EP1786883A1

EP1786883A1 - Organic solid self-supported electrochromic material

Info

Publication number: EP1786883A1
Application number: EP05769502A
Authority: EP
Inventors: Giuseppe Chidichimo; Daniela Cupelli; Maurizio De Benedittis; Giovanni De Filpo; Jessica Lanzo; Pasquale Nicoletta Fiore; Bartolo Gabriele; Giuseppe Salerno; Lucia Veltri
Original assignee: Consorzio per le Tecnologie Biomediche Avanzate - Tebaid
Current assignee: Consorzio per le Tecnologie Biomediche Avanzate - Tebaid
Priority date: 2004-07-20
Filing date: 2005-07-20
Publication date: 2007-05-23
Also published as: WO2006008776A1; ITCS20040008A1

Abstract

A new type of organic solid electrochromic material obtainable by means of drugging of solid preexistant polimeric films with electrochromic molecules and plastifizing molecules nas been invented. Such material has the self-support charatteristics and can, hence, be realized both in sheets, suitable to be subsequently laminated between glaze o plastic surfaces, in laminas with conducting surfaces utilizable without further supports, and in forms different from that planar. Both the products deprived of further supports, and the composits laminated between glaze or plastic supports, which will be obtained from the electrochromic film object of the present invention, are characterized by high transparence and electro-chromism, being it possible to change their colour by application of weak electric field. The film can also be obtained in a version containing mycrodrops of Liquid Crystals, such to possess beyond the electrochromic characteristics also those electro-optical of PDLC film. In such version it is possible to modulate both its colour and its transparence. The electrochromic reponse time can be graded varying the engaged chemical formulations. In a more rapid version the reponse time is inferior also to that of fluid electrochromic films. The material is prepared by cooling of mixtures obtained by dissolving on heat the preformed polymers and the percentages of electrochromic molecules or other eventual substances as conducting or plasticizing polymers or olygomers. The material. presented in this invention is innovative compared to previous electrochromic materials, not only for the particular composition and formulation of the materials, but it can also be realized without being necessary bordered with glaze or plastic supports. The films of the material can be subsequently laminated between other conducting supports. However, some versions of the materials can be engaged without further supports. In this case the layers of organic or inorganic material with high electrical conductivity and further layers of externa isolation will have to be applied on their surfaces. In one of the versions the material object of the invention can be produced also in a variable trasparence way, adding to the formulations opportune quantities of liquid crystalline plasticizers. (electrochromic PDLC).

Description

ORGANIC SOLD) SELF-SUPPORTED ELECTROCHROMIC MATERIAL

Technical field of invention

The present invention concerns an organic solid electrocliromic material obtainable by drugging of preexistant polymeric solid films, with electrochromic molecules and plasticizing molecules. Such material has a characteristic to self support and, hence, can be fabbricated both in sheets adapted to be subsequently laminated between glaze or plastic surfaces and in laminas with conducting surfaces utilizable without additional supports and in forms different from that planar.

State of the art

The traditional organic electrochromic materials are thin films which change their colour when an electric field, generally with low intensity, is applied to them. In such film, the active substances, which are responsable for electro-chromism, migrating towards the electrodes, are subjected to oxyde-reducting processes which change their colour. Such substances are defined anodic substances when they migrate towards the anode (positive electrode), and catodic substances when they migrate towards the catode (negative electrode).

Before the present invention, almost the totality of the electrochromic films of organic nature, consisting of organic electrochromic substances dissolved in other organic substances, could be classified as electrochromic fluid systems and electrochromic pseudosolid films. The main difference between these two categories of films consists in the fact that in the first ones the active substances, or the substances that change their colour, are dissolved in organic mixtures of liquid type. Anodic and catodic substances are free to move inside the fluid solution and can easily migrate towards the electrodes, guaranteeing a rather rapid cromatic reponse compared to electric stimules application. However, these systems have different disadvantages connected to their fluidity. First of all, in case of breaking of the electrochromic devices glaze supports, the spill out of undesired organic substances into the environment is possible, which can be dangerous both for parts and mechanisms of the structures they come in contact and for the effects on the human health. Another problem is constituted by low mechanical resistance of such electrochromic systems in which the glaze supports don't present mutual adhesion being separated by a fluid layer.

Because of these limitations, remarkable efforts were made in the past in order to "freeze" the electrochromic solutions adding the polimerizable monomers having a task to form, once polymerized, the polymeric structures capable to enhance the solutions viscosity. This is the example of electrochromic systems proposed in the patents Donnelly¹ and Gentex². The percentage of such polymerizable monomers compared to other fluid components must remain rather low, so that it is impossible to obtain self-supported films with high mechanical resistance. The enhancement of the polymeric component compared to that fluid, in these systems, obstacles the translational mobility of anodic and catodic substances, which, hence, are not able to migrate towards the electrodes to generate the electro-chromatic transition. The polymeric part must possess "grids" sufficiently broad to permit the diffusion of the molecules provided with electro- chromatic character. If the "freezing" process of electrochromic fluid solutions is pushed over certain limits enhancing the quantity of polymerizable monomers present in the formulations, a clear elongation of chromatic response period to the electric stimule is verified, compared to that of fluid systems. Another inconvenience of the freezing processes is constituted by the complexity of the industrial processes related to the self-supported films fabbrication. In a recent patent³ the possibility to obtain electrochromic self-supported solid films polymerizing, by exposing to U.V. rays, the monomeric component of a mixture containing, beyond the polymerizable monomer, electrochromic substances, solvents and plasticizers, has been claimed. According to these authors a plastic electro-chromic self-supported film could be produced by means of a process comprising a first phase of a monomer polimerization. However, the polimerization (gelation) should be realized suspending the initial fluid mixture between supports deprived of adhesion with the forming polymer. Subsequently, the solid sheet should be removed from these provisional supports and collected in order to be used as a film itself. Such procedure seems complex for the elevated number of the phases involved: 1) settling of fluid formulation, 2) suspension of such solution between the supports transparent to U.V. radiation and not adherable to the film generated during the following polymerization, 3) U.V. polymerization of the supported mixture, 4) separation and collecting of generated film. In the case of the invention that we propose here the number of phases necessary for the industrial fabbrication of a plastic electrochromic solid self-supported material, not necessarily planar- developed (film), is reduced to two: 1) realization on heat of a fluid mixture of all the components, 2) fabrication of electrochromic material in the desired form and geometry by means of extrusion proceedings (planar film), or of moulding (more complex forms) of obtained plastic mixture, in opportune temperature conditions.

THE PRESENT INVENTION

The material object of the present invention presents various innovative elements compared to those patented previously.

The chemical products necessary to the preparation of solid self-supported electrochromic material are the same that constitute it once it is realized in its definitive form and structure, without chemical transformations during the preparation process. This is made possible by the fact that all the components used for its preparation are such that it is possible to mix them homogeneously on heat, with the aim to origin a plastic mixture which will be possible to model in order to produce forms of any dimension and geometrical structure by means of extrusors or opportune moulds. It turns possible, so, to realize also solid electrochromic materials also of tri¬ dimensional form over than those of planar development (film). Also in case when it is desired to produce the simple bidimensional plastic films, to be subsequently laminated between other supports, the use of the material we propose facilities all industrial processes compared to other electrochromic materials presented in the state of the art. For example, it is to think over the extreme simplification due to the elimination of polymerization processes in sito necessary to product electrochromic films presented in previous patents. The main components of the film are:

- preformed polymers with high chemical resistance, excellent properties of adhesion with eventual supports and opportune elastical and mechanical properties: the final thermoplastic materials will conserve in large part these initial properties because these polymers will remain the more represented components in the final formulations. To such polymer classes polyvinylic, polyacrylic, polyuretanic, polyethylenic, polysulfonic, polycarbonatic and generally all thermoplastic polymers having the property to fluidificate on heat below the organic substances decomposition temperature (typically below 200 °C) can be related.

- Plasticizing substances of low molecular weight which have properties such to confer to the final electrochromic materials opportune optical, mechanical, laminability, adhesion, elastical properties.

- Electrochromic substances soluble in the polymers and plasticizers mentioned above having the spectral properties adequate to realize the desired electro-chromatic transitions.

- Highly boiling solvings (boiling temperature superior to 150°C) eventually necessary to facilitate the amalgamation of all the components or to favour the electrodic processes.

- Substances which are stabilizing compared to U.V. degradation and to aging slowing.

- Organic molecules capable to transport electronic charges through the material. The insertion of this last type of component constitutes an important innovative aspect of the electrochromic material object of the present invention.

In the electrochromic materials here presented the active electrochromic molecules don't migrate through the material in order to transport themselves on the electrodes, differently from what happens in the electrochromic films related to previous inventions, being the material itself constituted by a solid plastic matrix. The activation of the only electrochromic molecules mounted inside the matrix near the electrodes is not sufficient to impart the colorationis perceivable by a human eye. It is necessary to activate electrically the electrochromic molecules present in the entire or large part of the material volume in order to obtain effective chromatical transitions. It can be realized permitting the migration of electronic charges through the material by means of adequate molecular mechanisms of electronic charge transport. In order to instaurate efficient mechanisms of charge transport, molecules capable to realize processes of electronic charge transport are inserted in the material formulation together with the electro- chromichal molecules. Such materials can be represented by conductive polymers like polyacethylens, polythiophens, polyfurans or olygomers of low molecular weight of the same compost class. In such case the electronic conduction through the material can occur both by charge transfer between electrochromic and conductive molecules and between various conductive molecules, but also by means of typical polaronic mechanisms which are determined inside the conductive polymers and olygomers. However, other compost classes non-classifiable as conductive polymers or olygomers capable to form charge transfer complexes with electrochromic molecules even if their dimensions don't permit intermolecular transport mechanisms are also useful for the creation of an adequate electronic conduction through the electrochromic material, object of the present invention. In this case, above the opportune molecular concentrations, it is possible to realize an efficient electronic charges migration in the entire electrochromic material, which favours the electro-chromatical transition in entire or in large part of the material volume. The innovation realized by this approach is not reflected only in the fact that electrochromic self-supported materials with desired form and thickness can be fabricated, but also in other important electrochromic properties of the film. The examples which will be illustrated furtherly demonstrate that the graduation of the percentage of molecules capable to enhance the electronic conduction through the material and to transfer the electrones to the electrochromic molecules in sito, allows to obtain various operational conditions of the material which are optimal in different applications of electrochromic material. The reduction of conductive molecules concentration carries to the forming of memory materials in which the suddenly induced by an electrical impulse coloration remains for long periods of time. The enchancing, instead, carries to a realization of films in which the periods of coloration and delocoration in presence and absence of electric field occur in very rapid periods of time, also inferior to 1 second. The materials with long electrochromic memory will be able to find advantageous usages in the applications where it is needed to maintain the system coloured for a long time without using the current circuling through the material. This will allow to pilote devices of large surface with alimentators or batteries with very low energetic erogations. Another innovative aspect presented by the electrochromic materials object of the present invention is constituted by the fact that it is possible to diffuse outside the polymeric matrix a particular class of plasticizers of liquid crystalline nature. It is known that when liquid crystals are diffused inside a polymeric film, a part of this component is separated inside the material in mycroscopical anisotropic drops, which confer to the film interesting electro-optical properties. The so called Polymer Dispersed Liquid Crystals (PDLC)⁴ are obtained whose transparence can be varied from an opacity state to that of perfect transparence after the application of alternate electric field. An electrochromic film obtained according to present invention, in which the right percentage of a liquid crystalline plasticizer has been inserted, can, hence, have a double function of light transmission control. On one hand, it can be coloured by means of an electrical impulse DC (direct current) and on the other hand it can be carried from an opacity state to that of perfect transparency by application of alternating electric fields of opportune intensity and frequency. Such functions can be activated independently. The electrochromic effect is not, in fact, activated by alternating signals, above a certain frequency, while the continuos fields of low tension useful to obtain an electrochromic response are not sufficiently high to activate the trasparency modulation for which very much higher fields are requested. A film obtained with the material object of the present invention which contains a liquid crystalline plasticizer can find interesting applications, being able to generate "smart" windows which, on one hand can ensure the privacy using the variable opacity obtained by means of the PDLC mechanism, and on the other hand they can cut a parte of solar spectrum by means of electrochromic mechanism. With the present invention, it is possible, besides, to prepare electrochromic materials in which the electrochromic substance is active in the infrared band. The electric activation of the material by means of electric fields rather than produce a chromatic variation appreciable in the field of vision of the human eye, produces the absorption of radiation bands, which fall in the infrared field. These radiations transport major part of heat that is transmitted by means of radiation. Hence, the materials object of present invention can also be specialized for the modulation of the infrared radiation through large surfaces, and find interesting applications of solar control type. The solid electrochromic film object of the present invention can be prepared according to the following procedure.

A homogeneous mixture is prepared and may contain all or a part of the following components: 1. Organic thermoplastic polymers (polyethylens, polyvinyls, polyacrylics, polyesthers, polysulfonics, polycarbonatics); 2. One or more than one substances capable to transfer electronical charges changing them both with the electrochromic molecules and between each other or transferring them inside the substances themselves;

3. Anodic and/or cathodic electrochromic susbstances operating in the field of vision or in the infrared range⁵'⁶ ;

4. Plasticizer and solvent highly boiling additionals which can also be liquid-crystalline;

5. stabilizers .

Such mixture is prepared in bulk on heat at an opportune temperature, which allows the fluidification of the polymeric weight and the consequent incorporation in it of all the other components. Subsequently, the plastic mass become homogeneous is transported in the desired form by means of extrusion or mould processes according to the generation of a planar development film or electrochromic materials of different form. If needed, in order to facilitate the mixing of the components mentioned above, it is possible to add one or more than one low- boiling solvents, which can be removed in the mixing phase.

To be clear we precise that the film object of the invention can be obtained in different final formulations, according to the characteristics desired by the applicative exigences like: the electro-chromism type (colors between which the film operates), the reologic parameters, electrochromic reponse times, the tensions and the operational currents etc. In a more simple version the film can be composed only by a majoritary polymer, destinated to have a support function, by the only electrochromic substance, intrinsically capable to transfer electrical charges through the material, by a solvent and/or plasticizer highly boiling. This solution is suitable when: the memory films are needed to obtain in which the charging processes induced by the electrodes, being the slightly conducting material, endure also in absence of the electrodic polarization induced from outside. The more complex versions preview:

• the contemporary presence of different support polymers;

• the contemporary presence of several electrochromic substances in case it is desired to enlarge the absorption spectrum of the material, also realizing different colorations for different operational tensions; it was made possible choosing the electrochromic materials with different potential redox;

• the presence of high-boiling solvents/plasticizers mixtures (temperatures superior to 150 °C);

• the presence of liquid crystalline plasticizers in case it is needed to confer a bi-functional character to the material. In other words it is wanted to preview, beyond the electrochromic function, also the possibility to modulate the transparence of the material by means of alternate electric fields capable to change the configuration of the liquid crystalline molecules dissolved in the material itself.

The films of the electrochromic material object of present invention will be able to be laminated between the conductive glasses or analogous plastic conductive supports, in order to generate composite cells particularly useful in the housing and automobile industry. It is necessary to underline that the electrochromic material structure, being self-supporting and laminable, allows to extend the modern industrial processes of obtaining of special glasses to the obtaining of electrochromic special glasses of large surface.

Another innovation element, introduced by the material object of present invention in the field of the electrochromic devices, should be underlined: electrochromic cells can be obtained without recoursing to further support surfaces, depositing highly-conducting layers of both organic and inorganic type, on two opposite faces of a planar film. Superficial conductive layers of organic type can be realized on the faces of the film, putting the film in an opportunely concentrated solution of a conducting polymer, and evaporing subsequently the solvent. The conductive layers of inorganic type can, on the contrary, be realized by a deposition of metals or conductive oxydes in vacuum. After adding the conducting surface layers, it will be necessary to deposit isolating protection layers with analogous procedures. This procedure can be extended also by non planar forms, generating so tridimensional electrochromic objects. Before the description of some examples of the film object of present invention realization let us deliver the definition of achronyms and chemical formula of the components used in various formulations.

POLYMERS

Polymethylmetacrylate (PMMA)

Polyuretane (PU)

Polyvinyl butyral (PVB) Polycarbonate (PC)

+CH₂-CH₂-^

Poliethylen (PE) Polysulfone (PS)

PLASTICIZERS/SOLVENTS

with R that can be chosen inside the following group: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups. Carbonates

following group: H, alchylic linear r alcossiphenyl linear or ramate

.-Mir OH n can vary from 1 to 10.

Triethylen glycol di-2-ethyI hexanoate (EGO)

Di hexyl adipate (DHA)

Dibuthyl sebacate (DBS)

SUSBSTANCES CAPABLE TO TRANSFER ELECTRONIC CHARGES

The electronic charge tranferring molecules used have been chosen from the following composts classes: where R₁, R₂, R₃, and R₄, can be equal or different and can be chosen in the following groups: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups;

The film can contain charge transferers of conducting polymeric or olygomeric types of the following classes:

R₄, R₅, R₆, R₇, R₈, can be equal or chosen in the following groups: ramate chains, alchilphenyl or or ramate groups, aromatic groups with R.₉ alchylic linear or ramate chains or an aromatic group,

R₉ n can vary between 1 and 10.

or

alcossiphenyl linear or ramate groups, aromatic groups

with R₇ alchylic linear or ramate chains or an aromatic group, n can vary between 1 and 10.

can be equal or different and can be following groups: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups.

es from 1 to 3.

Benz oic acid (AB) 3,4-dihydroxybenzoic acid

Diphcnv Iethcr (DFE)

1,10- Phenantroline

Tetracyanochinodimethane (TCNQ)

Benzophenone 1 35-tri 4,4'-Diaminodiphenyl ether (DADF) hydroxybenzene (THB)

p-Phenylenedi .ami .ne Benzene tetracarbonitrile N,N,N',N'-Tetramethylbenzene-1,4- diamine

Diphenylthiocarbazone (DFTC)

Fumaric Acid

DMADA=N,N-Dimethyl-4,4'-azodianiline

Pararosaniline base

SUDAN m Imidazole 1,2,4 Triazole

Ethyl ferrocene (EF) N-EThylCarbazole

ELECTROCHROMIC SUBSTANCES ACTIVE IN THE INFRARED

where R can be: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups.

ELECTROCHROMIC SUBSTANCES ACTIVE IN THE FIELD OF VISION

The electrochromic molόecuiles absorbing in can the visible region can be chosen between the following composts classes:

aromatic groups; with R which can be a phenol or phenossi group, an alchylic linear or ramate chain or an alcossilic group, a normal or substituted cyclealcan; n is an integer comprised between 1 and 20.

.-hk OH with an integer n comprised between 1 and 20.

where R_1, R₂, R₃, R₄, R₅, R_6, R₇, R₈, and R₉ can be equal or different and can be chosen in the following groups: H, linear or ramate alchylic substitutents, alchilphenyl ramate or linear chains, or phenylic alcossis, phenyls and other aromatic groups, -CN, F, Cl, -OH. p can be comprised between 0 and 20, q and r can vary between 1 and 5.

, R₃, R₄, e R₅, can be equal or can be chosen in the following linear or ramate alchylic alcossilic or phenossilic, other aromatic groups, -CN, F,

where p and n vary independently one on another and can assume integer values from 1 to 12. Another category is the following: Where R_1, R₂, R₃, and R₄, that can be different or equal and can be chosen inside the following group: linear or ramate alchylic substitutents, alcossylic or phenossylic substitutents, phenylics.

methylesil and other alchylic linear or ramate linear or ramate groups or alcossiphenyl, aromatic groups.

be: H, ottil and other alchylic linear or , alchilphenyl linear or ramate groups or aromatic groups.

STABILIZING SUBSTANCES

4-hydroxyphenyl-methyIpropanoate

Ester of the 3,5-di-ter-butyI-4-hydroxyphenyl- propanoic acid and ethylengύcole (AO-2)

Ester of the 3,5-di-ter-butyl-4- hydroxyphenylpropanoic acid and pentaerythritol (AO-3)

Dimethyl-(3,5-di-ter-butyl-4-hydroxyben5jyI) phosphonate (AO-4)

Diphenyl-(3,5-di-ter-butyl-4-hydroxybenzyl) phosphonate (AO-5)

Phenyl ester of the 2,2'-methylen-bis-(4-methyl-6- butylphenyl) phosphoric acid (AO-6)

Tris(2,4-di-ter-butylphenyl) phosphite (AO-7)

EXAMPLES

Example 1

Film components: PVB + Hydroquinone + Viologen with X= Br^" Ri=R₃=R₄=Rn=H and with R₂= R₅= -(CH₂)iiOC(CH₂)₅CH3 (Vl) +Carbonate with R=-CH₃ (PC)+ EGO

A mixture containing PVB=30%, Vl=4%, Hydroquinone =4%, PC=37%, EGO=25% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec, and decolorizes spontaneously (after the electric field is off) in 1 second.

Example 2

Film components: PVB+ Hydroquinone + Vl +PC+ EGO+AO-1

A mixture containing PVB=30%, Vl=4%, Hydroquinone =4%, PC=35%, EGO=24%, AO-I= 3% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec, and decolorizes spontaneously (after the electric field is off) in 1 second.

Example 3

Film components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=30%, Vl=4%, Hydroquinone =4%, PC=42%, EGO=20% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec and decolorizes spontaneously (after the electric field is off) in 3 seconds.

Example 4

Film components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=30%, Vl=4%, Hydroquinone =4%, PC=27%, EGO=35% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec and decolorizes spontaneously (after the electric field is off) in 8 seconds.

Example 5

Film components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=30%, Vl=4%, Hydroquinone =4%, PC=22%, EGO=40% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 6 seconds and decolorizes spontaneously (after the electric field is off) in 10 seconds.

Example 6

Film components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=40%, V 1=4%, Hydroquinone =4%, PC=26%, EGO=26% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec and decolorizes spontaneously (after the electric field is off) in 2 minutes.

Example 7

Film components: PVB+ Hydroquinone + Vl +PC+ EGO A mixture containing PVB=40%, Vl=4%, Hydroquinone =4%, PC=32%, EGO=20% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 20 seconds and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 8

FUm components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=40%, Vl=4%, Hydroquinone =4%, PC=20%, EGO=32% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 20 seconds and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 9

FUm components: PVB+ Hydroquinone + Vl +PC+ EGO+AO-2

A mixture containing PVB=40%, Vl=4%, Hydroquinone =4%, PC=20%, EGO-30%, AO-2=

2% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm.

The film manifests a chromatic variation from yellow pale to blue in the period of 20 seconds and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 10

FUm components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=45%, Vl=4%, Hydroquinone =4%, PC=23.5%, EGO=23.5% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 20 seconds and decolorizes spontaneously (after the electric field is off) in 5 minutes.

Example 11

FUm components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=45%, Vl=4%, Hydroquinone =4%, PC=27%, EGO=20% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 30 seconds and decolorizes spontaneously (after the electric field is off) in 10 minutes.

Example 12

FUm components: PVB+ Hydroquinone + Vl +PC+ EGO

A mixture containing PVB=45%, Vl=4%, Hydroquinone =4%, PC=20%, EGO27% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 40 seconds and decolorizes spontaneously (after the electric field is off) in 10 minutes.

Example 13

Film components: PVB+ Oligothiophene with n= 1 in cui R₁=R₂=Ra=Re=R₇=Rs=H e

R4=R_S=-CH₂CO₂CH₃ (T3)+ Vl +PC+ EGO

A mixture containing PVB=52%, V 1=4%, T3=4%, PC=I 0%, EGO30% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 20 seconds and decolorizes spontaneously (after the electric field is off) in 30 minutes.

Example 14

Film components: PVB+ T3+ Vl +PC+ EGO+AO-3

A mixture containing PVB=45%, V 1=4%, T3=4%, PC=15%, EGO30%, AO-3= 2% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 3 seconds.

Example 15

Film components: PVB+ T3+ Vl +PC+ EGO

A mixture containing PVB=47%, V 1=4%, T3=4%, PC=I 5%, EGO30% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 2 minutes. Example 16

Film components: PVB+ T3+ Vl +PC+ EGO

A mixture containing PVB=42%, Vl=4%, T3=4%, PC=20%, EGO=30% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 17

Film components: PVB+ T3+ Vl +PC+ EGO

A mixture containing PVB=46%, Vl=4%, T3=10%, PC=10%, EGO30% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 5 seconds and decolorizes spontaneously (after the electric field is off) in 4 minutes.

Example 18

Film components: PVB+ T3+ Vl +PC+ EGO

A mixture containing PVB=41%, Vl=4%, T3=10%, PC=15%, EGO=30% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 5 seconds and decolorizes spontaneously (after the electric field is off) in 4 minutes.

Example 19

Film components: PVB+ T3+ Vl +PC+ EGO

A mixture containing PVB=36%, Vl=4%, T3=10%, PC=20%, EGO=30% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 3 seconds and decolorizes spontaneously (after the electric field is off) in 2 minutes.

Example 20

Film components: PVB+ T3+ Vl +PC+ EGO A mixture containing PVB=36%, Vl=4%, T3=15%, PC=15%, EGO=30% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 10 seconds and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 21

Film components: PVB+ T3+ Vl +PC+ EGO

A mixture containing PVB=31%, Vl=4%, T3=15%, PC=20%, EGO=30% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 2 minutes.

Example 22

Film components: PVB+ T3+ Vl +PC+ EGO

A mixture containing PVB=32%, Vl=4%, T3=15%, PC=15%, EGO=30% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 1 minute.

Example 23

Film components: PVB+ Vl +PC+ EGO

A mixture containing PVB=40%, Vl =10%, PC=30%, EGO=20% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 48 hours.

Example 24

Film components: PVB+ Benzoic acid+ Vl +PC+ EGO

A mixture containing PVB=40%, Vl=5%, Benzoic acid=5%, PC=25%, EGO=25% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to violet in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 25

Film components: PVB+ Benzoic acid+ Viologen with X= Br^", R₁=R₃=R₄=Re=H and with

R₂= R₅= -(CH₂)₁₁OCO(CH₂)₆CH₃ (V2) +PC+ EGO

A mixture containing PVB=40%, V2=5%, Benzoic acid=5%, PC=25%, EGO=25% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 26

Film components: PVB+ Benzoic acid+ Hydroquinone + V2 +PC+ EGO

A mixture containing PVB=40%, V2=4%, Hydroquinone =4%, Benzoic acid=2%, PC=25%, EGO=25% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 10 seconds and decolorizes spontaneously (after the electric field is off) in 4 minutes.

Example 27

Film components: PVB+ Benzoic acid+ Hydroquinone + V2 +PC+ EGO

A mixture containing PVB=30%, V2=4%, Hydroquinone =4%, Benzoic acid=12%, PC=25%,

EGO=25% has been prepared and homogenized under shaking with a temperature of 150-200°C.

After, the obtained film is deposited between conducting glasses using spacers with diameter of

65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 20 seconds.

Example 28

Film components: PVB+ 3,4 Di hydroxy benzoic acid+ V2 +PC+ EGO

A mixture containing PVB=30%, V2=4%, 3,4 Dihydrossibenzoic acid=4%, PC=31%, EGO=31% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 1 hour. Example 29

Film components: PVB+ Urea+ V2 +PC+ EGO

A mixture containing PVB=30%, V2=4%, Urea=4%, PC=31%, EGO=31% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 1 hour.

Example 30

Film components: PVB+ 3,4 Dihydroxybenzoic acid + Viologen with X> B(C₆Hs)₄ ^"

Ri=R₃=R₄=R₆=H e with R₂= R₅= -(CH₂)_IIOC(CH₂)_SCH₃ (V3) +PC+ EGO

A mixture containing PVB=30%, V3=4%, 3,4 Dihydroxybenzoic acid =4%, PC=31%,

EGO=31% has been prepared and homogenized under shaking with a temperature of 150-200⁰C.

65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 3 hours.

Example 31

Film components: PVB+ Urea+ V3 +PC+ EGO

A mixture containing PVB=30%, V3=4%, Urea=4%, PC=31%, EGO=31% has been prepared and homogenized under shaking with a temperature of 150-200⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 second and decolorizes spontaneously (after the electric field is off) in 3 hours.

Example 32

Film components: PVB+ Viologen with X= ClO₄ ^", R₁=R₃=R₄=R₆=H and with R₂= R₅= -

CH₂CH₃ (V4)+ Hydroquinone +PC+ EGO

A mixture containing PVB=48.91%, V4= 1.76%, Hydroquinone = 1.80%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 6 seconds.

Example 33

Film components: PVB+ V4+ Hydroquinone +PC+ EGO

A mixture containing PVB=48.97%, V4= 1.83%, Hydroquinone = 0.01%, PC=28.2%, EGO= 20.99% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 hours.

Example 34

Film components: PVB+ V4+ Hydroquinone +PC+ EGO+AO-4

A mixture containing PVB=45.97%, V4= 1.83%, Hydroquinone = 0.01%, PC=28.2%, EGO= 20.99% AO-4= 3% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 hours.

Example 35

Film components: PVB + V4 + DFE+PC+ EGO

A mixture containing PVB=48.91%, V4= 1.76%, DFE= 1.8%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 5 hours.

Example 36

Film components: PVB + V4 + phenantrolene+PC+ EGO A mixture containing PVB=48.91%, V4= 1.76%, phenantrolene= 1.8%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 6 hours.

Example 37

FUm components: PVB + V4 + Biphenol+PC+ EGO

A mixture containing PVB=48.91%, V4= 1.76%, Biphenol= 1.8%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 30 minutes.

Example 38

FUm components: PVB + V4 + Biphenol+PC+ EGO+AO-5

A mixture containing PVB=45.91%, V4= 1.76%, Biphenol= 1.8%, PC=26.53%, EGO= 21%, AO-5= 3% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 30 minutes.

Example 39

FUm components: PVB + V4 + ACN+PC+ EGO

A mixture containing PVB=48.91%, V4= 1.76%, ACN= 1.8%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained firm is deposited between conducting glasses using spacers with diameter of 65 μm.

The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 1 hour.

Example 40

Film components: PVB + V4 + Benzophenone+PC+ EGO

A mixture containing PVB=48.91%, V4= 1.76%, Benzophenone= 1.8%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 hours.

Example 41

Film components: PVB + V4 + Benzophenone+PC+ EGO+AO-6

A mixture containing PVB-45.91%, V4= 1.76%, Benzophenone= 1.8%, PC=26.53%, EGO= 21%, AO-6= 3% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 hours.

Example 42

Film components: PVB + EV diperchlorate + DFC+PC+ EGO

A mixture containing PVB=48.97%, EV diperchlorate = 1.83%, DFC= 0.01%, PC=28.2%, EGO= 20.99% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 40 minutes.

Example 43

Film components: PVB + V4 + DFTC+PC+ EGO A mixture containing PVB=48.97%, V4 = 1.83%, DFTC= 0.01%, PC=28.2%, EGO= 20.99% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 35 minutes.

Example 44

Film components: PVB + V4 + DADF+PC+ EGO

A mixture containing PVB=48.91%, V4= 1.76%, DADF= 1.8%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 50 minutes.

Example 45

Film components: PVB + V4 + TIB+PC+ EGO

A mixture containing PVB=48.91%, V4= 1.76%, TIB= 1.8%, PC=26.53%, EGO= 21% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 38 minutes.

Example 46

Film components: PVB + Biphenol + Oligothiophene with n= 3 in cui

R₁=R₂=R₃=R₆=R₇=R₈=H e R₄=R₅^CH₂CO₂CH₃ (T9)+TCE+DMF+ EGO

A mixture containing PVB=48.91%, Biphenol= 1.224%, T9= 0.006%, TCE=I.873%, DMF=26.53%, EGO= 21.457% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. Il film manifesta una variazione cromatica dal trasparente al giallo in un tempo inferiore ad 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 37 minutes.

Example 47

FUm components PVB+ T9+TCE+V4 +PC+EGO

A mixture containing PVB=48.473%, PC=26.967%, TCE=I.873%, T9=0.006%, VΦ=1.224%, EGO=21.457% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 6 hours.

Example 48

FUm components PVB+ DMADA +TCE+V4 +PC+EGO

A mixture containing PVB=48.473%, PC=26.967%, TCE=I.873%, DMADA=0.006%,

V4=1.224%, EGO=21.457% to which dimethylformammide (DMF) was added has been prepared. After having homogenized the mixture under shaking, the solvent (DMF) is eliminated by heating at ca. 160 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 10 hours.

Example 49

FUm components: PMMA+ V4+TCE+PC

A mixture containing PMMA=70.00%, PC=27.00%, TCE=I.8%, V4=1.2% to which dichlorometane has been added. After having homogenized the mixture put under shaking, the solvent (dichlorometane) is eliminated by heating at 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from transparent to deep blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 minutes.

Example 50 Film components: PMMA+ V4+TCE+PC +AO7

A mixture containing PMMA=66.00%, PC=27.00%, TCE=I.8%, V4=1.2%, AO-7= 4% to which dichlorometane has been added. After having homogenized the mixture put under shaking, the solvent (dichlorometane) is eliminated by heating at 40-50 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from transparent to deep blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 minutes.

Example 51

Film components: PMMA+ Oligothiophene with n= 2 in cui H e

R₄=R₅^CH₂CO₂CH₃ (T6) +TCE+V4+PC

A mixture containing PMMA=69.930%, PC=26.967%, TCE=I.873%, T6=0.006%, V4 = 1.224% to which dichlorometane has been added. After having homogenized the mixture put under shaking, the solvent (dichlorometane) is eliminated by heating at 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 5 minutes.

Example 52

Film components: PMMA+ Oligothiophene with n= 1 in cui e

R₄=R₅^CH₂CH₂OCH₃ (T31)+TCE+V4+PC

A mixture containing PMMA=67,20%, PC=28.90%, TCE=2.30%, T31=0.01%, V4=1.59% to which dichlorometane has been added. After having homogenized the mixture put under shaking, the solvent (dichlorometane) is eliminated by heating at 40-50 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation dal trasparente al blue in the period inferior to 0.1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 minutes.

Example 53

Film components: PMMA+PT5 +TCE+V4+PC

PT5

A mixture containing PMMA=65.300%, PC=30.700%, TCE=2.300%, PT5=0.011%, V4=1.689% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from light pink to violet in the period inferior to 0.1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 5 minutes.

Example 54

Film components: PMMA + T3 + TCE + V4 + PC

A mixture containing PMMA=66,80%, PC=29.20%, TCE=2.599%, T3=0.011%, V4=1.39% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from yellow pale to blue in the period inferior to 0.1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 2 minutes.

Example 55

FUm components: PMMA+ T9+TCE+EF+PC

A mixture containing PMMA= 60.000%, T9=0.010%, TCE=2.910%, EF=2.360%, PC=34.720% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from dark yellow to deep green in the period of 2-3 seconds order under the action of a very weak intensity tension and decolorizes spontaneously (after the electric field is off) in 15 minutes. Example 56

Film components: PC+ T9+TCE+V4+PC

A mixture containing PC=59.840%,- PC=36.016%, TCE=2.502%, T9=0.008%, V4=1.634% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from pale yellow to deep blue in the period inferior to 0.1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 3 minutes.

Example 57

FUm components: PS+ ParaRosAniline+T9+TCE +PC

A mixture containing PS=60.000%, ParaRosAniline=0.008%, T9=0.009%, TCE=5.163%, PC=34.820 to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. The film manifests a chromatic variation from pale pink to blue in the period of 2-3 seconds order under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 5 minutes.

Example 58

Film components: PolyUretane (PU)+ T9+TCE+V4+PC

The film containing PU=80.007% PC=17.953%, V4=1.240%, TCE=0.797%, T9=0.003% has been prepared.

The PU has been obtained making react polytetrahydrofurane (I) = 57.373%, 1,3-Bis (1- isocyanate-l-methylethyl)-benzen (II) = 28.033%, 4,4'-Methylenebis (2,6-dimethylaniline) (IV)

= 14.594%.

65 μm. The film manifests a chromatic variation from yellow pale to blue in the period of 1 sec under the action of a very weak intensity voltage and decolorizes spontaneously (after the electric field is off) in 10 hours.

Example 59

Film components: PolyUretane+ DMADA +V4+PC The film containing PU=64.000% PC=33.419%, DMADA=0.102%, V4=2.400% has been prepared.

= 14.594%.

65 μm. The film manifests a chromatic variation from pale yellow to blue in the period of 2-3 seconds order under the action of a very weak intensity tension and decolorizes spontaneously

(after the electric field is off) in 10 hours.

Example 60

Film components : PVB+E49+ V4+Hydroquinone +PC

A mixture containing PVB=30%, E49=30%, V4=2.5%, Hydroquinone =2.7%, PC=34.8% has been prepared and homogenized under shaking with a temperature of 150-200°C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm.

After the phase separation thermal process the electrochromic PDLC film is obtained. The alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 1 V/μm, while the continuous electric field to be applied in order to obtain a chromatic variation from pale yellow to blue is of 0.03 V/μm (i^lmA) (t up < lsec, t down = 2-3 sec).

Example 61

Film components: PMMA+TN10427+ T9+TCE+V4+PC

A mixture containing PMMA=58.500%, TNl 0427=19.400%, T9=0.005%, TCE=I .377%, V4=0.918%, PC=19.800% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. After the phase separation thermal process the electrochromic PDLC film is obtained. The alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 1.2 V/μm, while the continuous electric field to be applied in order to obtain a chromatic variation from pale yellow to blue is of 0.03 V/μm (i=lmA) (t up< lsec, t down = 2-3 sec).

Example 62

Film components: PMMA+E49+ T9+TCE+V4+PC

A mixture containing PMMA=57.500%, E49=20.400%, T9=0.01%, TCE=3.03%, V4=0.817%, PPC=I 8.200% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. After the phase separation thermal process the electrochromic PDLC film is obtained. The alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 0.9 V/μm, while the continuous electric field to be applied in order to obtain a chromatic variation from pale yellow to blue is of 0.01 V/μm (i=lmA) (t up< lsec, t down = 2-3 sec).

Example 63

Film components: PVB+TN10427+ DMAD+TCE+V4+PC

A mixture containing PVB=55.500%, TNl 0427=22.400%, DMAD=0.01%, TCE=1.09%, V4=1.2%, PC=I 9.800% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. After the phase separation thermal process the electrochromic PDLC film is obtained. The alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 1.0 V/μm, while the continuous electric field to be applied in order to obtain a chromatic variation from pale yellow to blue is of 0.02 V/μm (i=lmA) (t up< lsec, t down = 2-3 sec).

Example 64

Film components: PVB+E49+ T9+TCE+V4+PC

A mixture containing PVB=58.300%, E49=19.2%, T9=0.008%, TCE=I.492%, V4=1.208%, PC=19.800% a cui e stato aggiunto un eccesso di dichlorometane. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 ⁰C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. After the phase separation thermal process the electrochromic PDLC film is obtained. The alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 1.0 V/μm, while the continuous electric field to be applied in order to obtain a chromatic variation from pale yellow to blue is of 0.02 V/μm (i=lmA) (t up< lsec, t down = 2-3 sec).

Example 65

Film components: PMMA+E7+ TCE+V4+PC

A mixture containing PMMA=60.82%, E7=25.60%, TCE=1.00%, V4=2.4%, PC=10.180% to which dichlorometane was added has been prepared. After having homogenized the mixture under shaking, the solvent (dichlorometane) is eliminated by heating at ca. 40-50 °C. After, the obtained film is deposited between conducting glasses using spacers with diameter of 65 μm. After the phase separation thermal process the electrochromic PDLC film is obtained. The alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 0.7 V/μm, while the continuous electric field to be applied in order to obtain a chromatic variation from pale yellow to blue is of 0.01 V/μm (i=lmA) (t up< lsec, t down = 2-3 sec).

BIBLIOGRAPHY:

1. U.S.A. Patent n° U.S. 6,002,511 del 1999.

2. U.S.A. Patent n° U.S. 4,902,108 del 1990.

3. U.S.A. Patent n° U.S. 6,420,036 del 2002.

4. J.W. Doane, G.Chidichimo andN.A. Vaz, U.S., No. 4,688,900 (1987).

5. H. Meng and F. Wudl, Macromolecules, 34, 1910 (2001).

6. H. Meng, D. Tucker, S. Chaffms, Y. Chen, R. Helgeson, B. Dunn and F. Wudl, Advanced Materials, 15, 146 (2003).

Claims

1. Organic solid self-supported electrochromic material characterized by the fact that it is obtained by mixing on heat: one or more than one thermoplastic polymers which have the property to fluidificate themselves on heat below the temperatures inferior to those of organic substances decomposition; plastifying and/or solvent high-boiling substances;

- electrochromic substances which are soluble in the polymers and plastifiers mentioned above;

- organic substances capable to transport electronic charges through the material or onto the electrodes; substances which are stabylizing comparing to U.V. degradation and to the olding slowing; and by subsequent cooling of the obtained mixture.

2. Organic solid self-supported electrochromic material, according to claim 1 in which the thermoplastic polymer belongs to the polyuretanic, polyethylenic, polisulfonic, polycarbonatic, polyvinylic class.

3. Organic solid self-supported electrochromic material, according to claim 1 in which said electrochromic substances belong to the electrochromic materials classes in the infrared and they are of this type:

4. Organic solid self-supported electrochromic material, according to claim 1 in which the electrochromic substances belong to the electrochromic materials classes in the field of vision and they are of this type The electrochromic composts in the field of can vision can be chosen between the following compost classes:

aromatic groups;

with R which can be a phenyl or phenossy group, a linear or ramate alchylic chain or an alcossylic group, a normal or substituted cycloalcane; n is an integer comprised between 1 and 20.

Λ^~k OH n is an integer comprised between 1 and 20.

where R_1, R₂, R₃, R₄, R₅, R_6, R₇, R₈, and R₉ can be equal or different and can be chosen in the following groups: H, linear or ramate alchylic substitutents, alchilphenyl ramate or linear chains, or phenyl or phenylic alcossi and other aromatic groups, -CN, F, Cl, -OH. p can be comprised between 0 and 20, q and r can vary between 1 and 5. R₃, R₄, e R₅, can be equal or can be chosen in the following linear or ramate alchylic alcossylic or phenossylic, phenol and other aromatic groups, -CN,

where p and n vary independently one on another and can assume integer values from 1 to 12. Another category is the following:

where R_1, R₂, R₃, e R₄, that can be different or equal, and can be chosen inside the following group: linear or ramate alchylic substitutents, alcossylic or phenossylic, phenylic substitutents.

methylesil and other linear or ramate alchylic l or alcossiphenyl linear or ramate groups aromatic groups.

other linear or ramate alcossiphenyl linear or

5. Organic solid self-supported electrochromic material, according to claim 1 in which the organic substances capable to transport electronic charges through the material belong to the classes of substances tansferers of electronic charge of the type

The electronic charge transferring molecules utilized have been chosen from the following compost classes: where R₁, R₂, R₃, and R₄, can be equal or different and can be chosen in the following groups: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups;

The film can contain transferers of charge of conductive polymeric or olygomeric type in the following classes:

R₄, R₅, R₆, R₇, R₈, can be equal or chosen in the following groups: ramate chains, alchilphenyl or or ramate groups, aromatic groups with R-₉ alchylic linear or ramate chains or an aromatic group, n can vary between 1 and 10.

or

alcossiphenyl linear or ramate groups, aromatic groups

with R₇ linear or ramate alchylic chains or an aromatic group, n can vary between 1 and 10.

R₂, can be equal or different and can be following groups: H₅ linear or ramate alchylic chains, alchilphenyl linear or ramate groups or alcossiphenyl, aromatic groups.

varies from 1 to 3.

Benzoic acid (AB), Urea, 3,4-dihydroxybenzoic acid, DiphenylEther (DFE)₅ Tetracyanochinodimetane (TCNQ)₅ 1,10- Phenantroline, Benzophenone, 1,3,5-tri hydroxybenzene (TIB)₅ 4,4'-Diaminodiphenylether (DADF)₅ p-phenylendiamina, Benzentetracarbonitrile, N₅N₅N' ,N' -Tetramethylbenzene- 1 ,4-diamine, Diphenylthiocarbazone (DFTC)₅ Fumaric acid, DMADA=N,N-Dimethyl-4₅4'-azodianiline₅ Pararosaniline base, SUDAN III, Imidazole, 1,2,4 Triazole, Ethyl ferrocene (EF)₅ N-EthylCarbazole.

6. Organic solid self-supported electrochromic material, according to claim 1 in which the plastifying and/or solvent substances of low molecular weight are of type:

with R which can be chosen inside the following group: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups. Carbonates

llowing group: H₅ alchylic or alcossiphenyl linear or

where n can vary from 1 to 10.

γ-butyrolactone, Dimethylformamide (DMF), 1,1,2,2-Tetrachloroetane, Triethylen glicol di- 2-ethyl hexanoate (EGO), Di hexyl adipate (DHA), Dibuthyl sebacato (DBS).

7. Organic solid self-supported electrochromic material, according to claim 1 in which the stabylizing substances are of the type:

3,5-di ter-butyl-4-hydroxyphenyl-methylpropanoate (AO-I), Ester of the 3,5-di-ter-butyl-4- hydroxyphenyl-propanoic acid and ethylenglicole (AO-2), Ester of the 3,5-di-ter-butyl-4- hydroxyphenylpropanoic acid and pentaerythritol (AO-3), Dimethyl-(3,5-di-ter-butyl-4- hydroxybenzyl) phosphonate (AO-4), Diphenyl-(3,5-di-ter-butyl-4-hydroxybenzyl) phosphonate (AO-5), Phenyl ester of the 2,2'-methylen-bis-(4-methyl-6-butylphenyl) phosphoric acid (AO-6), Tris(2,4-di-ter-butylphenyl) phosphite (AO-7)

8. Organic solid self-supported electrochromic material, according to one of previous claims, characterized by the fact that it is composed by a majoritary polymer, destinated to have a support function, by the only one electrochromic substance, capable to transfer electric charges through the material, by a solvent and/or plastifying high-boiling substance.

9. Organic solid self-supported electrochromic material, according to one of previous claims, characterized by the fact that the conductive substance is capable to confer electrochromic properties to the material.

10. Organic solid self-supported electrochromic material, according to one of previous claims, characterized by the fact that one of organic plastifiers is a liquid crystal such that in the film the mycro drops of liquid crystal are present, so that the film beyond having electrochromic properties has also electro-optical properties of PDLC type and is capable the change its transparence after electric fields application.

11. Organic solid self-supported electrochromic material, according to one of previous claims, characterized by the fact that organic and/or inorganic conductive layers and isolating layers are depositated on it. These layers are such that the material can be used as an electrochromic material without being substained by prefabbricated supports.

12. The cell obtained by lamination of a film of the material according to previous claims characterized by the fact that the film is contained between rigid or flexible transparent preformed supports, having the conductive internal surfaces.