.

In some preferred items (as defined above), the separation layer (B-1) further comprises (i '') at least one electrolyte dissolved in the aprotic organic liquid (g ''), H ^+, cations of the total concentration of Li ^+, Na ⁺ and K ⁺ cations of the group, wherein the separation layer (B-1) selected free H ^+, Li ^+, Na ⁺ and K ⁺ exceeds the group consisting of The total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in the} first composite layer (A-2) is 5 times or more, more preferably 25 times or more, more preferably 50 times or Larger and best 100 times or larger.

Generally, in the separation layer, the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ is greater than 100 ppm, preferably greater than 200 ppm, and more preferably greater than 1000 ppm.

As used herein, "ppm" means "parts per million" in terms of the total weight of the separation layer (B-1).

The term "electrolyte" is known in the art and means a substance capable of dissociating into mobile ions. For specific and preferred electrolytes (i ''), see below.

This type of preferred article is suitable for combination with the second composite layer (C-2) as defined above as the counter electrode, and is selected from the group consisting of H ⁺ , Li ⁺ when in the second composite layer (C-2). The total concentration of cations in the group consisting of Na, K ^+, and K ⁺ is 100 ppm or less, preferably 20 ppm or less, and most preferably 2 ppm or less. As used herein, "ppm" means "parts per million" in terms of the total weight of the second composite layer (C-2).

Therefore, advantageously, the second composite layer (C-2) can be obtained from an ink in the same manner as the first composite layer, the ink being selected from the group of cations consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ The total concentration is 2 ppm or less, preferably 0.02 ppm or less, and most preferably 0.002 ppm or less. Ions from the electrolyte (i '') present in the separation layer can enter the first and second composite layers (C-2) by diffusion and migration, which has a significantly lower concentration selected from the group consisting of H ⁺ , Li ⁺ Cations of the group consisting of Na ⁺ , K ⁺ , and K ⁺ , thereby providing sufficient ionic conductivity in the first and second composite layers.

Such preferred objects (as defined above) are also suitable for combination with opposing electrodes of the second composite layer (C-2) which is not as defined above. For example, an opposite electrode layer is obtained by depositing an electroactive material on the surface of the second solid substrate. Deposition of an electroactive material, such as an electrochromic material, can be achieved by means of sputtering. The counter electrode layer may contain an electroactive material independently of its oxidation state. The electroactive material is substantially optically transparent or has an electrochromic metal oxide in a nano-object (a) involving a specific electrochromic composite layer. The obvious color change is significantly less electrochromic effect. Suitable electroactive materials are known in the art and include, but are not limited to, tin oxide, cerium oxide, and transparent polymers capable of intercalating lithium ions. Alternatively, the counter electrode layer comprises an electroactive material that exhibits an electrochromic effect that is dependent on the applied electrochemical potential and is opposite to the electrochromic effect of the electrochromic metal oxide in the electrochromic composite layer. For example, the electrochromic oxide of the electrochromic composite layer is colored during anodic oxidation and faded during cathodic reduction, and the electrochromic material in the opposite electrode is colored during cathodic reduction and faded during anodizing, or vice versa The same is true. Alternatively, the electrochromic oxide of the electrochromic composite layer adopts a dark color during anodization and a less dark color during cathodic reduction, and the electrochromic material in the opposite electrode adopts a dark color during cathodic reduction and the anode Less dark colors are used during oxidation, or vice versa.

Alternatively, in the separation layer (B-1), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 20 ppm or less, preferably 4 ppm or less, most 0.4 ppm or lower. When the second composite layer (C-2) contains at least one cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ , (i ') dissolved in the aprotic organic liquid (g') In the case of an electrolyte, such an article is suitable for combination with a second composite layer (C-2) as an opposite electrode, wherein the second composite layer (C-2) is selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ The total concentration of cations in the group exceeds the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the separation layer and the first composite layer by 5 times or more, more preferably 25 times or Larger, better 50 times or larger and best 100 times or larger. Generally, in the second composite layer (C-2), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is more than 100 ppm, preferably more than 200 ppm, and most preferably more than 1000 ppm. Ions from the electrolyte (i '') present in the second composite layer can be diffused and migrated into a cation having a significantly lower concentration selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ The separation layer and the first composite layer provide sufficient ionic conductivity in the separation layer and the first composite layer.

A particularly preferred object according to a second aspect of the present invention includes a multilayer structure (A-1) a first substrate composed of (A-2) as described above disposed on a surface of the first substrate (A-1) The composite layer defined in the text, (C-1) a second solid substrate, (C-2) a second composite layer disposed on the surface of the substrate (C-1), and the second composite layer (C-2) Contains-a matrix formed of one or more organic polymers-and dispersed within the matrix: (a ') a nano-object comprising one or more electrochromic oxides of an element selected from the group consisting of: transition Metals, rare earth elements, and Group 12, 13 and 14 elements other than carbon, the one or more electrochromic oxides are different from the electricity contained in the nano-object (a) of the first composite layer (A-2) The color-changing oxide (b ') optionally exists one or more metal salts (g') according to formula (I), the aprotic organic liquid (B) having a boiling point of 120 ° C or higher is sandwiched in the first composite layer The separation layer (B) between (A-2) and the second composite layer (C-2) comprises-a matrix formed of one or more organic polymers-and (g '' ) Boiling point is 120 ° C or higher Aprotic organic liquid wherein at least one of the second composite layer (C-2) and the separation layer (B) further comprises (i ', i'') dissolved in the aprotic organic liquid (g', g '' ) At least one electrolyte having a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ wherein the layers (B), (C-2) are selected from H ⁺ , Li ⁺ , Na The total concentration of cations of the group consisting of ⁺ and K ⁺ exceeds the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the first composite layer (A-2) by 5 times or more , Better 25 times or more, better 50 times or more and best 100 times or more.

The object includes a multi-layer structure, which is composed of a first solid substrate (A-1), a first composite layer (A-2), a separation layer (B), and a second composite as defined above along a stacking direction. The layer (C-2) and the second solid substrate (C-1) are composed. In the object, the separation layer (B) has a first surface and a second surface opposite to the first surface, wherein the first surface of the separation layer (B) and the first solid substrate (A- 1) The surface of the first composite layer (A-2) is in contact, and the second surface of the separation layer (B) is in contact with the second composite layer (C) facing away from the second solid substrate (C-1) -2) surface contact.

The solid substrates (A-1) and (C-1) include one or more materials selected from the group consisting of glass, metal, and organic polymers. At least one of the solid substrates (A-1) and (C-1) exhibits a light transmittance of 80% or more as measured according to DIN EN 410.

The thickness of the first composite layer (A-2) disposed on the surface of the solid substrate (A-1) is in a range of 0.05 μm to 500 μm, preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 30 μm. The thickness of the second composite layer (C-2) disposed on the surface of the second solid substrate (C-1) is in a range of 0.05 μm to 500 μm, preferably 0.05 μm to 50 μm, and most preferably 0.1 μm to 30 μm .

This separation layer (B) is almost electronically insulated, but allows ion flow. Without being bound by theory, in the separation layer (B), the aprotic organic liquid (g ''), as defined above, is limited to extend through the pores of the matrix, so it is provided for the first composite layer and the A network of ion transport between the second composite layers.

The thickness of the separation layer is preferably in the range of 0.05 µm to 1500 µm, preferably 0.05 µm to 1000 µm, and most preferably 1 µm to 800 µm. Thickness can be determined by profilometry, atomic force microscopy, or electron microscopy.

In the second composite layer (C-2) and the separation layer (B), preferably, the substrate is formed of the same organic polymer as the substrate in the first composite layer, and has a boiling point of 120 ° C or higher. The aprotic organic liquid (g ') and (g' ') are the same as the aprotic organic liquid (g) in the first composite layer, respectively.

At least one of the separation layer (B) and the second composite layer (C-2) contains electrolytes (i ') and (i''), respectively, wherein the layers (B), (C-2) cation selected free H ^+, Li ^+, Na ⁺ and K ⁺ is selected from the group consisting of H ^+, Li ^+, Na ⁺ and K ⁺ cations of the total concentration of the composition of the group exceeds a first composite layer (a-2) The total concentration is 5 times or more, more preferably 25 times or more, more preferably 50 times or more, and most preferably 100 times or more.

It has been found that ions from an electrolyte present in the separation layer (B) or the second composite layer (C-2) can enter one or more other layers by diffusion and migration, which has a significantly lower concentration selected from the group consisting of The cations of the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ provide sufficient ionic conductivity across the respective layers.

In the case of the present invention, water does not belong to the electrolytes (i '), (i'') as defined above. Therefore, the electrolyte contains at least one anion different from OH ⁻ or at least one cation from a group consisting of Li ⁺ , Na ⁺ and K ⁺ .

Preferably, the electrolytes (i ') and (i' ') are lithium salts.

Preferably, the electrolytes (i ') and (i'') are selected from the group consisting of: lithium aluminum chloride (LiAlCl ₄ ); lithium hexafluorosilicate (Li ₂ SiF ₆ ); hexafluoroantimonic acid Lithium (LiSbF ₆ ); LiX (RSO ₂ ) _n , where n = 1 and X = O or S, n = 2 and X = N or P, n = 3 and X = C or Si, and R in each case C _m H _{2m + 1 - n} F _n , where m = 0-20, n = 0-21; lithium fluoride (LiF); lithium nitrate (LiNO ₃ ); lithium perchlorate (LiClO ₄ ); tetrafluoro Lithium borate (LiBF ₄ ); lithium (pentafluorophenyl) borate; lithium difluorophosphate (LiPO ₂ F ₂ ); lithium hexafluorophosphate (LiPF ₆ ); lithium hexafluoroarsenate (LiAsF ₆ ); bis (fluorosulfonyl) ) Lithium lithium imine (LiN (SO ₂ F) ₂ ); lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ); LiN (SO ₂ C _n F _{2n + 1} ) ₂ , where n = 2 to 20; LiC [(C _n F _{2n - 1} ) SO ₂ ] ₃ , where n = 2 to 20; Li (C _n F _{2n + 1} ) SO ₂ , where n = 2 to 20; bis (trifluoromethane) sulfonylimide Lithium (LiN (CF ₃ SO ₂ ) ₂ , also known as bis-trifluoromethylsulfonimide); reference trifluoromethylsulfonylmethyllithium (LiC (CF ₃ SO ₂ ) ₃ ); dioxalic acid root lithium borate _{(LiB (C 2 O 4)} 2); difluoro (oxalato) borate _{(LiBF 2 (C 2 O 4} )); difluoro (two oxalato) phosphate And tetrafluoro (oxalato) phosphate lithium.

Preferably, the electrolyte (i '), (i'') having a metal selected from the group consisting of as for formula (I) (b) the anion of the above defined Z ^{b -} anion of the group.

Preferably, the electrolytes (i ') and (i'') are selected from the group consisting of: lithium aluminum chloride (LiAlCl ₄ ); lithium hexafluoroantimonate (LiSbF ₆ ); LiX (RSO ₂ ) _n , Where n = 1 and X = O, n = 2 and X = N, n = 3 and X = C, and R is C _m H _{2m + 1 - n} F _n in each case, where m = 0-20 , N = 0-21; lithium perchlorate (LiClO ₄ ); lithium (pentafluorophenyl) borate; (LiPF ₆ ); lithium hexafluoroarsenate (LiAsF ₆ ); bis (fluorosulfonyl) fluorene Lithium imine (LiN (SO ₂ F) ₂ ); lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ); LiN (SO ₂ C _n F _{2n + 1} ) ₂ , where n = 2 to 20; LiC [( C _n F _{2n - 1} ) SO ₂ ] ₃ , where n = 2 to 20; lithium bis (trifluoromethane) sulfoimide (LiN (CF ₃ SO ₂ ) ₂ ); and trifluoromethylsulfonyl Methyl lithium (LiC (CF ₃ SO ₂ ) ₃ ).

Preferably, the electrolytes (i ') and (i' ') are selected from the group consisting of lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethane) sulfonimide, and bis ( Fluorosulfonyl) fluorenimide lithium.

The second composite layer serves as an opposite electrode with respect to the first composite layer in the electrochromic device. In the second composite layer, the nano-object (a ') contains an electrochromic oxide, which is different from the electro-chromic oxide contained in the nano-object (a) of the first composite layer. Preferably, the electrochromic oxide in the second composite layer is selected to exhibit electrical properties that are dependent on the applied electrochemical potential and are opposite to the electrochromic effect of the electrochromic metal oxide in the first composite layer. Discoloration effect. For example, the electrochromic oxide of the first composite layer is colored during anodization and fades during cathodic reduction, and the electrochromic material in the second composite layer is colored during cathodic reduction and faded during anodization, or vice versa. Alternatively, the electrochromic oxide of the first composite layer adopts a dark color during anodization and a less dark color during the cathodic reduction, and the electrochromic material in the second composite layer adopts a dark color during the cathodic reduction and the Less dark colors are used during anodizing, or vice versa.

In a particularly preferred case, the nano-object (a) of the first composite layer (A-2) contains one or more nickel oxides, and the nano-object (a ') of the second composite layer (C-2) contains One or more tungsten oxides, or vice versa.

The second composite layer (C-2) disposed on the surface of the second solid substrate (C-1) can be prepared and disposed on the first solid by the above-mentioned case of the first aspect of the present invention. Obtained by the method described in the first composite layer (A-2) on the surface of the substrate (A-1).

Optionally, the second composite layer (C-2), as defined above, further contains (h ') an electronically conductive nano-object, which does not include any compound selected from the group consisting of elemental oxides, which elements are selected from A group consisting of transition metals, rare earth elements and Groups 12, 13 and 14 is dispersed in the matrix formed of one or more organic polymers.

In the first particularly preferred object comprising the multilayer structure as defined above, the second composite layer (C-2) further comprises (i ') at least one electrolyte dissolved in the aprotic organic liquid (g'), It has a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ , wherein the second composite layer (C-2) is selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ The total concentration of cations exceeds the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the first composite layer (A-2) 5 times or more, more preferably 25 times or more 50 times better or better and 100 times better or better.

Generally, in the second composite layer (C-2), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is more than 100 ppm, preferably more than 200 ppm, more preferably more than 1000 ppm.

With regard to the first particularly preferred object, it is more preferable that in the separation layer (B), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 20 ppm or less, It is preferably 4 ppm or less, and most preferably 0.4 ppm or less. The ions from the electrolyte present in the second composite layer (C-2) can diffuse and migrate into cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ with a significantly lower concentration. The separation layer (B) and the first composite layer (A-2) provide sufficient ionic conductivity in the separation layer and the first composite layer.

In a second particularly preferred object comprising a multilayer structure as defined above, the separation layer (B) further comprises (i '') at least one electrolyte dissolved in the aprotic organic liquid (g ''), which has selected from the group consisting of H ^+, Li ^+, Na ⁺ and K ⁺ cations of the group consisting of wherein the separating layer (B) selected free H ^+, Li ^+, Na ⁺ and K ⁺ cations of the total concentration of the composition exceeds the second group A composite layer (A-2) has a total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ 5 times or more, more preferably 25 times or more, more preferably 50 times or more Large and optimal 100 times or larger.

Generally, in the separation layer (B), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ is more than 100 ppm, preferably more than 200 ppm, more preferably more than 1000 ppm. As used herein, "ppm" means "parts per million" in terms of the total weight of the separation layer (B).

With regard to the second particularly preferred object, it is more preferred that in the second composite layer (C-2), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 2 ppm Or less, preferably 0.02 ppm or less, and most preferably 0.002 ppm or less.

Therefore, in the particularly preferred object including the multilayer structure defined above,-in the first composite layer (A-2) and the second composite layer (C-2), selected from H ⁺ , Li ⁺ The total concentration of cations of the group consisting of Na, Na ⁺ and K ⁺ is 100 ppm or less, preferably 20 ppm or less, and most preferably 2 ppm or less-and the separation layer (B) contains (i '') At least one electrolyte dissolved in the aprotic organic liquid (g ''), which has a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ , wherein the separation layer (B) is selected from H ⁺ , The total concentration of cations of the group consisting of Li ⁺ , Na ⁺ and K ⁺ exceeds the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the first composite layer (A-2), and The total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the second composite layer (C-2) is 5 times or more, more preferably 25 times or more, and more preferably 50 times. Or larger and preferably 100 times or larger.

Ions from the electrolyte present in the separation layer (B) can diffuse and migrate into the first composite layer having a significantly lower concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ (A-2) and the second composite layer (C-2), thereby providing sufficient ionic conductivity in the first and second composite layers.

An article comprising the manufacture of a power-chromic device or the multilayer structure defined above used therein can be obtained by a method comprising-preparing-a first layer assembly (A) comprising a first solid having a surface A substrate (A-1) and a first composite layer (A-2) as defined above, and a separation layer (B-1) as defined above, which is disposed on the surface of the first solid substrate ), The separation layer is disposed on the surface of the first composite layer (A-2) facing the first solid substrate (A-1), or a wet film. The surface of the first composite layer (A-2) of the substrate (A-1) is obtained by coating the composition (B-0) as defined above, and the second layer assembly (C) includes A second solid substrate (C-1) on the surface and a second composite layer (C-2) as defined above, which is disposed on the surface of the second solid substrate, and a separation as defined above, as appropriate Layer (B-2), the separation layer is disposed on the surface of the second composite layer (C-2) facing the second solid substrate (C-1), or a wet film, which is On the second solid substrate (C-1 The surface of the second composite layer (C-2) is obtained by coating the composition (B-0) as defined above, and the restrictions are-the first layer assembly (A) and the second layer At least one of the assemblies (C) includes a separation layer (B-1), (B-2) or a wet film obtained by coating the composition (B-0) defined above-and the second At least one of the composite layer (C-2) and each of these separation layers (B-1), (B-2) and the wet film obtained by coating the composition (B-0) as defined above One further comprises (i ', i'') at least one electrolyte dissolved in the aprotic organic liquid (g', g ''), which has a group selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ Cations, wherein the separation layers (B-1), (B-2), and the cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ^{+ in} the wet film and the layer (C-2) The total concentration exceeds the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in the} first composite layer (A-2) by 5 times or more, more preferably 25 times or more, 50 times or more better and 100 times or more better,-stacking and combining the layer assemblies to have the first composite layer (A-2) sandwiched with A separation layer (B) of the object between the second composite layer (C-2).

The separation layer (B-2) on the surface of the second composite layer (C-2) can be obtained by, for example, obtaining the separation layer (B-1) on the surface of the first composite layer (A-2). Obtained by the method described in the text.

The combination can be achieved as follows: By polymerizing the monomer (d '') in the wet film, the wet film is coated with the composition (B-0) as defined above on the first as defined above, respectively. And on the surface of the second composite layer, or by completing the polymerization of the polymerizable portions (d), (d '), (d' ') in the layers to be combined, respectively.

For further details of the above-mentioned combination, please refer to the unpublished patent application with application number PCT / EP2017 / 055320.

When the first layer assembly (A) includes the separation layer (B-1) and the second layer assembly (C) does not include the separation layer, the separation layer (B-1) and the first layer assembly are combined Achieved between the two composite layers (C-2), and the obtained object includes a separation layer (B-1) sandwiched between the first composite layer (A-2) and the second composite layer (C-2) ).

When the first layer assembly (A) does not include a separation layer and the second layer assembly (C) includes a separation layer (B-2), the combination is between the first composite layer (A-2) and the second layer assembly Reached between the separation layers (B-2), and the obtained object includes a separation layer (B-2) sandwiched between the first composite layer (A-2) and the second composite layer (C-2) ).

When the first layer assembly (A) includes the separation layer (B-1) and the second layer assembly (C) includes the separation layer (B-2), the bonding is on the separation layer (B- 1) Achieved with the separation layer (B-2) of the second layer assembly, and the obtained objects include the sandwiched between the first composite layer (A-2) and the second composite layer (C-2) The resulting separation layer (B-1 / B-2).

Regardless of its origin from the first layer assembly (A), the second layer assembly (C), or both, the separation layers (B-1), (B-2), (B-1 / B-2) are appropriate In this paper, it is often called "separation layer (B)".

The first composite layer (A-2) disposed on the surface of the first solid substrate (A-1) and the second composite layer (C) disposed on the surface of the second solid substrate (C-1) -2) Obtainable by the method as described above in the case of the first aspect of the present invention.

To prepare the first composite layer (A-2), the composition (A-0) according to the first aspect of the present invention is used. To prepare the second composite layer (C-2), a composition (C-0) as defined above is used, which contains (a ') a nano-object, which contains one or more elements selected from the group consisting of Electrochromic oxide: transition metals, rare earth elements, and Group 12, 13 and 14 elements other than carbon, the one or more electrochromic oxides are different from those used to prepare the first composite layer (A-2) The electrochromic oxide (b ') contained in the nano-object (a) of the composition (A-0), as the case may be, as defined above, the metal salt (c') according to formula (I) has a boiling point below 120 ° C carrier liquid (d ') One or more types of polymerizable moiety (e') Optionally one or more initiators, which are used to initiate radical polymerization of the one or more types of polymerizable moiety (f ') As appropriate, one or more organic polymers (g') suspended or dissolved in the carrier liquid (a ') aprotic organic liquids (h') with a boiling point of 120 ° C or higher, as appropriate, electronically conductive nano-objects , Which does not contain any compounds selected from the group consisting of elemental oxides, which are selected from Transition metals, rare earth elements and the second group 12, 13 and 14 elements of the group.

In the ink (C-0), the nano-object (a ') contains an electrochromic oxide, which is different from the electro-chromic oxide contained in the nano-object (a) of the first composite layer. See above for criteria for selecting this electrochromic material. In a particularly preferred case, the nano-object (a) of the composition (A-0) contains one or more nickel oxides, and the nano-object (a ') of the composition (C-0) contains one or more tungsten Oxide, or vice versa.

Regarding the composition (C-0), the preferred and specific metal salt (b '), carrier (c'), polymerizable portion (d '), initiator (e'), polymer (f '), and boiling point are Aprotic organic liquids (g ') and conductive nano-objects (h') at 120 ° C or higher, as described above in the case of the first aspect of the present invention, respectively, for the composition according to the first aspect of the present invention (A-0) metal salt (b), carrier liquid (c), polymerizable portion (d), initiator (e), aprotic organic liquid (g) having a boiling point of 120 ° C or higher, and conductive nanometers The situation revealed by object (h) applies.

In the composition (C-0) for preparing the second composite layer (C-2), preferably, the polymerizable portion (d ') and the composition for preparing the first composite layer (A-2) The polymerizable part (d) in (A-0) is the same as the aprotic organic liquid (g ') having a boiling point of 120 ° C or higher and the composition (A) for preparing the first composite layer (A-2) The aprotic organic liquid (g) in -0) is the same.

To prepare the separation layer (B), a composition (B-0) as defined above is used.

At least one of the compositions (B-0) and (C-0) comprises (i ', i'') at least one electrolyte having a composition selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ The amount of cations of the group is suitable for preparing the layers (B), (C-2). The total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ exceeds the first composite layer (A -2) The total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 5 times or more, more preferably 25 times or more, more preferably 50 times or more, and most preferably 100 Times or larger.

In a first particularly preferred method, the composition (C-0) comprises (i ') at least one electrolyte having a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ , wherein In the composition, the total concentration of these electrolytes is preferably in the range of 0.001% to 0.4% by weight.

With regard to this first particularly preferred method, it is more preferable that in the composition (B-0), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 20 ppm or less , Preferably 4 ppm or less, most preferably 0.4 ppm or less, and the composition (B-0) does not contain a carrier liquid.

By using these compositions (B-0) and (C-0) and the composition as defined above in the case of the first aspect of the invention in the first particularly preferred method defined above ( A-0), an object can be obtained, wherein the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the second composite layer (C-2) exceeds the first composite layer ( A-2) and the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the separation layer (B) is 5 times or more, more preferably 25 times or more, more preferably 50 Times or more and preferably 100 times or more.

Generally, in the second composite layer (C-2), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is more than 100 ppm, preferably more than 200 ppm, and most preferably more than 1000 ppm, and in the separation layer (B), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ is 20 ppm or less, preferably 4 ppm or less, most preferably 0.4 ppm or lower.

In a second particularly preferred method, the composition (B-0) comprises (i '') at least one electrolyte having a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ , wherein In the composition (B-0), based on the total weight of the composition, the total concentration of the electrolytes is in a range of 0.5% to 15% by weight and does not include a carrier liquid (c '').

With regard to this second particularly preferred method, it is more preferable that in the composition (C-0), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 2 ppm or less , Preferably 0.02 ppm or less, and most preferably 0.002 ppm or less. This is advantageous because the composition (C-0) contains a nano-object (a ') and a high concentration of an electrolyte pair with a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ Rice objects have an adverse effect on the stability of coalescence and settlement. On the other hand, the composition (B-0) does not contain any suspended nano-objects, and therefore an electrolyte having a significant concentration of a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ is} not disadvantageous.

By using these compositions (B-0) and (C-0) and the composition as defined above in the case of the first aspect of the invention in the second particularly preferred method defined above ( A-0), an object can be obtained, wherein the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the separation layer (B) exceeds the first composite layer (A-2) And the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the second composite layer (C-2) is 5 times or more, more preferably 25 times or more, more preferably 50 Times or more and preferably 100 times or more.

Generally, in the separation layer (B), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is more than 100 ppm, preferably more than 200 ppm, and most preferably more than 1000 ppm, and In the second composite layer (C-2), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 20 ppm or less, preferably 4 ppm or less, and most preferably 0.4 ppm or lower.

According to a third aspect, there is provided a method of manufacturing or using a multilayer structure for a pre-treated electrochromic device, the method comprising the steps of:-providing an object comprising a multilayer structure as defined above-at a first composite layer A voltage is applied to the second composite layer to allow cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ^{+ to} migrate across the separation layer to the first composite layer.

According to a fourth aspect, the present invention relates to the use of an article comprising the manufacture of a power-supplying color-changing device or a multilayer structure as defined hereinabove.

In some cases, the manufacture or use of an electrochromic device further includes a support layer attached to the surface of the first solid substrate facing away from the composite layer and / or attached to the opposite electrode layer facing away. A support layer on the surface of the second solid substrate. Preferably, the first support layer is attached to the surface of the first solid substrate facing away from the composite layer, and the second support layer is connected to the surface of the second solid substrate facing away from the opposite electrode layer. In this regard, it is particularly preferred that the first solid substrate and the second solid substrate include materials from the group of organic polymers and are in the form of a foil, a film, or a mesh, and the first support layer and the second support layer include glass.

In addition, the third support layer may be attached to the surface of the first support layer facing away from the first solid substrate and / or the fourth support layer may be attached to the surface of the second support layer facing away from the second solid substrate. In this regard, it is particularly preferred that the third support layer is attached to the surface of the first support layer facing away from the first solid substrate, and the fourth support layer is attached to the second surface facing away from the second solid substrate. The surface of the support layer. In this regard, it is particularly preferred that the first support layer, the second support layer, the third support layer, and the fourth support layer include glass.

The support layers include one or more materials selected from the group consisting of glass, metal, and organic polymers. Preferred types of glass are, for example, float glass, low-iron float glass, heat strengthened glass, and chemically strengthened glass. Optionally, the glass has a low-emissivity / low-e coating, a solar protection coating, or any other coating on the exterior-facing surface.

Attaching the first and second support layers to the corresponding first and second solid substrates, respectively, preferably includes applying an adhesive between the support layer and the surface of the solid substrate to which the support layer must be attached. Attaching the third and fourth support layers to the corresponding first and second support layers, respectively, preferably includes applying an adhesive. Suitable adhesives are thermoplastics, such as polyvinyl butyral, polyvinyl alcohol, polyvinyl acetate, ethylene-vinyl acetate copolymers, polyurethanes, ionomer resins (such as commercially available under the trade name SentryGlas® ) And polymethyl methacrylate (PMMA).

The invention further relates to the use of objects as defined above and electrochromic devices as defined above in buildings, furniture, automobiles, trains, aircraft and ships, respectively, and on roofs, skylights, glass roofs, stair steps, Uses in glass bridges, canopies, railings, automotive glass, train glass.

The invention further relates to insulating glass blocks, windows, revolving windows, interior windows, tilt-turn windows, upper hanging windows, swing windows, box windows, horizontal sliding windows, vertical sliding windows, side windows, shop windows, skylights , Ceiling light, door, double wall, closed cavity wall, all-glass construction, horizontal sliding door in D3 wall (Dual, Dynamic Durable Facade), glass structural elements (such as but not (Limited to burrs, shading grids), interactive walls (walls that respond to external impacts, such as but not limited to motion control, radiation sensors, other sensors) curved glass, formed glass, 3D 3D glass, wood Glass combination, skylight glass, roof glass, bus stop, shower wall, interior wall, open space office and room interior separation elements, outdoor wall, stair pedal, glass bridge, canopy, railing, fish pond, balcony, adjustment Light glass and patterned glass.

The invention further relates to thermal insulation (ie thermal insulation), thermal insulation, sound insulation, shading and / or vision protection. The present invention is preferably applicable to insulating glass spacers (IGU) when combined with other glass layers, which can be used on building walls. The IGU can have double glass (glass plate 1 + glass plate 2) or triple glass (glass plate 1 + glass plate 2 + glass plate 3), or more glass plates. Glass plates can have different thicknesses and different sizes. The glass plate may be tempered glass, tempered safety glass, laminated glass, laminated tempered glass or safety glass. The device according to the present application can be used in any of the glass plates 1, 2, 3. The material can be placed in the space between the glass plates. Such materials may be, for example, but are not limited to, argon, xenon, nitrogen, wooden objects, expanded metals, prismatic objects, shutters, shading grids, light guides, light guide films, light guide shutters, 3-D guides Light Objects, Sun Blinds, Movable Blinds, Roller Blinds, Roller Blinds from Membrane, Translucent Materials, Capillary Objects, Honeycomb Objects, Micro Blinds, Micro Sheets, Lithography, Micro Mirror Insulation Materials, Aerogels, Integrated Vacuum Insulating plates, holographic elements, integrated photovoltaic devices, or combinations thereof.

The invention further relates to the use in heat mirror glass, vacuum glass, multilayer glass and laminated safety glass.

The invention further relates to applications in transport units, preferably boats, ships, space ships, aircraft, helicopters, trains, cars, trucks, cars, such as (but not limited to) windows, partition walls, light surfaces and backgrounds Lighting, signage, bypass protection, use as skylight.

The present invention is preferably applicable to insulating glass spacers (IGU) when combined with other glass layers, which can be used on building walls.

Examples The invention will now be further illustrated by means of non-limiting examples.

All compositions were obtained according to the examples disclosed in WO 2016/128133. Nanoparticles are commercially available or obtained by flame spray pyrolysis. All other ingredients are commercially available.

The composition - (2 A) for the preparation of the first composite layer (A - 0) Preparation of a composition comprising (A-0) (a) tungsten oxide nanoparticles comprising (c) a water and 2-propanol The mixture (d) of alcohols is selected from the group consisting of monomers consisting of alkyl acrylates and alkyl methacrylates, and the monomers (e) consisting of groups consisting of hydroxyalkyl acrylates and hydroxyalkyl methacrylates. ) An initiator (g) for initiating the copolymerization of the monomer (d) by UV irradiation.

The concentrations of all ingredients are within the preferred ranges defined above.

The composition - (2 C) for preparing the second composite layer (C - 0) Preparation of a composition comprising (C-0) (a ' ) comprising nickel oxide nanoparticles (b') Y (NO ₃ ) ₃ × 6 H ₂ O (c ') ethanol (d') selected from the group consisting of alkyl acrylates and alkyl methacrylates and monomers selected from the group consisting of hydroxyalkyl acrylates and hydroxyalkyl methacrylates The monomer (e ') of the ester group is an initiator (g') for initiating the copolymerization of the monomer (d) by UV irradiation.

The concentrations of all ingredients are within the preferred ranges defined above.

An electrolyte containing a cation selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ^{+ has not been} used to prepare these compositions (A-0) and (C-0). In the composition (A-0) and the composition (C-0), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is less than 2 ppm.

Composition ( B - 0 ) for preparing a separation layer Preparation of the composition (B-0) (d '') comprising a monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate, and Monomer (e '') of a group consisting of hydroxyalkyl acrylate and hydroxyalkyl methacrylateInitiator (g '') for initiating copolymerization of monomer (d) by UV irradiation Carbonic acid 1, 2-propenyl (i '') lithium bis (trifluoromethane) sulfonylimide.

The composition (B-0) does not include a carrier liquid having a boiling point below 120 ° C.

The concentrations of all ingredients are within the preferred ranges defined above.

The monomers (d), (d '), and (d' ') in the compositions (A-0), (C-0), and (B-0) are the same.

Preparation of composite layer ( A - 2 ) , ( C - 2 ) composition (A-0) for preparing a first composite comprising nanoparticle (a) as defined above on a first substrate (A-1) Layer (A-2).

The composition (C-0) is used as an ink for preparing a second composite layer (C-2) containing nano particles (a ') as defined above on a second substrate (C-1).

The substrates (A-1) and (C-1) are each a PET foil having a surface coated with indium tin oxide (ITO). The wet film was formed by blade-coating the ink on the ITO-coated surface in each case. After the carrier liquids (c) and (c '') are evaporated under ambient conditions, the monomers (d) and (d ') are copolymerized. The copolymerization is initiated by UV irradiation. Thereafter, the coated substrate is heated on a hot plate.

The manufacture of the electrochromic device or the multilayer structure used thereon is applied on the surface of the first composite layer (A-2) facing away from the substrate (A-1), and the composition (B- 0) to form a wet film. A layer assembly consisting of a second substrate (C-1) and a second composite layer (C-2) disposed on the surface of the second substrate (C-1) is placed on top of the wet film so that the wet film Facing the composite layer (C-2).

A multilayer structure thus obtained having a wet film of the composition (B-0) sandwiched between the first composite layer (A-2) and the second composite layer (C-2) is exposed to UV radiation using a mercury UV lamp The monomer (d '') in the wet film is polymerized for 60 seconds to form a separation layer (B) sandwiched between the first composite layer (A-2) and the second composite layer (C-2). Therefore, a multilayer structure is obtained, which is composed of the first solid substrate (A-1), the first composite layer (A-2), the separation layer (B), and the second composite as defined above along the stacking direction. The layer (C-2) and the second solid substrate (C-1) are composed.

Spectroelectrochemical studies of multi-layer structures with the use of multi-cycle cyclic voltammetry with a two-electrode configuration (working electrode: composite layer (A-2), opposite and reference electrode: composite layer (C-2)) are studied as described above The obtained electrochromic properties of the multilayer structure.

The first five cycles (in the pre-processing phase, with a scan rate of 5 mV / s in each case) were performed using the following voltage ranges: 1st CV cycle: -0.5V to 1.2V 2nd CV cycle: -1.2V to 1.2 V 3rd CV cycle: -1.7V to 1.2V 4th CV cycle: -1.8V to 1.4V 5th CV cycle: -2.2V to 2.4V

Subsequently, the electrochromic device was switched on and off repeatedly at a scan rate of 10 mV / s in a voltage range of -1.6 / + 2.6 V (288 working cycles, 6-293). By in-situ UV-Vis measurement while monitoring the color change, it confirms the stable coloration and fading of the electrochromic device.

During the five cycles of the pre-treatment phase, the shape of the cyclic voltammogram changed due to the anode and cathode peaks generated from the significant growth from the first to fifth cycles, see Figures 1 to 5. This is evidence to increase the anodization / cathode reduction of the electrochromic nanoparticle (a) in the first composite layer (A-2), which is caused by the increase of Li ⁺ cations from the electrolyte (present in the separation layer (B)) i '') Diffusion and migration to the first composite layer (A-2) are promoted by balancing the reduction of the oxidation state of tungsten in the tungsten oxide nanoparticle (a) during the cathode scan.

During the working phase, the cyclic voltammogram changes less significantly than during the preprocessing phase, see Figure 6. Therefore, almost reproducible electrochromic characteristics are achieved, as also demonstrated by reproducible optical adjustment at a fixed wavelength of 550 nm during the working phase (ie, voltammetric cycles 6 to 293) (see Figure 7).

Figures 1 to 5 show the cyclic voltammograms during the preprocessing phase. Figure 6 shows the cyclic voltammogram during the working phase. Figure 7 shows the optical adjustment at a fixed wavelength of 550 nm during the working phase.

Claims (15)

A composition (A-0) comprising (a) a nano-object comprising one or more electrochromic oxides of an element selected from the group consisting of a transition metal, a rare earth element, and Groups 12, 13, and 14 elements (c) Carrier liquids with a boiling point below 120 ° C (d) One or more types of polymerizable fractions (g) Aprotic organic liquids with a boiling point of 120 ° C or higher Where in the composition ( In A-0), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 2 ppm or less, preferably 0.02 ppm or less, with respect to the total weight of the composition. Best 0.002 ppm or less. The composition of claim 1, further comprising (e) one or more initiators for initiating free-radical polymerization of the one or more types of polymerizable moieties and / or (f) one or more organic polymers and / Or (h) electronically conductive nano-objects, which do not contain any compounds selected from the group consisting of elemental oxides, which are selected from the group consisting of transition metals, rare earth elements, and elements of groups 12, 13, and 14. If the composition of claim 1 or 2 wherein (a) the nanoparticle system is selected from the group consisting of nanowires and nanoparticle and / or (c) the carrier liquid having a boiling point lower than 120 ° C is selected from A group consisting of alcohols, amines, carbonic acid, esters, ketones, organic carbonates, polyethers, sulfides and nitriles and mixtures thereof and / or (d) the polymerizable moieties are selected from the group consisting of: alkyl acrylates Base ester, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, vinyl chloride, vinyl fluoride, acrylonitrile, vinylidene fluoride, vinylidene chloride, hexafluoropropylene, trifluoroethylene , Tetrafluoroethylene, tetrahydrofuran, vinylpyrrolidone, polyisocyanate, combined with a polyol and / or diamine, and / or (f) These organic polymers are selected from the group consisting of: polyalkyl acrylates, Polyalkyl methacrylate, polyhydroxyalkyl acrylate, polyhydroxyalkyl methacrylate, polyvinyl chloride, polyvinyl fluoride, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polyhexaene Fluoropropylene, polytrifluoroethylene, polytetrafluoroethylene Polytetrahydrofuran, polyvinylpyrrolidone, polyurethane, polyethylene oxide and / or (g) The non-polymerizable aprotic organic liquid system having a boiling point of 120 ° C or higher is selected from the group consisting of : Organic carbonates, alcohols, amidines, carboxylic acid esters, ethers, polyethers, ketones, lactones, lactams, phosphates, amidines, sulfonates, sulfonates and urea derivatives and mixtures thereof and / or h) The nano-objects are nano-wires comprising materials selected from the group consisting of: silver, copper, gold, platinum, tungsten and nickel, and selected from the group consisting of silver, copper, gold, platinum, tungsten and nickel. An alloy of two or more metals in a group. A composition as claimed in claim 1 or 2, comprising (a) nano particles comprising one or more tungsten oxides or nano particles comprising one or more nickel oxides (c) a carrier liquid selected from the group consisting of : Ethanol, methanol, 2-propanol, 2-methyltetrahydrofuran and mixtures thereof (d) one or more types of monomers selected from the group consisting of alkyl acrylates and alkyl methacrylates, and One or more types of monomers in the group consisting of alkyl esters and hydroxyalkyl methacrylates (e) Initiators that decompose to free radicals when exposed to radiation (g) Aprotic organic compounds selected from the group consisting of Liquid: Ethyl carbonate, Ethyl carbonate, Ethylene carbonate, Ethylene carbonate, Ethylene carbonate, Ethylene carbonate, Ethylene carbonate, Ethylene carbonate Propylene esters and their mixtures (h) Silver nanowires as appropriate. An article comprising (A-1) a substrate, (A-2) a composite layer disposed on a surface of the substrate (A-1), the composite layer including a matrix formed of one or more organic polymers, and Dispersed in the matrix: (a) Nano-objects containing one or more electrochromic oxides of elements selected from the group consisting of transition metals, rare earth elements, and 12th, 13th, and Group 14 element (g) an aprotic organic liquid having a boiling point of 120 ° C or higher, wherein in the composite layer (A-2), relative to the total weight of the composite layer (A-2), selected from H ⁺ , Li The total concentration of cations of the group consisting of ⁺ , Na ^+, and K ⁺ is 100 ppm or less, preferably 20 ppm or less, and most preferably 2 ppm or less. (B-1) is disposed on the substrate ( A-1) a separation layer on the surface of the composite layer (A-2), the separation layer (B-1) comprising a matrix formed of one or more organic polymers and (g '' ) Aprotic organic liquids with a boiling point of 120 ° C or higher. For example, the article of claim 5, wherein the article includes a multilayer structure (A-1) a first substrate consisting of (A-2) a first composite layer disposed on a surface of the first substrate (A-1) , Which is a composite layer as defined in claim 5, (C-1) a second solid substrate, (C-2) a second composite layer disposed on the surface of the substrate (C-1), the second The composite layer (C-2) comprises a matrix formed of one or more organic polymers and dispersed in the matrix: (a ') a nano-object comprising one or more elements selected from the group consisting of Color-changing oxides: transition metals, rare-earth elements, and Group 12, 13, and 14 elements other than carbon, the one or more electrochromic oxides are different from the nanometers of the first composite layer (A-2) The electrochromic oxide (g ') contained in the object (a) and the aprotic organic liquid (B) having a boiling point of 120 ° C or higher is sandwiched between the first composite layer (A-2) and the second composite layer Separation layer (B) between (C-2), which comprises a matrix formed of one or more organic polymers and (g '') an aprotic organic liquid having a boiling point of 120 ° C or higher dispersed in the matrix Which the second At least one of the combined layer (C-2) and the separation layer (B) further comprises (i ', i'') at least one electrolyte dissolved in the aprotic organic liquid (g', g ''), which A cation having a group selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ wherein one of the layers (B) and (C-2) is selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ The total concentration of the cations in the composed group exceeds the total concentration of the cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} the first composite layer (A-2) by 5 times or more, more preferably 25 Times or more, more preferably 50 times or more, and most preferably 100 times or more. The article of claim 5 or 6, wherein the separation layer (B-1), (B) further comprises (i '') at least one electrolyte dissolved in the aprotic organic liquid (g ''), which has an electrolyte selected from the group consisting of H ^+, Li ^+, Na ⁺ and K ⁺ cations of the group consisting of wherein the separating layer (B) selected free H ^+, Li ^+, Na ⁺ and K ⁺ cations of the total concentration of the composition of the group exceeds the first complex The total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} layer (A-2) is 5 times or more, more preferably 25 times or more, more preferably 50 times or more and Best 100 times or more. The article of claim 5 or 6, wherein in the separation layer (B-1), (B), relative to the total weight of the separation layer (B-1), is selected from H ⁺ , Li ⁺ , Na ⁺ and The total concentration of cations of the K ⁺ group is 20 ppm or less, preferably 4 ppm or less, and most preferably 0.4 ppm or less. The article of claim 6, wherein the electrochromic composite layer (C-2) further comprises (i ') at least one electrolyte dissolved in the aprotic organic liquid (g'), which has an electrolyte selected from the group consisting of H ⁺ , Li ⁺ Cations of the group consisting of Na, Na ^+, and K ⁺ wherein the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ^{+ in} the second composite layer (C-2) exceeds the first composite layer The total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ^{+ in} (A-2) is 5 times or more, more preferably 25 times or more, more preferably 50 times or more, and most 100 times better or better. The article as claimed in claim 6, wherein in the electrochromic composite layer (C-2), with respect to the total weight of the second composite layer (C-2), selected from H ⁺ , Li ⁺ , Na ⁺ and K The total concentration of the cations of the ⁺ group is 100 ppm or less, preferably 20 ppm or less, and most preferably 2 ppm or less. The article as claimed in claim 6, wherein in the first composite layer (A-2), relative to the total weight of the first composite layer (A-2), is selected from H ⁺ , Li ⁺ , Na ⁺ and K ⁺ The total concentration of the cations of the constituent group is 100 ppm or less, preferably 20 ppm or less, and most preferably 2 ppm or less, in the second composite layer (C-2), relative to the second composite The total weight of layer (C-2), the total concentration of cations selected from the group consisting of H ⁺ , Li ⁺ , Na ⁺ and K ⁺ is 100 ppm or less, preferably 20 ppm or less, and most preferably 2 ppm Or lower and the separation layer (B) contains (i '') at least one electrolyte dissolved in the aprotic organic liquid (g ''), which has a member selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ The total concentration of cations in the separation layer (B) selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ⁺ exceeds the total concentration of cations selected from H ⁺ , Li in the first composite layer (A-2) ^+, Na ⁺ and K ⁺ cations of the total concentration and the second composite layer consisting of the group (C-2) selected consisting of H ^+, Li ^+, Na ⁺ and K ⁺ cations of the total concentration of the group consisting of 5-fold Or greater, better 25 times or greater, better 50 times or greater and best 100 Or greater. As the article of claim 6, wherein the electrolytes (i ') and (i' ') are lithium salts, preferably selected from the group consisting of lithium salts: lithium perchlorate, lithium trifluoromethanesulfonate, bis (Trifluoromethane) lithium sulfonimide and lithium bis (fluorosulfonyl) imide. The article of claim 6, wherein in the second composite layer (C-2) and the separation layer (B), the matrix is made of the same organic polymer as the matrix in the first composite layer (A-2) Formed, and the boiling point of the aprotic organic liquid (g ") in the separation layer (B) is 120 ° C or higher and the boiling point in the second composite layer (C-2) is 120 ° C or higher The aprotic organic liquid (g ') is the same as the aprotic organic liquid (g) in the first composite layer, and the nano-objects (a) of the first composite layer (A-2) include one or more Tungsten oxide, and the nano-objects (a ') of the second composite layer (C-2) include one or more nickel oxides. As in the item of claim 6, wherein the solid substrates (A-1, C-1) comprise one or more materials selected from the group consisting of glass, metal and organic polymers, wherein the solid substrates (A-1, At least one of C-1) exhibits a light transmittance of 80% or more as measured according to DIN EN 410. A method for manufacturing or using a multi-layer structure for a pre-treated electrochromic device, the method comprising the steps of: providing an object comprising a multi-layer structure as defined in claim 6 between a first composite layer and a second composite layer A voltage is applied to allow cations selected from the group consisting of H ⁺ , Li ⁺ , Na ^+, and K ^{+ to} migrate across the separation layer to the first composite layer.