Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
  • C09K9/02—Organic tenebrescent materials
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
  • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
  • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1007—Non-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
  • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
  • G02F2001/15145—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material the electrochromic layer comprises a mixture of anodic and cathodic compounds

Definitions

• 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.
• the traditional organic electrochromic materials are thin films which change their colour when an electric field, generally with low intensity, is applied to them.
• the active substances which are specific 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).
• electrochromic films of organic nature consisting of organic electrochromic substances dissolved in other organic substances
• 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.
• these systems have different disadvantages connected to their fluidity.
• 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 patent 3 the possibility to obtain electrochromic self-supported solid films polymerizing, by exposing to U.V.
• the material object of the present invention presents various innovative elements compared to those patented previously.
• thermoplastic materials will conserve in large part these initial properties because these polymers will remain the more represented components in the final formulations.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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 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.
• 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.
• 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.
• the film object of the invention can be obtained in different final formulations, according to the characteristics desired by the applicative responsibilities like: the electro-chromism type (colors between which the film operates), the reologic parameters, electrochromic reponse times, the tensions and the operational currents etc.
• 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 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.
• 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.
• R can be chosen inside the following group: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups.
• .-Mir OH n can vary from 1 to 10.
• DHA Di hexyl adipate
• the electronic charge tranferring molecules used have been chosen from the following composts classes: where R 1 , R 2 , R 3 , and R 4 , 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:
• R 4 , R 5 , R 6 , R 7 , R 8 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,
• R 9 n can vary between 1 and 10.
• alcossiphenyl linear or ramate groups aromatic groups
• n can vary between 1 and 10.
• H alchylic linear or ramate chains
• alchilphenyl or alcossiphenyl linear or ramate groups aromatic groups.
• Benzophenone 1 35-tri 4,4'-Diaminodiphenyl ether (DADF) hydroxybenzene (THB)
• R can be: H, alchylic linear or ramate chains, alchilphenyl or alcossiphenyl linear or ramate groups, aromatic groups.
• the electrochromic mol ⁇ ecuiles absorbing in can the visible region can be chosen between the following composts classes:
• 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.
• n comprised between 1 and 20.
• R 1, R 2 , R 3 , R 4 , R 5 , R 6, R 7 , R 8 , and R 9 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.
• R 3 , R 4 , e R 5 can be equal or can be chosen in the following linear or ramate alchylic alcossilic or phenossilic, other aromatic groups, -CN, F,
• R 1, R 2 , R 3 , and R 4 that can be different or equal and can be chosen inside the following group: linear or ramate alchylic substitutents, alcossylic or phenossylic substitutents, phenylics.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m.
• 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m.
• 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m.
• 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m.
• 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.
• 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m.
• 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m.
• 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of
• 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.
• EGO 31% has been prepared and homogenized under shaking with a temperature of 150-200 0 C.
• the obtained film is deposited between conducting glasses using spacers with diameter of
• 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.
• DMF dimethylformammide
• DMF dimethylformammide
• DMF dimethylformammide
• DMF dimethylformammide
• DMF dimethylformammide
• DMF dimethylformammide
• 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.
• DMF dimethylformammide
• DMF dimethylformammide
• DMF dimethylformammide
• DMF dimethylformammide
• DMF dimethylformammide
• R 4 R 5 ⁇ CH 2 CO 2 CH 3 (T9)+TCE+DMF+ EGO
• DMF dimethylformammide
• V4 1.224%
• the solvent (DMF) is eliminated by heating at ca. 160 °C.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m. 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 50 Film components: PMMA+ V4+TCE+PC +AO7
• the solvent (dichlorometane) is eliminated by heating at 40-50 0 C.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m. 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.
• R 4 R 5 ⁇ CH 2 CO 2 CH 3 (T6) +TCE+V4+PC
• R 4 R 5 ⁇ CH 2 CH 2 OCH 3 (T31)+TCE+V4+PC
• the solvent (dichlorometane) is eliminated by heating at ca. 40-50 0 C.
• the obtained film is deposited between conducting glasses using spacers with diameter of 65 ⁇ m. 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of
• 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.
• the obtained film is deposited between conducting glasses using spacers with diameter of
• 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
• 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/ ⁇ m
• the alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 1.2 V/ ⁇ m
• the alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 0.9 V/ ⁇ m
• the alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 1.0 V/ ⁇ m
• the alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 1.0 V/ ⁇ m
• the alternate electric field to be applied in order to obtain a pure opaque transparent transition is of 0.7 V/ ⁇ m

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• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

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• 2004
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• 2005
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