CZ20001628A3 - Electrochrome system - Google Patents

Abstract

The invention relates to an electrochromic device consisting of a pair Transparent and conductively coated glass or plastic plates, one of which may be mirrored and in which it may be a conductive layer of either of the two plates or both two plates divided into separate, individually electrically joined segments that are joined together at the sides their conductive coatings using the sticky hem to which they spacers can be inserted and where the volume is formed of two plates and sticky hem, filled electrochromic fluid, and where the filling or apertures required for introducing an electrochromic fluid is or is sealed glue after the filling has taken place while being sticky for the construction of an electrochromic device uses thermally or a photochemically cured epoxy adhesive, or an epoxy adhesive that thermally cures photochemical initiation and by being used for sealing photochemically cured acrylate adhesive or epoxy an adhesive that cures photochemically or at temperature photochemical initiation room.

Description

Technical field

The invention relates to an electrochromic device and its manufacture.

BACKGROUND OF THE INVENTION

Electrochromic devices including an electrochromic system are already known.

The electrochromic system of these devices generally comprises pairs of reducing-oxidants - reducing-oxidizing cells - dissolved in an inert solvent. In addition, conductive salts, light stabilizers and viscosity modifiers may be present.

The reducing-oxidizing cell used comprises one reducible and one oxidizable substance. Both substances are colorless or have only a slight coloration. As a result of the electrical voltage, one substance is reduced and the other is oxidized, with at least one becoming colored. When the voltage is off, then both original redox substances are recreated, accompanied by the disappearance or fading of the ink.

This process can be illustrated as follows: • ftftftft • · • «

RED- £ + 0 ^ 2 - (colorless) (low energy cell)> OX4 4 “RED 2 (color) (high energy cell)

US-A 4,902,108 discloses that such suitable redox oxidation cells are those wherein the reducible substance has at least two chemically reversible reduction waves in a cyclic voltammogram and the oxidizable substance has correspondingly two chemically reversible oxidation waves.

Electrochromic devices can find a wide and versatile application. For example, they can be used as rear-view mirrors in cars, which can be darkened when driving at night using voltage, preventing the driver from being dazzled by the headlights of other cars (eg US-A 3,280,701, US-A 4,902,108, EP-A 0 435,689). Devices of this type may also be used in window panes or roof sunroofs of automobiles, where they provide shading from sunlight after applying voltage. Finally, it is possible to use these devices to construct a display device for graphically displaying information, for example in the form of letters, numbers and symbols.

The electrochromic device normally consists of a pair of glass or plastic plates, one of which is provided with a mirror in the case of automobile mirrors. One side of these plates is coated with a transparent, electrically conductive layer, eg indium tin oxide (ITO). These plates are then used to construct the cell: an electrically conductive coated side is attached to this end of their front side, preferably using an adhesive connection to an annular or rectangular sealing ring. The gasket creates a uniform seal

ΦΦΦ · · · · · Φ · · · · · · · · ·

ΦΦΦΦ · Φ Φ ΦΦΦΦ

Φ * ΦΦ ΦΦ ΦΦΦ φφ ΦΦ distance between plates, for example from 0.01 to 0.5 mm. This cell is then filled through the opening with an electrochromic solution and the cell is tightly sealed. Using the ITO layer it is possible to join two layers separately.

Electrochromic systems known in the past include reduction-oxidation cells which, upon reduction and oxidation, form colored free radicals, cationic free radicals or anionic free radicals that are chemically reactive. As is known, for example, from Topics in Current Chemistry, Vol. 92, pp. 1-44 (1980), these (ionic) free radicals may be sensitive to electrophiles or nucleophiles or other free radicals. Therefore, in order to achieve a high level of stability in an electrochromic device that includes an electrochromic system of this type - a system designed to withstand several thousand switching cycles - it is necessary to ensure that the solvent used is completely free of electrophiles such as protons, nucleophiles and oxygen. It must also be ensured that such reactive substances are not formed by electrochemical processes taking place on the electrodes during operation of the electrochromic device.

Suitable solvents are known from the aforementioned patents.

In addition, however, the sealing and sealing material of the electrochemical cell must be such that it does not contain any reactive components imparting or contacting the electrochromic system, which react with the electrochromic substances or compounds formed therefrom electrochemically, such as the above-mentioned free-form substances. radicals or substances with ionic free radicals or with double-reduced or double-oxidized substances, * 99 * ·· * 9 * 9 99 99 • 9 9 9 9 9 * 9 * 9

Λ ~ 9,999 9 9 9 9,999

- * 9 9 9 9 * 9 9 »98»

9 * 99 99,999 «9 <9 i

which are always present in equilibrium or are produced electrochemically.

The back-reaction to RED or OX ₂ described in the above equation also takes place continuously outside the electrodes in solution when the electrochromic device is in operation. Due to the dangers of the above described degradation reactions of (ionic) free radicals by electrophiles, nucleophiles or free radicals, it is important for the long-term stability of imaging so that the feedback reaction according to the above equation can proceed as quickly as possible without side reactions.

It has now been found that by linking RED 1 and O ₂ through a covalent chemical bond, electron transfer is enabled and thus the feedback reaction according to the above equation can be accelerated and side reactions can be avoided.

Furthermore, suitable binder materials have been found which can be used as sealing and sealing materials of the electrochromic device after filling and suitable curing conditions for these binder materials so that there is no risk of side reactions occurring.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides an electrochromic device consisting of a pair of transparent and conductively coated glass or plastic plates in which one may be coated with a mirror layer and in which the conductive layer of one or both plates may be separated into separate, individually electrically connected segments , which

4 »· 4 · 4 · ♦ ··· · * · · · ·

B 4 4 1 ·· 44 are joined together on the sides of their conductive adhesive-coated liners into which spacers may be inserted and where the volume formed by the two plates and the adhesive-liner is filled with electrochromic liquid and where the filling opening or holes required for insertion electrochromic fluids are sealed with a post-fill adhesive which is characterized in that the thermally or photochemically cured epoxy adhesive, or epoxy adhesives that are cured by thermal or photochemical initiation, are used for the adhesive border to form the electrochromic device and a photochemically cured acrylate adhesive or epoxy adhesive that is cured by photochemical or subsequent photochemical initiation at room temperature is used in the seal.

Epoxy adhesives are known, for example, from J.V. Muskopf, S.B. McCollister in the Ullmannoos Encyclopedia of Organic Chemistry, VCH Verlaggesellschaft mbH, edition,

Vol. A 9, p. 547 ff., 1987. Curing may take place by an anionic or cationic mechanism.

Acrylate adhesives are known, for example, from V. Dierichs et al. in Ullmanns Encyklopadie der technischen Chemie, VCH Verlagsgesellschaft mbH, ¹ ^ 4 edition, Volume 14, p. 233 ff., 1977. Curing proceeds free radical mechanism, which can be initiated by ultraviolet radiation with the aid of added photoinitiators.

The epoxy adhesive according to the invention for the adhesive bead that holds two transparent sheets together at a desired distance is a two-component or one-component adhesive. Preferably, it is a two-component epoxy adhesive wherein, for example, one component consists of an epoxy compound and the other component consists of an amine, anhydride or Lewis acid or Lewis &apos; ftftft ftftftft ftftftft ftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftft Ft ft »» ft ft ft zásad zásad zásad zásad zásad zásad zásad zásad * zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad zásad Brpnsted acid or Lewis or Brpnsted basic compounds which upon exposure to light or heat release a Lewis or Brpnsted acid or Lewis or Brpnsted base compound.

Particularly preferably, the epoxy component comprises an epoxy having the formula

in which

V represents a bridge which may also carry epoxy groups and the amine component is a primary or secondary aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic, at least a bifunctional amine and the Lewis acid compound which is in closed form is a non-metal halide and Brnnsted acid compound which In closed form, it is a strong protic acid which is derived from non-metal halides.

Examples of these non-metal halides are boron trifluoride, boron trichloride, phosphorus pentafluoride, arsenic fluoride, antimony fluoride or antimony chloride. Protic acids that are derived from, for example, are HBF ₄ HBCI4, HaSFg, HaSClg, HSbFg, HSbClg. Examples of closed i

to · to · to to to to tot tot tot tot tot tot tot ot ot ot ot ot ot ot ot · This halides are adducts of amines with these non-metallic halides, for example BF ₃ .NH (C ₂ H ₅ ) ₂ , BF ₃ .NH (CH ₃ ) C ₂ H ₅ , etc. These compounds release non-metal halides upon heating. The aromatic or heterocyclic diazonium salt tetrafluoroborates are also closed non-metal halides. These compounds release BF ₃ photochemically. Diaryl iodonium or triarylsulfonium salts with anions of the aforementioned protic acids, e.g., (C 8 H 4) ₂ I ⁺ PF 8 -, decompose photochemically to the corresponding protic acids, e.g. HPF 4. These sealed products are known, for example, from RS Bauer, RV Tess, GV Poehlein (eds.) Applied Polymer Science, 2 ^nd ed. , ACS Symposium Series 285, ACS Vashington, 1985. P.931-961.

These adhesives may further comprise other components such as glycidyl ethers or glycidyl esters, phenols or alcohols and, in the case of photochemically curable adhesives, also peroxides or ferrocenes. Examples are glycidyl neodecanoate, hexanediol glycidyl ether, phenol, benzyl alcohol and cumene hydroperoxide.

The spacers can be added to these adhesives so that the adhesive border also simply ensures a constant distance between the two transparent plates. Typical distances are, for example, from 0.005 to 2 mm, preferably 0.01 to 0.5 mm. Examples of suitable spacers are glass or plastic rims, as well as cross-linked fractions of sand, silicon carbide or similar materials.

The adhesive for sealing the electrochromic device after filling it with an electrochromic liquid is preferably a one-component epoxy adhesive, consisting, for example, of an epoxy compound and a closed Lewis or Br0nsted acidic or Lewis or Br0nsted base compound, * 9 9 9 9 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31

Which, upon exposure to heat or light, in particular light, releases a Lewis or Brsted acid or Lewis or Brsted base compound, or an acrylate adhesive, preferably consisting of a bis- and tris-acrylate compound into which a photoinitiator is added which releases free radicals upon exposure to light in the UV or adjacent blue spectral range.

Particularly preferably, the epoxy component comprises an epoxy having the formula

in which

V is a bridge which can also carry epoxy groups, and the Lewis acid compound in the closed form is a non-metal halide and the Bronsted acid compound in the closed form is a strong protic acid which is derived from non-metal halides.

Lewis and Bronsted acids have been described in more detail above in their closed forms.

Also particularly preferably, the acrylate mixture comprises a compound of the formula:

09 09 9 9 9 9 9 9 99 99 9 9 9 9 9 9 9

9 9 99

wherein n is an integer from 0 to 20, preferably 0 to 10, and r 101 is hydrogen or methyl, and

in which

02 /

R is hydrogen or methyl.

The composition of the acrylate mixture (CI) and (CI1) is particularly preferably in the range (CI parts) / (CI1 parts) = 1 to 5.

Photoinciators are particularly preferably benzophenone or thioxanthone derivative compounds which provide free radicals in photolysis. In this context, the use of UV curing photoinitiators is particularly preferred, examples being Irgacure ® 651 (Ciba-Geigy), Darocur ® 1116, Darocur ® 1173, Darocur ® 1664, and the like.

 φ · * · · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

99 Φ 9 9 9

Darocur ^ 2273, Darocur ^ 4043 (all from E. Merck, Darmstadt). A particularly preferred concentration range of these photoinitiators is 0.01 to 5% by weight.

Very particularly preferably, the epoxy component of the adhesive according to the invention for an adhesive bead that holds two transparent plates together at a desired distance is an epoxy having the formula

OH

O (Clil) or

P (CIV), in which the map independently represents an integer of 0 to 20, preferably 0 to 5, and ftft ftft ftft ftft ftftftft ft ft ···· ftftftft ftft ftftftft ft ftft ftft ft • ftftft ftft · ftftft * • ft ftft ftftftft · ftft ftft r100 represents hydrogen or methyl and the amine component is an aliphatic polyamine of the formula

(CV) _: wherein q is an integer from 2 to 10, preferably up to 4, or is an araliphatic amine such as α, α'-diamino-m- or p-xylene or is a polyaminoimidazoline or an aromatic amine such as is bis (-4-aminophenyl) methane or bis (4-aminophenyl) sulfone and the closed Lewis acid compound is an adduct of boron trifluoride with secondary amines such as BF ₃ -NH (CH ₃ ) ₂ H ₃ or is a diazonium salt, such as Ar-N ₂ ⁺ BF 4 ^- , or the closed Brstedn acid compound is an iodonium salt, such as (Ar) 2I ⁺ BF 4 ^- or (Ar) 2I ⁺ PF 8 or a sulfonium salt, such as (Ar) 3 S ⁺ BF 4 or (Ar ) ₃ S ⁺ PFg ~ where

Ar represents an aromatic radical, preferably phenyl.

9 9 99 9 •

9999

9 9 •

9 9 * 9 99

9 9

9 999

9 9 · 9

999

9 9 9

9 9 9

9 9 9

9 9 9

9 99

Very particularly preferably, the epoxy component of the epoxy adhesive of the invention for sealing the cell is an epoxy having the formula

(Clil) or

(CIV), wherein the map independently represents an integer from 0 to 20, preferably from 0 to 5, and r100 represents hydrogen or methyl, and the closed Lewis acid compound is a luoride adduct of this "to" this · to · ♦ ·· · · · * · <Tot tot tot tot tot tot tot tot tot tot tot tot tot tot tot to to to to to this boron with secondary amines such as BF 4 -NH (CH 2) 2 H 5 or is a diazonium salt such as Ar - + BF 4 or the closed Brpnsted acid compound is an iodonium salt such as (Ar 2 -). I + BF? ^- or (Ar? 1 + PFg ^- or a sulfonium salt such as (Ar 1? S + BF? ^- or (Ar) ₃ S ⁺ PFg ^-) wherein:

Ar represents an aromatic radical, preferably phenyl.

Also very particularly preferably the acrylates for sealing the cells consist of a mixture of compounds of the formula

(Cl) wherein n is an integer of 0 to 20, preferably 5 to 15, and r 101 is hydrogen or methyl, and

(Target) «·« ··· 99 * 9 9 9 9 9 9 9 9 9

9 9 9 9 9 9 9 _. 9 9 9 9 9 9 9 9 9 9 9

- 9 9 · * 9 9 · 9 9 9 9

99 99 999 99 99 in which

102

R is hydrogen or methyl.

The composition of the acrylate mixture (CI) and (CI1) is very particularly preferably in the range (CI parts) / (CI1 parts) = 1 to 2.

Very particularly preferably, the photoinitiators consist of compounds based on benzophenone derivatives or thioxanthones which provide free radicals in photolysis. In this context, the use of UV curing photoinitiators is particularly preferred, examples being Darocur ® 1173 (E. Merck, Darmstadt) and Irgacure ® 651 (Ciba-Geigy). A particularly preferred concentration range of these photoinitiators is from 0.1 to 3% by weight.

Particularly preferred, thermally cured epoxy adhesives consist of epoxides of the formula (ClII) in which m is a number from 2 to 5 and amines of the formula (CV) in which q is a number from 2 to 4, and also α, a'-diamino-m -xylene or a mixture thereof, and also optionally other epoxy compounds such as glycidyl esters, φφ ····

4444 44 44 4 Φ φ přičemž přičemž 4 4 4 4 4 přičemž přičemž φ přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž přičemž hexanediol glycidyl ether.

Particularly preferred photochemically cured epoxy adhesives, or photochemically initiated cured epoxy adhesives, consist of epoxides of the formula (ClII) in which m represents a number 2-5 and as a closed Lewis acid compound a diazonium donor such as Ar-N2 ⁺ BF4, or closed Br0nstedova acidic compound iodonium salt such as (Ar ^ i ^ + BF ^- or (Ar) 2 I ⁺ PFG or sulfonium salt, such as (Ar) 3 S ⁺ BF 4 ^- or (Ar) 3 S ⁺ PF6přičemž

Ar represents an aromatic radical, preferably phenyl.

Particularly preferred photochemically cured acrylate adhesives consist of acrylates of the formula (CI) in which n represents a number of 5 to 10 and

R ¹ represents hydrogen, and (C ¹¹ ) wherein i

99 * 9 • 9 9 99 9

9 9 * 9 999 · 9 9 9 9 9 9 9 9 9 9 9 9 9

9999 98 9 9999

99 99 99 99 99

09 /

R is hydrogen.

A particularly preferred composition of the acrylate mixture (CI) and (CI1) is (CI parts) / (CI1 parts) = 5/3.

A particularly preferred photoinitiator Darocur® 1173 (E. Merck, Darmstadt) is used in this context at a concentration of 0.5% by weight.

Epoxy and acrylate adhesives preferably have a high viscosity. This facilitates the application of the adhesives when the two transparent sheets are joined together and the glue lip does not move during curing. This avoids problems, especially when sealing the cells filled with the electrochromic liquid according to the invention, since the relatively high viscosity adhesives do not readily mix with the liquid, as do the low viscosity adhesives. Examples of such mixing may lead to undue sticking effects, but may also in some cases lead to undesirable bonding and thus to deactivation of the conductive coating in the inner part of the cell. Highly suitable viscosities are, for example, > 10,000 mPas, preferably > 20,000 mPas and particularly preferably > 30,000 mPas. The viscosity can be influenced by the adhesive components themselves, for example the degree of oligomerization of n, m, p and / or q in the above formulas (CI) and (ClII) to (CV). However, it can also be affected by additives such as fillers. These fillers may be aerosols, for example based on silica gel or the like, clay soils, organic clay soils, cements, silicates, sands, silicocarbide powder, glass powder or quartz powder, powdered organic polymers or polymer particles, or organic oligomers such as ureas , urethanes, amides, polyesters and the like. Priority

4444

4444

4 4 4 4 4 4 • 4 4 4 4 444 4

4 444 4 444 • 444 44 4 4444 • 4 4 · 44 * 44 * 4 ·· gives aerosols. These fillers also reduce shrinkage during curing and therefore prevent the shape of the glue or even the formation of cracks in the glue.

The curing of adhesives depends on their chemical composition.

Thermosetting epoxy-based epoxy adhesives of the formula (ClII) in which m is from 2 to 5, and amines of the formula (CV) in which q is from 2 to 4, and also α, α'-diamino-m-xylene or mixtures thereof and optionally other epoxy compounds, such as glycidyl esters, exemplified by glycidyl neodecanoate, are cured, for example, at temperatures of 90 to 170 ° C, preferably 110 to 150 ° C for, for example, 5 to 60 minutes, preferably 10 to 30 minutes.

Epoxy adhesives which are cured by photochemical or photochemical initiation and are based on epoxides with the formula (Clil) in which it represents the number 2 to 5 ftft ftftft · ftft ftftftft ftftft · · · · · · ··· · · · · · · And closed Lewis acid compounds, for example

NC? -Cgl? -N? + BF ^- , or Brpnsted acid compounds, for example (CgH?) 21 ⁺ BF4 or (CgH?) 2? ^{+ P} ? 6? ^Not (CgH?) 2 S ⁺ BF4 'or (CgH); ^) + BFG -jS ^- are either fully cured using visible or UV light, or are more preferably only initiated by visible or UV light, the adhesive is not subject to complete curing, and curing is then completed at room temperature or elevated temperature, for example 30-150 ° C preferably 70 to 130 ° C. Curing time depends on temperature. For example, at room temperature, the time may be 10 to 24 hours, but at 110 ° C to 10 to 30 minutes. Exposure can be carried out using a UV lamp of a flashlight or otherwise daylight or daylight luminaires.

In adhesives that have been fully cured in this manner, the adhesive components, especially the epoxy and amine components, are so rigid and completely incorporated into the macromolecular structure that they are no longer capable of reacting with the electrochromic liquid of the invention or with substances formed by reduction or oxidation. The bonds are so strong that they easily withstand and withstand thermal loads, for example between -40 ° C and + 105 ° C, and within this temperature range, the electrochromic liquid of the invention does not start to dissolve them, which could cause them to swell or leak.

Photochemically curable acrylate adhesives based on acrylates of the formula (Cl) in which it represents the number 5 to 15 and

ΦΦ φ φ φ φ φ φ »» φ φ φ ΦΦΦ ΦΦΦ ΦΦΦ ΦΦΦ ΦΦΦ ΦΦΦ ΦΦΦ • • • φ φ φ φ φ · • • φ φ φ φ kterém kterém kterém IO 12 represents hydrogen, with an acrylate composition (parts Cl) / (parts Cl1) = 5/3 and a concentration of Darocur 1173 of 0.5% by weight of the photoinitiators are fully cured at room temperature using UV light or suitable lighting equipment.

In this way, the cured adhesives are easy to withstand and withstand thermal loads of, for example, between -40 ° C and + 105 ° C, and within this temperature range the electrochromic liquid of the invention does not start to dissolve them, which could cause them to swell or leak.

Preferably, the electrochromic liquid is comprised of at least one oxidizable substance RED 2 which releases electrons at the anode and at least one reducible substance 0X ₂ which receives electrons at the cathode and thereby switch to their respective forms OX 2 and RED ₂ , at least one of which releases or receives electrons that are associated with a change in absorbance over the visible range of the spectrum, so that the original forms RED 1 and O _{2 2} are re-formed in each case after the charge is equalized. Specifically, at least one of the RED 0X ₂ substances present is covalently attached to the other via a bridge.

The methods of reduction and oxidation in the liquid of an electrochromic device according to the invention are generally carried out by means of electrons which are received or released at the cathode or φφφφφ ««φφφφφφφφφφφφφ φ φ · · · · ·

Odφ φφ φφφ φφ φφ anode and reaching a potential difference of 0.3 to 3 V between the electrodes. When the electrical potential has been switched off, the charges are balanced - generally spontaneously - between RED2 and 0X ₁ , accompanied by the disappearance or weakening of the paint. This charge alignment also occurs even when the current flows through the inner part of the electrolyte volume.

In its electrochromic liquid, the electrochromic device according to the invention preferably consists of at least one electrochromic substance having the formula (I) y 4 - (β-ζΗβ-υΗβ- ^ζ (i), in which

Y and Z independently represent OX2 and RED4, provided that at least one Y is OX2 and at least one Z is RED4, wherein

OX2 represents the remainder of the reversibly electrochemically reducible reduction-oxidation system, and

RED ^ represents the remainder of the reversibly electrochemically oxidizable reduction-oxidation system,

B represents a bridging member, c represents an integer from 0 to 1000, preferably 0 to 1000

100, particularly preferably 0 to 5, and

* A and b independently represent an integer from 0 to 100, preferably an integer from 0 to 10, particularly preferably from 0 to 3.

Preferably (a + b) - c is <10,000, particularly preferably 100.

In its electrochromic liquid, the electrochromic device according to the invention preferably consists of at least one compound of formula (I) in which:

Y is OX ₂ and

Z represents RED

Y and Z alternate in sequence.

Particularly preferably, with respect to its electrochromic liquid, the electrochromic device according to the invention preferably consists of at least one substance of the formula ox ₂ -b-red ₁ ox ₂ -b-red ₁ -b-ox ₂

RED ₁ -B-OX ₂ -b-RED ₁

0X ₂ - (B-RED ₁ -B-OX ₂ ) dB-RED ₁ (1a), (1b), (1c), or (1d) wherein

0X ₂ RED- £ Β and have the meanings given above and represents an integer of 1 to 5

* • to e to to to to to to to to to to to to to to to to to to to to to to to to to ··

Particularly preferably, with respect to its electrochromic liquid, the electrochromic device according to the invention preferably consists of at least one substance of the formulas (Ia) - (Id) in which:

OX2 is the remainder of a cathodically reducible substance which, in its cyclic voltammogram recorded in an inert solvent at room temperature, exhibits at least two chemically reversible reduction waves, the first of which leads to an increase in absorbance at least one wavelength within the visible range of the electromagnetic spectrum

RED - represents a residue of an anodically reversible oxidizable substance which, in its cyclic voltamogram recorded in an inert solvent at room temperature, exhibits at least two chemically reversible oxidation waves, the first of which leads to an increase in absorbance at least one wavelength in the visible range electromagnetic spectrum; and

B represents a bridging member.

Particular preference is given to an electrochromic device according to the invention comprising at least one compound of the formula (Ia) - (Id) in which:

OX2 represents a residue of the formula 4

X • 4 44 · 4 4

4 4 4

4 4 · 4

· * 4 «

wherein up to R ⁸ , R ⁹ , R ¹¹ to R ¹⁹ independently of one another denote C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl,

C ₃ - to Cy-cycloalkyl, C7- to _C15 -aralkyl or Cg- to ^C io ~ y ^ ¹ »or

R ⁴ and r ⁵ , or R ⁸ and R ⁹ together form a - (CH ₂ ) 2 - or (CH ₂ ) 3-bridge, _r 6 _r 7 _{and R} 22 _r 25 independently of one another denote hydrogen or

C ^ - C4 - alkoxycarbonyl, or R 22 _{and Ar} 23 / ebo _n R ²⁴ form a -CH = CH-CH = CH- bridge, · · · • • • • 1 ··· · · ·

R -Ι and rH, R ^ ² and R ^ ³ ; R 4 and R 4 independently represent hydrogen or in pairs

- (CH ₂ ) ₂ -, - (CH ₂ ) ₃ - ^or -CH = CH- bridge,

R ² ® and R ²¹ independently of one another denote 0, N-CN, C (CN) ₂ or N-C ₈ to C ₁₀ -aryl,

R ^2b denotes hydrogen, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, halogen, cyano, nitro, C 1 -C ₄ -alkoxycarbonyl or C ₈ -C ₁₀ -aryl, R 69 _and R 6 ²⁴ independently of one another denotes hydrogen or C1-C6-alkyl;

R ⁶⁹ ; R ¹² and / or R ⁷⁰ ; R ¹³ forms a -CH = CH-CH = CH- bridge,

E 1 and E ² independently represent O, S, NR 4 - or C (CH ₃ ) ₂ or

E ¹ and E ² together form an -N- (CH ₂ ) ₂ -N- bridge,

R ¹ represents C ¹ -C ₁₈ -alkyl, C ₂ -C ₁₂ -alkenyl, C ₄ -C ₈ -cycloalkyl, C ₇ -C ₈ -aralkyl or C 8 -C 8 -aryl,

Z ¹ denotes a direct bond, -CH = CH-, -C (CH ₃ ) = CH-, -C (CN) = CH-, -CCl = CC 1 -, -C (OH) = CH-, -CCl = CH -, -C = C-, -CH = NN = CH-, -C (CH ₃ ) = NN = C (CH ₃ ) - or -CCl = NN = CC 1,

Z ² is - (CH ₂ ) _r - or -CH ₂ -C ₈ H ₄ -CH ₂ -,

R stands for an integer from 1 to 10 • ftft ftft ftft ftftftft ft ftftft ftft ftftft ftft ftft ftft ftft ftft ftft ftft ftftft ftftft

X 'denotes an anion which is redox-inert under the given conditions,

19 wherein the bond to the bridging member B is through the radicals R-R, _R 22 _-R 27 is _not b _> if E ¹ or E ² represents NR ¹ , it is through R ¹ and in this case the radicals referred to represent a direct bond,

RED2 represents any of the following residues.

(XIII) φφφφ

(XVIII)

ΦΦ ΦΦ · ♦ · 4 4 4 4 • 4 4 94 φ · · · · · · · · · ·

4 · · Φ φφ Φ * (XIX) «· ··· · · · · · · ·

· ---- »« · • · · ···· »· • · * *** c · _t ·. · •« «·» · · · «··» · ♦ · ·· · · «»

R '

(XX) in which

R _{^28, and} R31, R34, R35, R38, R39, R46, R53 _and R56, independently, an _before each represents

C £ - to C ^ g alkyl, C2 to C ₁ 2 ^_a lkenyl, C3-Cy-cycloalkyl, Cy- to C ^ aralkyl or Cg- C10-aryl, and R ^{4 R} \ R 53 and R ⁴ additionally denotes hydrogen, r33 r36, 37, 40

^J R ', R ** M, R ⁴² to R ^45, R ⁴⁷ ,, R ^48, R ⁴⁹ to R ⁵² each independently represent hydrogen, C ^ - to

C4-alkyl, C1- to C4-alkoxy, halogen, cyano, nitro, C1- to C4-alkoxycarbonyl or C3- to Cyg-aryl and R ⁵⁷ and R ⁵⁸ additionally represent optionally benzocondensed aromatic or quasiaromatic five- or 40-membered six heterocyclic ring and R additionally denote NR ⁷⁵ R ⁷⁶ .

and R f _and R $ ⁷

R ⁴⁹ and R ⁵⁰ and / or R ¹ and R ² form - (0 ^) 3-, - _{(CH2) 4} -,

- (CH ₂ ) ₅ - or -CH = CH-CH = CH bridge

7? denotes a direct bond or -CH = CH- or -N = N- bridge, = Z ⁴ = denotes a direct double bond or = CH-CH = or = NN = bridge, this is to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to

E ³ to ³ Ε, Ε ^ -θ and E ^ · ^ independently represents 0, S, NR @ ³ or C (CH _{3) 2} and Eg additionally represents C = 0 or S0 _2, or

E ³ and E ^{4 are each} independently -CH = CH-,

E ^ E ^ independently represents S, Se or NR ^^, R59, R75 _and R76, independently, an _before each represents C - ^ - to C ^ -alkyl,

C ₂ - to C-alkenyl, C ₃ - to Cy-cycloalkyl, Cy * ^ i -C 7-7 -aralkyl or Cg- to C ^ Q-aryl, and R ^{/ S} additionally denotes hydrogen, or

R S _and R76 _{in the} definition of NR ^ R ^ -t fi _in together with the N atom to which they are attached, a five- or six-membered, saturated chain which may contain further heteroatoms, R61 to R68 each independently represents hydrogen, C C1-C6-alkyl, C1-C6-alkoxy, cyano, C1-C4-alkoxycarbonyl or C1-C6-aryl, or r61, r62 _and r67. jj68 is independently - (CH ₂ ) ₃ -,

- (CH _{2) 4} - or -CH = CH-CH = CH- bridge, v is an integer between 0 and 10, wherein the bond to the bridge member B is via one of the radicals r28_r58, R61, R62, R67, R68 _n Ebo when one of the radicals E ³ -E 1 represents NR 4 ', it is over R ^3'' and said radicals in this case represent a direct bond, and

B represents a bridging member with the formula - (CH 2) _n - or

- [Y ¹ s (CH ₂ ) _m Y ² ] o - (CH ₂ ) _p -Y ³ q -, each of which is optionally substituted with C 1 -C 4 -alkyl, C 1 -C ₄ -alkoxy, halogen or phenyl , γΐ to independently represent O, S, ^β ^ θ, C00,

CONH, NHCONH, cyclopentanediyl, cyclohexanediyl, phenylene or naphthylene, denotes C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 4 -C 8 -alkenyl;

Cycycloalkyl, C7- to C1-4-aralkyl or C8-Cigars 1, n denotes an integer from 1 to 12, the map independently denotes an integer from 0 to 8, o denotes an integer from 0 to 6, and q and denotes independently an integer of 0 or 1.

Very particular preference is given to an electrochromic system according to the invention which consists of at least one compound of the formula (Ia) - (Id) in which:

OX2 represents a radical of formula (II), (III), (IV) or (V) wherein 9 9 9 9 9 9 9 9 9 9 9 9 9 · * * * ·

999

99

9 9 9

9 9 9

9 9 9

9 9 9

99

R ³ , R ³ , R 4? r ³ , r ⁸ and r ⁹ independently represent C 1 -C 12 -alkyl, C 2 -C 8 -alkenyl, C 8 -C 8 -alkyl;

Cycycloalkyl, C8-C18-aralkyl or C8-C10-aryl,

R ⁶ and R? independently of one another are hydrogen, methyl, ethyl, methoxy, ethoxy, fluoro, chloro, bromo, cyano, nitro, methoxycarbonyl or ethoxycarbonyl,

R -'- θ, rUjR · ¹ · ^ r! 3 and R, R ³ independently represent hydrogen, or when a direct bond, in each case together represent - _(CH2) 2-, - (CH ₂ ) 3- or -CH = CH- bridge, or

R 1, R ⁵ _and r 8, R 4 independently of one another in pairs together represent an i - (CH ₂ ) 2 - or - (0112) 3-bridge when

Z * indicates a direct bond.

r69 r74 independently of one another denotes hydrogen or C1-C4-alkyl,

E ¹ and E 2 are identical and represent O, S, NR 4 or

0 (0113) 2, or together form N (CH 2) 2 ^- N- bridge,

R ¹ represents C ¹ -C ₄ -alkyl, C ₂ -C ₄ -alkenyl,

Cgaž Cy - cycloalkyl, Cy- to ^C 15 -aralkyl or C _1Q Cgaž -aryl Z3 represents a direct bond, -CH = CH-, -C (CH) = C'H-, -C (CN) = CH-, -CO or -CH = NN = CH-, represents - (CH) _r - or -CH 2 -C 8 H ₄ -CH 2 -,

- 32 φ * φφφφ. . ♦ · · ♦ »» »», »,,,, · · · · · · · · · · · · · · · · · · · · · · · ·· * r represents cell number 1 to 6

X represents, under the given conditions, a redox-inert colorless anion, wherein the bond to the bridging member B is via one of the radicals R-R 1 or, when one of the radicals E or E represents NR ¹ , is via R ¹ and said radicals x in this case represent a direct link,

RED 1 represents a radical of formula (X), (XI), (XII), (XIII), (XVI), (XVII), (XVIII) or (XX), wherein up to R ²¹ , R ⁶ , r 35, r 38, r 39 , r46, r53 _and r54 are independently of one another

Ci - to C £ ₂ -alkyl, C ₂ - to C-alkenyl, C ^ - to Cy-cycloalkyl, Cy- to C ^ aralkyl or Cg- to C ^ Q-aryl, and R46, R53 R54 _H additionally denotes hydrogen,

Tj33 _d 36 d> 37 _d 40 _d 41 _d 47, 56

^RJ , ^RJD , R ° ', R ^HU , R' ^tx , R * ^z to R ⁵² , R ⁵⁵ and R ^; independently of one another are hydrogen, methyl, ethyl, methoxy, ethoxy, fluoro, chloro, bromo, cyano, nitro, methoxycarbonyl, ethoxycarbonyl or phenyl; and

CQ

R and R additionally denote 2- or 4-pyridyl and additionally denote NR ²² R ² denotes a direct bond or a -CH = CH- or N = N bridge, • · to to to to.........

= Z ⁴ = represents a direct double bond or a = CH-CH = or = NN = bridge, E ^, Ε ^ θ and each independently represents O, S, NR ^ or C (CH ₃₎ 2, but E ^ and E ⁴ have the same meaning,

E ^ to E ^ are the same to each other and denote S, Se or NR ^ 9 _and E ^ additionally denotes C = O,

E ^ represents NR ^ ^ where it represents a direct bond to the bridge

B, a

E? E ^ are as defined above, but may be another stej no, R75 _and R76 each independently represent Cy- to Cy2 ^- alkyl,

C 2 -C 8 -alkenyl, C 8 -C 8 -cycloalkyl,

C 1- to C 3-8 aralkyl or C 3- to C 1-7 -aryl and r 73 additionally denote hydrogen, or

R 5 _and r 76 _{in the} definition of NR 6 R 6, together with the N atom to which they are attached, represent pyrrolidine, piperidine or morpholine, r 61, r 62 _and r 67, r 68 independently of one another are hydrogen,

C 1- to C 1-4 -alkyl, methoxycarbonyl, ethoxycarbonyl or phenyl or in pairs together represent - (¢ 112) 3- or - (O ^) 4-bridge, ♦ 0 0000 • 0 • 000

0000 0 0 0 0 0 0 0 0

0 00 F R63 _and R66 are hydrogen, and v is an integer from 1 to 6, wherein the bond to the bridge member B is via one of the radicals R ²⁸ -R ^41, R ⁴⁶ -R ^56, R ^61, R ^62, R ^67, R ^68, or when one of the radicals e is NR -eH ^ ^ j ^ _e through R _{and the} radicals mentioned in that case represent a direct bond,

Β represents a bridge member with the formula

- (CH ₂ ) _m -O- (CH ₂ ) _p ,

- (CH) _m -NR ⁶⁰ - (CH 2) p -, - (CH 2) _m -C ₆ H ₄ - (CH ₂ ) _p -, - [O- (CH ₂ ) _p ] _o -O-,

- [NR ⁶⁰ - (CH 2) p] o -'- ^{NR60 [C} 6 ^H 4- ^(CH 2) p] o ^{-C 6 H} 4-5

- (CH 2) _m -OCO-C ₆ H ₄ -COO- (CH 2) _p -,

- (CH 2) _m -NHCO-C ₆ H ₄ -CONH- (CH 2) p -,

-tCH 2) _m -NHCONH-C ₆ H ₄ -NHCONH- (CH 2) p -,

- (CH 2) _m -OCO- (CH 2) t -COO- (CH ₂ ) -,

- (CH 2) _m -NHCO- (CH ₂ ) _r CONH- (CH) p -,

- (CH 2) _m -NHCONH- (CH 2) t -NHCONH- (CH ₂ ) _p R 6 Q represents methyl, ethyl, benzyl or phenyl, n represents an integer from 1 to 10, the maps independently represent integers from 0 to 4 , o is an integer from 0 to 2 and t is an integer from 1 to 6.

Particular preference is given to the electrochromic system.

44

4 4

I · · ·

4 4

4 4

4 according to the invention, which consists at least of formula (Ia) - (Id) of one substance in which:

X ₂ is a radical of formula (II), (IV) or (V) in which

R ² , and r 8 represent a direct bond to the bridging member B,

R ² , R 4 and R 4 independently represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or, in the case of formula Ic or Id, also represent a direct bond to the bridging member B, r 6 and R ² are identical and represent hydrogen, methyl, methoxy, chloro, bromo, cyano or methoxycarbonyl,

RLO, R · R · * ^2, and R @ ¹ independently represent hydrogen, or when tG represents a direct bond, in each case in pairs together represent a --CH.dbd.CH-- bridge, R 69 _and R ²² are identical and denote hydrogen, methyl or ethyl,

R ² _and R ^ ² ^ is hydrogen,

E · * · and E ² are identical and denote 0 or S, τλ represents a direct bond or -CH = CH-,

Under the given conditions, X represents a redox-inert colorless

4 aniont,

RED ^ represents a radical of formula (X), (XII), (XIII), (XIV) or (XVII);

4 4 444 ·· · · ♦ · ftft · · ·· 4

4 4 4

44

R ²⁸ , R ³⁴

R ⁴⁶ and R ⁴⁹ also represent a direct bond to the bridge member B,

R ²⁹ to R ^3, R ³³ and R ^{39 are each} independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or, in the case of formula Ib or Id, R and R also represent a direct bond per bridge member Β,

R ^32, R ⁴² and R ⁴⁸ represent hydrogen, R36, R37, R40, R41 R50 R52 _Nez and _v i _s i _{e to SO} It runs represent hydrogen, methyl, methoxy, chlorine, cyano, methoxycarbonyl or phenyl or, in the case of the formula Ib or Id, R ^{3 '} also represents a direct bond to the bridging member B 10

Z represents a direct bond or -CH = CH- or -N = N bridge, = Z ⁴ = represents a direct double bond or = CH-CH = or = NN = bridge,

E ³ to E ³ independently represent 0, S or NR ³⁹ , but E ³ and E ^{4 have the} same meaning,

E 1 to E ⁹ are identical to each other and represent S, Se or NR ³⁹ ; represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or phenyl, or in the case of formula XVI in 1b or Id also represents a direct bond to the bridging member B,

B represents a bridging member with the formula - (CH ₂ ) _n -,

- (CH ₂ ) _m -O- (CH ₂ ) _p ,

- (CH ₂ ) _m -NR 60 - (CH ₂ ) _p -, - (CH 2) _m -C ₆ H ₄ - (CH ₂ ) p -,

-O- (CH ₂ ) _p -O-, -NR 60. (CH ₂ ) _p -NR 60 -, - (CH ₂ ) _m -OCO-C ₆ H ₄ -COO- (CH ₂ ) _p -, - (CH _{2) m} -NHCO-C ₆ H 4 -CONH- (CH2) p-, - (CH _{2) m -NHCONH-C6} H4 NHCONH _{(CH2) p} -, - (CH _{2) m} -OCO- ( CH ₂ ) _t -COO- (CH ₂ ) _p -, - (CH ₂ ) _m -NHCO- (CH ₂ ) _t -CONH (CH ₂ ) p -, - (CH ₂ ) _m -NHCONH- (CH ₂ ) _t -NHCONH- (CH ₂ ) _{p r} 60 represents methyl, n represents an integer from 1 to 10, the maps are identical and represent an integer from 0 to 2 and _t represents an integer from 1 to 6.

Very particularly preferred is an electrochromic device according to the invention comprising at least one compound of formula (Ia) corresponding to one of the formulas or at least one compound of formula (1b) corresponding to one of the formulas

4 4 4

4 4 • 4 4 4

4 4 • 4 4 ·· 4 44

4 444 4 4 4 · • · 44444 4 · · 4 4 4 4 4 ·· ··· 44 44

(XXI),

2X-

(XXII),

- 39 ** ·· «· • · <

4 1 • · r 4 4 4

49 · 444

4 4 9

4 4

1 4 44

44

4 4 i 4 4 4

4 4 4 1

4 4 4

44

R ³⁷ //

2X //

(XXV),

35.

R. .. A ' ^N ^ ^{£ 4} ii .N

N

V // (XXIII),

NE ⁴ * y .N

'E'

(XXIV),

(XXVIII),

or at least one substance of the formula (Ib) corresponds to one of the formulas (Ib)

R ‘

(XXXI) ft · ···· ftft ftftftft ftft ftft • ft · ··· ftftft · ftft ft «ftftftft ft Φ · <

· Ft ft ft ft ft ft ft ft ft ft ft ft ft ft «« ««

R ⁷ (XXXIV).

· »·· · · · ·

(XXXV) + 70

(XXXVI)

R ⁷ ftft · ft * ftftftft ft ftftft ftft ftft ftftft ft ftftftft ft ft ftft ftft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft · ft • ft or at least one substance of formula (Ic) corresponding to one of the formulas

(XXXVII)

(XXXVIII),

(XXXIX)

• • • • to ··

This to this to this to this

R ⁶

<XLD.

in which

R ³ , R ³ , R ³³ and R ³ independently represent methyl, ethyl, propyl, butyl, pentyl, hexyl or benzyl,

R 1, r 7 _and r 36, r 37 _y pairs are identical and represent hydrogen, methyl, methoxy, chloro, cyano, or methoxycarbonyl, to this to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · to · Β «to to to to to f

«·· · • ·· · this i o ï i

R and R are hydrogen, or when Z is a direct bond, they together represent a -CH = CH- bridge,

R ^oy and R 'are identical and represent hydrogen or methyl,

9

E and R are identical and represent O or S, z / represents a direct bond or -CH = CH- a bridge, r 32, r 47 _and r 48 represent hydrogen,

E ^ to E $ independently represent O, S or NR ^, but E ^ and E ⁴ are identical,

2Q a-i 59

R to R and R ^{J1 J>} each independently represent methyl, ethyl, propyl, butyl, pentyl, hexyl or ben99 Oi of Y, and R to R are preferably identical,

R ⁴⁰ and R ⁴⁰ are identical and represent hydrogen, methyl, ethyl, propyl, butyl or phenyl, and

Z represents a direct bond, -CH = CH- or -N = N-,

R @ 4 to R @ 52 independently represent hydrogen, methyl, methoxy, chloro, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl, but are preferably identical;

E ° to E ^y are identical to each other and represent S, Se or NR ⁵⁹ ,

Z ⁴ represents a direct double bond or = CH-CH = or = NN = bridge, • · ♦ ·

represents an integer from 1 to 5, represents 0 or 1 and

X represents a redox-inert colorless anion under given conditions.

In the above definitions of substituents, alkyl radicals, including modified versions, such as alkoxy or aralkyl radicals, are preferably those having 1 to 12 C atoms, especially those having 1 to 8 C atoms, unless otherwise indicated. They may be straight chains or branched chains and may optionally carry additional substituents, such as, for example, C 1 -C ₄ -alkoxy, fluorine, chlorine, hydroxyl, cyano, C 1 -C ₄ -alkoxycarbonyl or COOH.

Cycloalkyl radicals are preferably those having 3 to 7 C atoms, especially 5 or 6 C atoms.

Alkenyl radicals are preferably those having 2 to 8 C atoms, especially 2 to 4 C atoms.

Aryl residues, including those in aralkyl residues, are preferably phenyl or naphthyl residues, especially phenyl residues. These radicals may be substituted with 1 to 3 of the following groups: C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, fluorine, chlorine, bromine, cyano, hydroxyl, C 1 -C 8 -alkoxycarbonyl or nitro. The two adjacent residues may also form a chain.

The electrochromic liquid of the invention preferably comprises at least one solvent.

4

4 4 4 4 4

Suitable solvents are all solvents that are redox-inert at selected voltages and that cannot release electrophiles or nucleophiles or respond alone as sufficiently strong electrophiles or nucleophiles to react with colored free radical ions. Examples are propylene carbonate, τ-butyroacetone, acetonitrile, propionitrile, glutaronitrile, methylglutaronitrile, 3,3'-oxidopropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidine, sulfolane, 3-methylsulfolane or mixtures thereof. Propylene carbonate and mixtures thereof with glutaronitrile or 3-methylsulfolane are preferred.

The electrochromic liquid of the invention may comprise at least one inert conductive salt. Examples of suitable inert conductive salts are lithium, sodium and tetraalkylammonium salts, especially the latter. The alkyl groups may contain between 1 and 18 carbon atoms and may be identical or different. Tetrabutylammonium is preferred. Suitable anions of these salts as well as suitable anions X in formulas (I), (II), (IV) and (VII) are all redox-inert, colorless anions.

Examples are tetrafluoroborate, tetraphenylborate, kyanotrifenylborát, tetramethoxyborát, tetrapropoxyborát, tetrafenoxyborát, perchlorate, chloride, nitrate, sulfate, phosphate, methanesulfonate, ethanesulfonate, tetradecane, trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, benzenesulfonate, chlorobenzenesulfonate, toluenesulfonate, butylbenzensulfonát, tertbutylbenzensulfonát dodecylbenzenesulfonate, trifluormethylbenzensulfonát, hexafluorophosphate, hexafluorosenate, hexafluorosilicate, 7,8- or 7,9-dicarbonido-undecarborate (1-) or (2-), which are optionally substituted on B and / or C atoms by one or two methyl, ethyl, butyl or phenyl groups , dode- 49 ftftftft ftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftftft kahydro-dicarbadodecarborate (2-) or B-methyl-C-phenyldodecahydro-dicarbadodecarborate (1-).

In the case of polyvalent anions, X 'is one

0-equivalent, eg, represents 1/2 SiFg.

The conductive salts are preferably used in the range of 0 to 1 mol.

Thickening agents may be used as further additives to the electrochromic liquid to control the viscosity of the liquid. This may be important to avoid segregation, i.e., the formation of colored bands or spots during extended on-mode operation of an electrochromic device containing the electrochromic fluid of the invention, and to control the fade rate upon power off.

Suitable thickeners are all conventional and customary compounds intended for this purpose, such as polyacrylate, polymethyl acrylate (Luctite Lr), polycarbonate and polyurethane.

The electrochromic liquid may also be in gel form.

Other suitable additives for the electrochromic liquid are UV absorbers to improve light stability. Examples are Uvinol ® 3000 (2,4-dihydroxybenzophenone, BASF), SANDUVO ®

3035 (2-hydroxy-4-n-octyloxybenzophenone, Clariant), Tinuvin ® 571 (2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, Ciba), Cyasorb 24 ^ (2,2 ' -dihydroxy-4-methoxybenzophenone, American

Cyanamide Company), UVINUL ® 3035 (ethyl 2-cyano-3,3-diphenylacrylate, BASF), Uvinul ® 3039 (2-ethylhexyl 2-cyano-3,3-diphenylacrylate, BASF), UVINUL ® 3088 (2-ethylhexyl p) -met- 50 * · ··· 49 9 4 4 444 9 4 4 9

4 9 9 4 9 4 9 4 4 4 5

4 9 4 4 4 4 4 4 4 9

4 4 9 4 9 4 94 4 4 4 4 Hoxycinnamate (BASF) and CHIMASSORB ® 90 (4-methoxy 2-hydroxybenzophenone, Ciba).

UV absorbers are used in the range of 0.01 to 2 mol / l, preferably 0.04 to 1 mol / l and can also be mixed.

The electrochromic liquid according to the invention comprises substances of formula (I), in particular of formulas (Ia) to (Id), in each case in a concentration of at least 10 mol / l, preferably 0.001 to 1 mol / l. It is also possible to use mixtures of two or more electrochromic substances of formula (I).

The electrochromic device according to the invention is constructed, for example, as follows. In this context, it is necessary to distinguish between three basic types:

Type 1: full-area electrochromic devices, eg for window panes.

Type 2: mirror-mounted devices that can be shielded electrically, such as car mirrors.

Type 3: electrochromic display devices, such as segmented or matrix displays.

In the case of type 1, the device is made of glass or plastic sheets which are coated on one side with a transparent conductive layer.

This conductive layer consists, for example, of indium tin oxide (ITO), tin oxide with antimony or fluorine additives, zinc oxide with antimony or aluminum ft. Ftftftftft. Ftft ftftft ftft ftft ftft ftft ftftft ftftft ftftftftftftftftftftftftftftftftftftftftft additives, tin oxide or conductive organic polymers such as polythienyls, polypyrroles, polyanilines, polyacetylene. These substances form a transmissive electrochromic device that can be viewed in transmitted light.

In the case of type 2, the plates are used as for type 1. In addition, one of the two plates is provided with a mirror. This mirror arrangement can be applied to the other, non-conductive coated side of one of the two plates. Alternatively, it may be applied to one of the two plates instead of the above conductive coating and thus simultaneously perform the function of the conductive coating and mirroring. In this case, the plate may also be opaque. Silver, chromium, aluminum, palladium or rhodium, or else palladium on chromium or rhodium on chromium, or other known materials can be used for mirroring. In this way a reflective electrochromic device is obtained.

In the case of type 3, a construction method as for type 1 or 2 can be selected. In this way a permeable or reflective electrochromic display device is obtained.

In both cases, however, at least one of the two conductive layers is or is divided into segments that are electrically separated from each other and can be connected individually. Alternatively, it is possible that only one of the two plates is conductively coated and divided into segments. The segments may be separated, for example, by mechanically removing the conductive coating using, for example, creasing, scratching, abrasion or milling, or chemically, for example, using etching, for example, with FeCl 3 and SnCl 3 in hydrochloric acid. This removal of the conductive layer may be locally controlled by the use of masking caps, for example a photoresist mask. However, it is also possible to produce electrically separated segments

99

9 9 9

9 9 9 •

9 9 9

99

9999 9 9 9 9 9 9 9 9

9 99

9999

9 9

9

9 9

9 9

999 using controlled application - controlled, for example, by the use of masking covers, consisting, for example, of a spray-coated or printed conductive layer. Segment joining takes place, for example, by using fine strips of conductive material, using means whose segment is brought into an electrically conductive communication with the contact on the edge of the electrochromic device. These fine contact strips consist of the same material as the conductive coating itself and can be prepared, for example, concurrently with said coating at the same time as it is divided into segments as described above. Alternatively, in order, for example, to improve conductivity, the strips may consist of various materials, such as fine metal conductors, made, for example, of copper or silver. A combination of a metallic material and a conductive coating material is another possibility. These metal conductors may, for example, be applied, eg bonded in the form of fine wires, or they may also be printed. All of these methods just described are generally known from the manufacture of liquid crystal displays (LCD).

The displays can be viewed in transmitted light or also reflectively through a mirror coating.

The conductively coated side in this manner - using, for example, a syringe or an automatic dosing device - leaves at least one filling opening 3 open in order to obtain a sticky rim 2. The filling opening (s) may also be formed on the other side of the edge of the plate 1. They may also be formed at two different edges, for example opposite edges. The second plate 4 with the conductive coating side is then placed on the glue edge and pressed. The spacers set the desired coating distance. This cell is then cured according to the type of adhesive selected as described

to • to · it · to · it to above. This curing may take place thermally, photochemically or thermally with photochemical initiation.

In an atmosphere of an inert gas, such as nitrogen or argon, the cell is then filled through the filling apertures 3 with an electrochromic liquid according to the invention which is not itself oxygen-free and has either been degassed or charged with an inert gas. The filling may take place, for example, by using a pipette or syringe with a gas displacement through the second opening 3. The filling may also be performed in such a way that the cell and the electrochromic device are placed in a vacuumable vessel. The container is evacuated.

The cell with its filling opening 3 (in the case of two or more openings must all lie on one edge) is immersed in an electrochromic liquid. The vessel is then metered with inert gas, whereby the electrochromic liquid rises into the cell until it is completely filled except for possible small gas bubbles.

Regardless of the filling method, the filled cell is cleaned with a paper cloth, for example under an inert gas in the filling openings 3 to remove any adherent electrochromic liquid. Then, the opening (s) 3 is / are sealed with one of the adhesives of the invention for sealing the cell. The adhesive is applied to the aperture 3 and optionally to the area immediately around the aperture using, for example, a syringe or an automatic dispensing device and can also be pressed into the aperture 3. This can be done by placing a small gas bubble in the filling opening between the electrochromic liquid and the adhesive, or also in such a way that the bubble is eliminated. Subsequently, the adhesive is cured as described above for these adhesives.

φ · · · • φ · · φ · · · · φ φ φ φ φ φ φ · φ · φ · · · · · · φ φ φ φ φ φ φ φ φ φ φ φφ φφφ

Depending on the type of adhesive, this can be done using light alone or also thermally with photoinitiation. Here, thermally denotes non-photochemical curing, which should preferably take place at room temperature or at a temperature prevailing during the filling and application of the adhesive. Heating during the curing process, even in pure photo curing, should be avoided, as heating may increase the cell content and therefore not yet fully cured sealant can be squeezed out and a safe seal can be prevented.

The distance between the two plates 1 and 4 is generally 0.005 to 2 mm, preferably 0.01 to 0.5 mm.

Specific embodiments of the above types 1 to 3 may be, for example, the following and are also an object of the present invention:

Type 1: from light protection / light filters:

window panes, for example, for buildings, road vehicles, airplanes, trains, ships, skylights, sliding roofs of cars, glasshouses and conservatories and light filters of any type;

in the area of security / secrecy: separating boards such as room counters in offices, road vehicles, airplanes, trains, transparent protective windows such as bank counters, glass doors and helmets for motorcyclists or pilots;

from the design area: glass oven, microwave, other household electrical appliances, furniture;

·· 9999

9 9

9 9

99

9999

9 9

9 999

9 9 9

9 9

999

9 9

9 9

9 9

9 9

99

Type 2: mirrors of any type, for example rear-view mirrors for road vehicles, trains, in particular planar, spherical and non-spherical mirrors and combinations thereof, for example spherical / non-spherical mirror glazing in furniture;

Type 3: display devices of any type, such as segmented or matrix displays for watches, computers, electrical appliances, electronic devices such as radios, amplifiers, televisions, CD players, etc., bus and train station displays, railway station departure displays and aerodromes, flat screens, all type 1 and 2 applications that include at least one switchable, static or variable display device, for example, separators that contain displays such as Do Not Disturb, Bulkhead busy, for example, car mirrors that may include a display of any desired type such as temperature displays, car breakdowns (eg oil temperature, door open), time, direction, etc.

The self-erasing, single-cell, electrochromic device of the invention may also include other such agents, as described, for example, in US-P 4,902,108, Topics, in addition to the above-described electrochromic agents of formula (I), in particular of formulas (Ia) to (Id). in Current Chemictry

Vol.92, s. 1-44 (1980) and Angew, Chem. 90, 927 (1978). These electrochromic substances come, for example, from the groups listed under formulas (II) to (XX) above, in which case none of the radicals are capable of meeting the definition of a direct bond to bridge B. Examples of other suitable electrochromic substances are tetrazolium salts and salts; ft ft ftft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft metal complexes such as [Fe (C5H5) ^ ⁺ 21θ · Addition of such redox systems may be advantageous, for example to correct colors in the case of the electrochromic device of the invention, such as the display in the on state or intensive shade settings specified color.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

An ITO-coated glass plate (1) was coated in accordance with FIG. 2 with a ring 2 consisting of a mixture of two-component epoxy adhesive KORRAPOX 733 from Kommerling, Pirmasens (component A: epoxy of formula (Clil) sm statistically = 2, maintained as thixotropic by aerosol, viscosity = 20,000 mPas; component B: polyaminoimidazoline, tetraethylpentamine, triethylenetetramine, benzyl alcohol, α, α'-diamino-m-xylene, phenol, viscosity 3500 mPas; A: B = 2: 1 parts by weight) and 3% glass beads with a diameter of 200 mm as spacers and in this ring two filling holes 3 were formed. A second ITO coated glass plate 4 was placed with its coated layer on this glue edge. After 5 minutes at room temperature, the adhesive was cured at 150 ° C for 20 minutes.

In a Glove-Box, a pipette of 0.02 moles of an electrochromic compound of the formula

(CVI)

and 0.04 moles of UV absorber of formula (CVII)

in anhydrous, oxygen-free propylene carbonate. The filling holes (3) were sealed with a mixture consisting of a photochemically initiable epoxy adhesive

DELO-Katiobond ^ 4594, Cannon Industrieklebstoffe, Landsberg,

VE 4218, Cannon-Industrieklebstoffe, Landsberg, which was already maintained thixotropni. The joints were then exposed to daylight for 10 minutes near the window and were cured overnight at room temperature.

Alternatively, this exposure of the CANON adhesive could also be performed using a photographic bulb or a 1 minute exposure using the DELOLUX 03, CANON Industrieklebstoffe, Landsberg bulb at a distance of 30 cm.

In either case, the curing was overnight at room temperature.

The solution in the cell was virtually colorless. Applying a voltage of 0.9 V, the solution turned intense green-blue with peaks at 466 and 607 nm. After switching off the power supply and short circuiting the contents again lost their color within 10

• ft • ft • ft • ft • ft • ft

44 seconds

No change was found after more than 100,000 such cycles.

Example 2

The procedure of Example 1 was repeated except that instead of the 2-component epoxy adhesive, the cell was constructed using a photochemically initiable mixture

D epoxy adhesive DELO-Kationbond 4594 or

DELO-Kationbond ^R VE 4218, Cannon Industrieklebstoffe,

Landsberg and 3% glass beads with a diameter of 200 mm. Curing took place for 10 minutes in daylight near the window and then after 20 minutes at 105 ° C without exposure. Alternatively, this exposure can be performed using a photographic bulb or a 1 minute exposure using a DELOLUX 03 bulb, Cannon Industrieklebstoffe, Landsberg at a distance of 30 cm. After filling the cell as described in Example 1, the filler openings (3) were sealed with a mixture consisting of 3 parts trimethylpropane triacrylate, 5 parts polyethylene glycol and 0.5% by weight Darocur 1173 UV initiator, E. Merck, Darmstadt. The adhesive was cured for 1 minute exposure to the DELOLUX 03, CANON bulb

Industrieklebstoffe, Landsberg at a distance of 30 cm.

The properties of the cell were the same as described in Example 1.

Example 3

The procedure described in Example 1 was repeated except that the filling holes (3) were sealed photochemically

000 *

V 0 0 »<0» 0 0 • 0 00 • 4 »···· 0 0 0

4468

Cannon with DELO-Photobond curable acrylic adhesive (not maintained thixotropic, viscosity = 7000 mPas), Industrieklebstoffe, Landsberg. The bond was then exposed for 1 minute under a stream of nitrogen to the DELOLUX 03 bulb, Cannon Industrieklebstoffe, Landsberg at a distance of 8 cm and cured overnight at room temperature in a glove box.

The properties of the cell were the same as described in Example 1.

Example 4

The procedure described in Example 3 was repeated except that the filler openings (3) were sealed with a photochemically curable DELO-Photobond 4497 acrylic adhesive (4468, which was maintained thixotropic, viscosity = 30,000 mPas), by Cannon Industrieklebstoffe, Landsberg. The bond was then exposed for 1 minute under a stream of nitrogen to the DELOLUX 03 bulb, Cannon Industrieklebstoffe, Landsberg at a distance of 8 cm and cured overnight at room temperature in a glove box.

The properties of the cell were the same as described in Example 1.

Example 5

The ITO coated glass plate was sprayed on the coated layer with a conventional, commercial photoresist, such as Positiv 20 from Kontakt Chemie, Iffezheim, and was dried in the dark at 50-70 ° C for 1 hour. The resistant layer was then coated with a film that covered the film. 2, contains black segments in a transparent environment. This film was printed using a laser printer according to a computer-generated template. The photoresist coating was then exposed through this film using UV light (from a mercury lamp such as HBO 200V / 2 from Osram or from a high pressure Xenon lamp XBO 75V / 2 from Osram) for 1 to 5 minutes. The film was removed and the resistant layer was treated in a sodium hydroxide bath (7 g sodium hydroxide per liter of water) so that the unexposed areas were washed away. The plate thus prepared was then placed in a bath consisting of 67 g of FeCl ₂ x 4 H ₂ O, 6 g of SnCl ₂ x 2 H ₂ O, 104 ml of water and 113 ml of 37% by weight hydrochloric acid. was to remove the ITO layer in non-resistant, previously exposed areas. The remaining resistant layer was removed using acetone. This provides a glass plate 11 having segments 14, conductive connections 13 and contacts 12 thereon.

Mixture consisting of photochemically initiable n epoxy adhesive DELO-Kationbond 4594 or

DELO-Kationbond ^ VE 4218, Cannon Industrieklebstoffe,

Landsberg and 3% 50 mm glass beads were applied in ring 15 on the ITO coated side of the second glass plate 17 with the aperture 16 formed. Then, an etched glass plate 11 as described above was placed on the glue edge in such a way that The ITO layers of the two plates 11 and 17 were facing each other and the resulting geometry was as shown in Fig. 3. The adhesive was cured by exposure to daylight near the window for 10 minutes and then without exposure at 105 ° C for 20 minutes.

Under the atmosphere of nitrogen or argon, the cell was then - 4 4 9 4 9 9 4 9 4 4 9 9 ^w 9 4 9 4 9 4 9 4

44 44 994 99 99 placed vertically downwards into a container containing a solution having a concentration of 0.06 mol of an electrochromic compound of the formula

(CVI) in anhydrous, oxygen-free propylene carbonate in such a way that the orifice 16 was below the surface of the liquid. The vessel containing the cell was placed in a desiccator and evacuated at a pressure of 50 bar. The desiccator was then carefully charged with nitrogen or argon. The electrochromic solution penetrated the cell and filled the entire volume except for small gas bubbles. The cell was removed from the solution, wiped with, for example, a paper cloth in hole 16 under a nitrogen or argon atmosphere, and then sealed using a photochemically initiable epoxy adhesive DELO-Cationbond ^ 4594,

Industrieklebstoffe, Landsberg, concentrated 2% silica gel aerosol. The bond was then exposed to daylight near the window for 10 minutes and cured at room temperature overnight.

Applying a voltage of 0.8 V to the contacts of the 12 segments, such as the cathode, and an etched second plate 17, such as the anodes, quickly formed a saturated green-blue image of the contacted segments. In this way, it was possible to create all the numbers and letters that can be represented by 7 segments in a saturated • 4,444

44 4 green-blue color on light yellow background. When the voltage was turned off and the contacts shorted, the image quickly disappeared again.

Example 6 (comparative example)

The procedure of Example 1 was repeated except that during the design of the cell, KORRAPOX 733 was cured not at 150 ° C, but instead at room temperature overnight.

When the cell was connected to a voltage of 0.9 V, the solution obtained an intense green-blue coloration. After switching off the voltage and short-circuiting the cell, this color disappeared again. Over a period of several days with the cell just shut down, or also at the applied voltage, there has been a gradual development of a blue residual coloration that could be observed in a short-circuited voltage-free state.

Example 7 (comparative example)

The procedure of Example 1 was repeated except that the cell was sealed using KORAPOX 733 epoxy adhesive from Kommerling, Pirmasens (for composition, see Example 1). Cure was overnight at room temperature. During this time, near the filling holes (3), the electrochromic solution obtained a deep blue color, which gradually separated itself throughout the cell and no longer disappeared.

When the cell was connected to a voltage of 0.9 V, the solution obtained an intense green-blue coloration. After the voltage was switched off and the cell was short-circuited, the color disappeared again, but the original color disappeared, but the original color disappeared. · ♦ · · · · · · · · ·

the blue base coloring remained. This residual blue color increased gradually over a period of several days when the cell was just shut down or also at the applied voltage.

Example 8 (temperature test)

The cells of Examples 1 and 4 and 6 and 7 were placed in a heated cabinet at 105 ° C for 1 to 3 hours. The results are shown in the table below:

Article 1 hour 3 hours Color Tightness Color Tightness Example 1 colorless tight colorless tight Example 2 colorless tight colorless tight Example 3 colorless tight colorless tight Example 4 colorless tight colorless tight Example 6 blue podcházel - - Example 7 blue tight blue podcházel

Example 9

a) 9.2 g of phenazine were suspended in 60 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere. 30.8 ml of a 20% by weight solution of phenyllithium in 7: 3 cyclohexane / diethyl ether was added dropwise over 15 minutes, during which the temperature was maintained at a maximum of 35 ° C. The solution was then stirred at room temperature for 30 minutes.

At 15 ° C, 30.2 ml of 1,4-dibromobutane was added in a single batch. During this addition, the temperature rose to 38 ° C. After 6 hours at room temperature, 200 mL of water was added and the pH was adjusted to 7.0. The organic phase was separated, washed three times with 100 ml of water each time and concentrated in vacuo. Finally, the excess 1,4-dibromobutane was distilled off under a pressure of 2.105 MPa. The oily residue was hot dissolved in 400 ml of ethanol. The product which precipitated on cooling was filtered off with suction, washed with ethanol and hexane and dried. 8.0 g (41% of theory) of a pale yellow powder of the formula 9,10-dihydrophenazine were thus obtained

b) 7.5 g of 9,10-dihydrophenazine of formula (CVIII) of a) and 6.1 g of 4,4 &apos; -bipyrridil were stirred in 100 ml of acetonitrile at 70 [deg.] C. under nitrogen for 24 hours. After cooling, the mixture was filtered with suction and the solid product was washed with 50 ml of acetone. Drying gave 6.3 g (60% of theory) of the salt of formula

Br '(CIX) ftft ftft ft ft ftft ft ft ft ft ft ft ft ft ft ft 4 4 4 4 9 9 4 4 4 4 ft ft ft ftft 4 4 994 · Ftft ftft

c) 6.1 g of the salt obtained in b) was mixed into 70 ml

Of N-methyl-2-pyrrolidine together with 2.7 ml of benzyl bromide at 70 ° C under nitrogen for 7 hours. After cooling, the mixture was diluted with 150 ml of toluene and the precipitated product was filtered off with suction. The product was washed thoroughly with 150 ml of toluene and 500 ml of hexane and dried. Thus, 5.5 g (69% of theory) of the dipyridinium salt of the formula were obtained

where X = Br ”.

d) 4.0 g of the product of c) was dissolved in 100 ml of methanol at 65 ° C under a nitrogen atmosphere.

7.4 g of tetrabutylammonium tetrafluoroborate were sprayed over 5 minutes. Precipitation occurred. After 5 minutes at 65 ° C, the mixture was cooled and the precipitate was filtered off with suction, washed with 200 ml of methanol and 50 ml of hexane and dried in vacuo. 3.4 g (83% of theory) of a light beige powder of formula (CX) with X '= BF ₄ ' (= CVI) were thus obtained.

In the electrochromic device according to Examples 1 to 5, a green-blue color was obtained with peaks = 466 and 607 nm.

Claims (14)

PATENT CLAIMS 1. Electrochromic equipment, consisting of a pair of transparent and conductively coated glass or plastic plates, one of which may be provided with a mirror and in which the conductive layer of one or both of the two plates may be separated into separate, individually electrically connected segments which are connected together on the sides of their conductive coatings by means of an adhesive flange in which spacers may be inserted and where the volume formed from the two plates and the adhesive flange is filled with electrochromic liquid and where the filling opening or apertures required to introduce the electrochromic liquid are or are sealed with an adhesive after filling, characterized in that a thermoplastic or photochemically cured epoxy adhesive or an epoxy adhesive which cures thermally after photochemical initiation is used for the adhesive flange for the construction of the electrochromic device, and in that ije photochemically curing acrylate adhesive or an epoxy adhesive which cures photochemically or is at room temperature after photochemical initiation. Electrochromic device according to claim 1, characterized in that the epoxy adhesive is a one-component adhesive. Electrochromic device according to claim 1, characterized in that the epoxy adhesive comprises an epoxy compound, an amine compound and a closed Lewis acid or a closed Brpnsted φφ φφφφ »» φφφφ » An electrochromic device according to claim 1, characterized in that in the epoxy adhesive, the epoxy component comprises an epoxy having the formula: - - - - - - - - - - - - - - - - - - - - · Φφφ φφ φφ acid. χ (C). 5. An electrochromic device comprising spacers. 6. Electrochromic equipment in which V represents a bridge which may also carry epoxy groups and the amine component is a primary or secondary aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic, at least a bifunctional amine, and the Lewis acid compound that occurs in closed form is a non-metal halide and Brnnsted acid compound, which occurs in closed form is a strong protic acid which is derived from non-metal halides. according to claim 1, characterized in that the epoxy adhesive according to claim 1, characterized in that the epoxy adhesive comprises spacers with a diameter of 0.005 to 2 mm from 4444 to 4444. • 44 44 44 • 444 44 4 • 4 4 4 4 4 4 ••• 44 44 44 groups including glass beads, plastic beads, sand and silicon carbide beads. An electrochromic device according to claim 1, characterized in that the acrylic adhesive comprises a compound of the formula wherein n represents an integer of 0 to 20, preferably 0 to 10, and R-1-θΙ represents hydrogen or methyl, or with the formula (CII) wherein _r 120 represents hydrogen or methyl. 99 9999 • ft. 999 * • · 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 999 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 99 99 99 99 99 9 9 9 9 The electrochromic device of claim 1, wherein the viscosity of the adhesive is> 10,000 mPas. 9. The electrochromic device of claim 1, wherein the electrochromic liquid comprises at least one oxidizable substance RED, which releases electrons at the anode, and at least one reducible substance OX2, which receives electrons at the cathode, and so undergoes a transition from a weakly colored or a colorless form to an OX2 or RED color form, wherein in each case the transition is accompanied by an increase in absorbance over the visible spectrum so that the weakly colorless or colorless form is recovered after the charges have been aligned. The electrochromic device of claim 1, wherein at least one of RED _t and OX2 present in the electrochromic solution is covalently attached to the other via a bridge. Method for producing an electrochromic device according to claim 1, characterized in that the adhesive according to the invention, which comprises spacers, is applied to the conductively coated side of one of the plates (1) in such a way that an adhesive bead (2) is obtained. wherein at least one filling opening (3) is left open, the second plate (4) being positioned side of its conductive coating on the glue rim and being pressed, wherein the glue is subjected to thermal or photochemical cure or photochemical initiation thermal cure in an inert gas atmosphere the cell is filled through the filling apertures (3) with an electrochromic liquid according to the invention, which is itself oxygen-free and was either • ft ft. Degassed or treated with an inert gas, the openings (3) are sealed with one of the adhesives of the invention and the adhesive is cured using light alone or also at room temperature using light initiation. Use of the electrochromic device according to claim 1 in the form of window panes, separating panes and visor protective panes. Use of an electrochromic device according to claim 1 in the form of car mirrors. Use of electrochromic devices according to claim 1 in the form of a segmented or matrix display.