EP2374039A1 - Electrically controllable device with controlled thickness of the electroactive medium and simplified manufacturing, and method for making same - Google Patents
Electrically controllable device with controlled thickness of the electroactive medium and simplified manufacturing, and method for making sameInfo
- Publication number
- EP2374039A1 EP2374039A1 EP09796654A EP09796654A EP2374039A1 EP 2374039 A1 EP2374039 A1 EP 2374039A1 EP 09796654 A EP09796654 A EP 09796654A EP 09796654 A EP09796654 A EP 09796654A EP 2374039 A1 EP2374039 A1 EP 2374039A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- varnish
- electroactive
- glass
- electro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 69
- 239000011521 glass Substances 0.000 claims description 33
- 239000002966 varnish Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- -1 siloxanes Chemical class 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000005341 toughened glass Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- GVTGSIMRZRYNEI-UHFFFAOYSA-N 5,10-dimethylphenazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3N(C)C2=C1 GVTGSIMRZRYNEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- OHVSCUACGMLPGP-UHFFFAOYSA-N 1-methyl-10h-phenothiazine 5-oxide Chemical compound N1C2=CC=CC=C2S(=O)C2=C1C(C)=CC=C2 OHVSCUACGMLPGP-UHFFFAOYSA-N 0.000 claims description 2
- CJVYYDCBKKKIPD-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylbenzene-1,2-diamine Chemical compound CN(C)C1=CC=CC=C1N(C)C CJVYYDCBKKKIPD-UHFFFAOYSA-N 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical class [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000005340 laminated glass Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 150000002990 phenothiazines Chemical class 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000004053 quinones Chemical class 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 150000008648 triflates Chemical class 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 150000002019 disulfides Chemical class 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000011229 interlayer Substances 0.000 claims 1
- 238000003475 lamination Methods 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 239000004922 lacquer Substances 0.000 abstract description 2
- 239000003570 air Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- HTNDMKDAPWJPEX-UHFFFAOYSA-L 1-ethyl-4-(1-ethylpyridin-1-ium-4-yl)pyridin-1-ium;diperchlorate Chemical compound [O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.C1=C[N+](CC)=CC=C1C1=CC=[N+](CC)C=C1 HTNDMKDAPWJPEX-UHFFFAOYSA-L 0.000 description 2
- ALJHHTHBYJROOG-UHFFFAOYSA-N 7-(dimethylamino)phenothiazin-3-one Chemical compound C1=CC(=O)C=C2SC3=CC(N(C)C)=CC=C3N=C21 ALJHHTHBYJROOG-UHFFFAOYSA-N 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-P 4-pyridin-1-ium-4-ylpyridin-1-ium Chemical compound C1=[NH+]C=CC(C=2C=C[NH+]=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-P 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 description 1
Classifications
-
- 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
-
- 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
- G02F1/15165—Polymers
-
- 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
- G02F1/1503—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 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
-
- 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 is an improvement to electrically controllable devices with variable optical / energy properties, comprising the following stack of layers: a first glass-function substrate (V 1 );
- an electroactive system comprising or consisting of: at least one electroactive organic compound
- SUBSTITUTE SHEET (RULE 26) a second substrate with a glass function (v 2 ).
- TCC electronically conductive layers
- Transparent Conductive Coating an example of which is a transparent conductive oxide TCO ("Transparent Conductive
- the compound (eai + ) is electrochromic (being, for example, 1,1'-diethyl-4,4'-bipyridinium diperchlorate) and that the compound (ea2) is electrochromic (for example being 5, 10-dihydro-5,10-phenothiazine) or non-electrochromic (being for example a ferrocene)
- electrochromic being, for example, 1,1'-diethyl-4,4'-bipyridinium diperchlorate
- the compound (ea2) is electrochromic (for example being 5, 10-dihydro-5,10-phenothiazine) or non-electrochromic (being for example a ferrocene)
- the redox reactions which are established under the action of the electric current are as follows:
- the electroactive medium (ea) is a medium in solution or gelled. It can also be contained in a self-supported polymer matrix as described in the international application PCT / FR2008 / 051160 filed on 25/06/2008 or in the European application EP 1786883.
- the medium (ea) In the case where the medium (ea) is in solution or gelled and therefore has no mechanical strength, it must be encapsulated in the "reservoir" zone delimited by the two glass plates (v x ), (v 2 ) arranged face to face with their internal surfaces each coated by the layer respectively (TCCi), (TCC2), and by a seal or encapsulating peripheral frame, electrical insulator.
- the filling of this reservoir zone is carried out by a orifice made in this peripheral joint by a relatively complex vacuum technique.
- FIG. 1 of the accompanying drawing schematically illustrates the configuration s' such a double glazing, which comprises a third glass sheet (v 3 ), facing the glass sheet (v 2 ), with the interposition of a blade of air or another gas, such as argon, between the sheets (v 2 ) and (v 3 ), the peripheral seal (not shown) being adapted to hold the assembly.
- a blade of air or another gas such as argon
- the glass sheets (v1) and (v2), located on the outside must be made of tempered glass because of the coefficient of thermal expansion of the glass.
- tempered glass has mini-flatness defects, which will lead to a color homogeneity problem during operation of the electrically controllable device.
- the electro-active medium in the liquid phase must allow the mobility of the electro-active species (eal) and (ea2), (eai + ) and (ea 2 + )
- it must therefore have a certain thickness, which must also allow the filling and must also be adjusted precisely to be thick enough to overcome the problems of non-homogeneity of the color of the glazing but not too thick not to harm the speed of this color change and good visibility through the glazing.
- Such a thickness is in practice between 100 .mu.m and 700 .mu.m.
- the Applicant Company has therefore sought to eliminate or reduce at least one of these numerous disadvantages, and in particular it has sought ways to control the thickness of the active medium other than by controlling the distance between the two. substrates, everything by seeking to simplify the method of manufacturing the electrically controllable device.
- the electro-active medium could be deposited on a substrate coated with a first electronically conductive layer in the form of a varnish to be dried, the thickness of which is perfectly controlled, advantageously less than that of the prior state of the art, and which, once dried, has sufficient mechanical strength to allow direct deposition of the second electronically conductive layer.
- the present invention therefore firstly relates to an electrically controllable device with variable optical / energy properties, characterized in that it comprises the following stack of layers: a substrate with a glass function (Vi);
- a layer of electro-active varnish based on at least one binder polymer containing the constituents of an electroactive medium formed by: at least one electroactive organic compound (eai + ) capable of being reduced and / or accepting electrons and cations acting as compensation charges; at least one electroactive organic compound (ea2) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; at least one of said electroactive organic compounds (ea / ea2) being electrochromic to obtain a color contrast; and ionic charges able to allow, under the action of an electric current, reactions oxidizing and reducing said electroactive organic compounds (ea / ea2), which are necessary to obtain the color contrast; and a second electrically conductive layer (TCC2) with an associated current supply.
- VSA electro-active varnish
- the polymer (s) constituting the base of the varnish (VEA) are in particular chosen from acrylic polymers, siloxanes and silicones.
- the electroactive organic compound (s) are in particular chosen from acrylic polymers, siloxanes and silicones.
- (eai + ) may or may be chosen from bipyridiniums or viologenes such as 1,1'-diethyl-4,4'-bipyridinium diperchlorate, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums and tetrazoliums , verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulfides and disulphides, as well as all the electro-active polymeric derivatives of the electro-active compounds just mentioned; and the electroactive organic compound (s) (e ⁇ 2) is or are chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N ', N' -tetramethylphenylenediamine (TMPD), phenothiazines such as phenothiazine, dihydrophenazines
- the ionic charges may be borne by at least one ionic salt present in the layer of varnish, the ionic salt or salts being chosen in particular from lithium perchlorate, the salts trifluoromethanesulfonates or triflates, trifluoromethanesulfonylimide salts and ammonium salts.
- the varnish layer has a thickness at most equal to 100 microns.
- An electronically conductive layer (TCCi;
- TCC2 may be a layer of metal type, chosen in particular from the layers of silver, gold, platinum and copper; or transparent conductive oxide (TCO) layers, such as tin - doped indium oxide (In 2 Oa: Sn or ITO) layers, antimony - doped indium oxide (In 2 ⁇ 3: S b ), fluorine-doped tin oxide
- TCO transparent conductive oxide
- TCO / metal / TCO multilayers the TCO and the metal being in particular chosen from those enumerated above; or type of the multilayer of the NiCr / metal / NiCr type, the metal being chosen in particular from those enumerated above.
- the TCCi layer may also be in the form of a grid or a microgrid. It may also comprise an organic and / or inorganic sub-layer, particularly in the case of plastic substrates, as described in the international application WO 2007/057605.
- An organic varnish layer and / or a layer or a stack of inorganic layers may or may be deposited on the second electronically conductive layer (TCC 2 ) in order to protect electrically controllable device from mechanical aggression such as scratching or chemical attack due to example to oxygen or the humidity of the ambient air.
- the organic protection varnish of the TTC 2 may be based on siloxane and the inorganic layer or the stack of inorganic layers may be based on SiaN 4 or SiO x for example.
- Composite organic / organic layer composite stacks can also be used.
- the glass-function substrate (Vi) may be chosen from glass and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), poly (ethylene terephthalate) (PET), poly (ethylene naphthoate) (PEN) and copolymers of cycloolefins (COC).
- PMMA poly (methyl methacrylate)
- PC polycarbonate
- PET poly (ethylene terephthalate)
- PEN poly (ethylene naphthoate)
- COC copolymers of cycloolefins
- the glass-function substrate (Vi) disposed on the outside of the glazing may be a toughened glass or a laminated glass, the latter consisting of two sheets of glass (V ia ) and (V ib ) separated by an intermediate sheet laminating material (I), for example a polyvinyl butyral (PVB) sheet or an ethylene-vinyl acetate copolymer (EVA) sheet.
- I intermediate sheet laminating material
- PV ia polyvinyl butyral
- EVA ethylene-vinyl acetate copolymer
- the electrically controllable device of the invention may be configured to form: a roof for a motor vehicle, activatable autonomously, or a side window or a rear window for a motor vehicle or a rearview mirror; a windshield or a portion of a windshield of a motor vehicle or an airplane or a ship, an automobile roof; an airplane porthole; a display panel of graphical and / or alphanumeric information; indoor or outdoor glazing for the building; a roof window; a display stand, store counter; a protective glazing of an object of the table type; an anti-glare computer screen; glass furniture; a partition wall of two rooms inside a building.
- the electrically controllable device of the invention can be mounted in double glazing, a second glass-function substrate (V 2 ) being attached to the side of the second electronically conductive layer (TCC 2 ) with the interposition of a blade of a gas, such as that the air or argon, between it and said second electronically conductive layer (TCC2).
- the present invention also relates to a method of manufacturing an electrically controllable device as defined above, characterized in that it is deposited on a substrate with a glass function (Vi; Vi a -I-Vi b ) coated a first electronically conductive layer
- TMCi a layer of electro-active varnish (VEA) based on at least one binder polymer containing:
- At least one electroactive organic compound (eai + ) capable of being reduced and / or of accepting electrons and cations acting as compensation charges; at least one electroactive organic compound
- ionic charges capable of allowing, under the action of an electric current, oxidation and reduction reactions of said electroactive organic compounds (eai + & ea2), which are necessary to obtain the color contrast; then, after drying of the varnish (VEA), a second electronically conductive layer (TCC2), then, in the case where it is desired to produce a double glazing, a second substrate with a glass function is reported
- V 2 on the side of the second electronically conductive layer (TCC 2 ) with the interposition of a gas strip, such as air or argon, between it and said second electronically conductive layer (TCC2).
- a gas strip such as air or argon
- the varnish layer (VEA) can advantageously be deposited by application by spraying, watering or trickling, by screen printing or by rotational deposition or centrifugation technique or by an ink jet technique.
- PE-CVD magnetron plasma-assisted chemical vapor deposition
- FIG. 1 is a schematic cross-sectional view of a portion of a building double glazing incorporating the electrically controllable device in its conventional configuration
- Figure 2 is a view similar to Figure 1 but in a configuration of the invention.
- FIG. 3 is a view similar to Figure 2 but showing a variant of the configuration of the invention.
- the "K-glass TM” glass used in these examples is a glass covered with an electroconductive layer of SnO2: F (glass sold under this name by the company "Pilkington”)
- An electroactive varnish formulation was prepared by mixing 0.25 g of 5,10-dihydro-5,10-dimethylphenazine with 0.50 g of 1,1'-diethyl-diperchlorate.
- a masking of the areas of SnO2: F not covered with varnish is performed on the substrate coated with electroactive varnish.
- a layer of 300 nm of ITO is then deposited by magnetron sputtering onto K-glass TM glass coated with electroactive varnish.
Abstract
The device of the invention comprises a stack of the following layers: a substrate with a glazing function (V1); a first electronically conductive layer (TCC1) with an associated current supply; an electroactive lacquer layer (VEA) containing at least one binding polymer including the components of an electroactive medium formed by: at least on electroactive compound capable of reducing and/or accepting electrons and cations used as compensation charges; at least one electroactive organic compound capable of oxidising and/or ejecting electrons and cations used as compensation charges; at least one of said electro-active compounds being an electrochrome so as to obtain a colour contrast; and ionic charges capable of enabling, under the action of an electric current, oxidation and reduction reactions of said electroactive organic compounds, which are necessary for obtaining the colour contrast; and a second electronically conductive layer (TCC2) with an associated current supply.
Description
DISPOSITIF ELECTROCOMMANDABLE A EPAISSEUR CONTROLEE DE MILIEU ÉLECTRO-ACTIF ET DE FABRICATION SIMPLIFIEE ET SON PROCEDE DE FABRICATIONELECTROCOMMANDABLE DEVICE WITH CONTROLLED THICKNESS OF ELECTRO-ACTIVE MEDIUM AND SIMPLIFIED MANUFACTURE AND METHOD OF MANUFACTURE
La présente invention est un perfectionnement aux dispositifs électrocommandables à propriétés optiques/énergétiques variables, comportant l'empilement suivant de couches : - un premier substrat à fonction verrière (V1) ;The present invention is an improvement to electrically controllable devices with variable optical / energy properties, comprising the following stack of layers: a first glass-function substrate (V 1 );
- une première couche électroniquement conductricea first electrically conductive layer
(TCCi) avec une amenée de courant associée ;(TCCi) with an associated current supply;
- un système électro-actif (ea) comprenant ou constitué par : o au moins un composé organique électro-actifan electroactive system (ea) comprising or consisting of: at least one electroactive organic compound
(eax +) capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation ; o au moins un composé organique électro-actif (ea2) capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation ; au moins l'un desdits composés organiques électro-actifs (eaχ+ et ea2) étant électrochrome pour obtenir un contraste de couleur ; et o des charges ioniques aptes à permettre, sous l'action d'un courant électrique, des réactions d'oxydation et de réduction desdits composés organiques électro-actifs (ea^ & ea2) , lesquelles sont nécessaires pour obtenir le contraste de couleur ;(ea x + ) capable of being reduced and / or of accepting electrons and cations acting as compensation charges; at least one electroactive organic compound (ea 2 ) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; at least one of said electroactive organic compounds (eaχ + and ea 2 ) being electrochromic to obtain a color contrast; and o ionic charges able to allow, under the action of an electric current, oxidation and reduction reactions of said electroactive organic compounds (ea ^ & ea 2 ), which are necessary to obtain the color contrast ;
- une deuxième couche électroniquement conductricea second electrically conductive layer
(TCC2) avec une amenée de courant associée ; et(TCC 2 ) with an associated current supply; and
FEUILLE DE REMPLACEMENT (RÈGLE 26)
- un second substrat à fonction verrière (v2) .SUBSTITUTE SHEET (RULE 26) a second substrate with a glass function (v 2 ).
Les couches électroniquement conductrices sont notées « TCC », abréviation de l'expression anglaiseThe electronically conductive layers are denoted "TCC", abbreviation of the English expression
« Transparent Conductive Coating » , dont un exemple est un oxyde conducteur transparent TCO (« Transparent Conductive"Transparent Conductive Coating", an example of which is a transparent conductive oxide TCO ("Transparent Conductive
Oxide ».Oxide ".
Si l'on suppose que le composé (eai+) est électrochrome (étant par exemple du diperchlorate de 1,1'- diéthyl-4, 4' -bipyridinium) et que le composé (ea2) est électrochrome (étant par exemple de la 5, 10-dihydro-5, 10- phénothiazine) ou non électrochrome (étant par exemple un ferrocène) , les réactions redox qui s'établissent sous l'action du courant électrique sont les suivantes :
If it is supposed that the compound (eai + ) is electrochromic (being, for example, 1,1'-diethyl-4,4'-bipyridinium diperchlorate) and that the compound (ea2) is electrochromic (for example being 5, 10-dihydro-5,10-phenothiazine) or non-electrochromic (being for example a ferrocene), the redox reactions which are established under the action of the electric current are as follows:
ColoréColored
ea2 ^ ea2+ + e~ Coloré si électrochromeea2 ^ ea2 + + e ~ Colorful if electrochromic
Incolore si non électrochromeColorless if not electrochromic
Le milieu électro-actif (ea) est un milieu en solution ou gélifié. Il peut aussi être contenu dans une matrice polymère auto-supportée comme cela est décrit dans la demande internationale PCT/FR2008/051160 déposée le 25/06/2008 ou dans la demande européenne EP 1786883.The electroactive medium (ea) is a medium in solution or gelled. It can also be contained in a self-supported polymer matrix as described in the international application PCT / FR2008 / 051160 filed on 25/06/2008 or in the European application EP 1786883.
Dans le cas où le milieu (ea) est en solution ou gélifié et n'a donc aucune tenue mécanique, celui-ci doit être encapsulé dans la zone « réservoir » délimitée par les deux plaques de verre (vx) , (v2) disposées face à face avec leurs surfaces internes revêtues chacune par la couche respectivement (TCCi), (TCC2) , et par un joint ou cadre périphérique d' encapsulation, isolant électrique. Le remplissage de cette zone réservoir s'effectue par un
orifice pratiqué dans ce joint périphérique par une technique relativement complexe sous vide.In the case where the medium (ea) is in solution or gelled and therefore has no mechanical strength, it must be encapsulated in the "reservoir" zone delimited by the two glass plates (v x ), (v 2 ) arranged face to face with their internal surfaces each coated by the layer respectively (TCCi), (TCC2), and by a seal or encapsulating peripheral frame, electrical insulator. The filling of this reservoir zone is carried out by a orifice made in this peripheral joint by a relatively complex vacuum technique.
Une application particulière d'un tel dispositif électrocommandable est la réalisation de vitrages, et notamment de doubles vitrages pour le bâtiment. La Figure 1 du dessin annexé illustre schématiquement la configuration s' un tel double vitrage, lequel comporte une troisième feuille de verre (v3) , en regard de la feuille de verre (v2) , avec interposition d'une lame d'air ou d'un autre gaz, tel que l'argon, entre les feuilles (v2) et (v3), le joint périphérique (non représenté) étant adapté pour le maintien de l'ensemble.A particular application of such an electrically controllable device is the production of glazing, and in particular double glazing for the building. Figure 1 of the accompanying drawing schematically illustrates the configuration s' such a double glazing, which comprises a third glass sheet (v 3 ), facing the glass sheet (v 2 ), with the interposition of a blade of air or another gas, such as argon, between the sheets (v 2 ) and (v 3 ), the peripheral seal (not shown) being adapted to hold the assembly.
En raison de l'emploi de la technique précitée de remplissage sous vide, on voit donc qu'il n'est pas aisé de fabriquer de tels vitrages, a fortiori de tels doubles vitrages. On peut même dire qu'il est pratiquement impossible d'adapter cette technique à des vitrages et doubles vitrages de grande dimension.Because of the use of the aforementioned vacuum filling technique, we see that it is not easy to manufacture such glazing, especially for such double glazing. It can even be said that it is practically impossible to adapt this technique to large glazing and double glazing.
De plus, dans le cas des doubles vitrages de bâtiment notamment, les feuilles de verre (vl) et (v2), situées du côté extérieur, doivent être en verre trempé en raison du coefficient de dilatation thermique du verre. Or, le verre trempé présente des mini-défauts de planéité, lesquels conduiront à un problème d'homogénéité de coloration lors du fonctionnement du dispositif électrocommandable. Sachant que le milieu électro-actif en phase liquide doit permettre la mobilité des espèces électro-actives (eal) et (ea2), (eai+) et (ea2 +) il doit donc avoir une certaine épaisseur , laquelle doit également permettre le remplissage et doit par ailleurs être ajustée avec précision pour être suffisamment épaisse pour pallier les problèmes de non-homogénéité de la coloration du vitrage mais pas trop épaisse pour ne pas nuire à la
rapidité de ce changement de couleur ainsi qu'à une bonne visibilité à travers la le vitrage. Une telle épaisseur est en pratique comprise entre 100 μm et 700μm.In addition, in the case of building double glazings in particular, the glass sheets (v1) and (v2), located on the outside, must be made of tempered glass because of the coefficient of thermal expansion of the glass. However, tempered glass has mini-flatness defects, which will lead to a color homogeneity problem during operation of the electrically controllable device. Given that the electro-active medium in the liquid phase must allow the mobility of the electro-active species (eal) and (ea2), (eai + ) and (ea 2 + ), it must therefore have a certain thickness, which must also allow the filling and must also be adjusted precisely to be thick enough to overcome the problems of non-homogeneity of the color of the glazing but not too thick not to harm the speed of this color change and good visibility through the glazing. Such a thickness is in practice between 100 .mu.m and 700 .mu.m.
Ce problème de défaut de planéité se présente également dans le cas des substrats souples de verre organique, tels que les substrats de poly (téréphtalate d' éthylène) .This problem of unevenness also occurs in the case of flexible substrates of organic glass, such as poly (ethylene terephthalate) substrates.
On peut également noter qu'une trop grande épaisseur de la couche électro-active n'est pas recherchée compte tenu du risque de diminution de la valeur de la transmission lumineuse de la couche électro-active lorsqu' aucun courant électrique n'est appliqué, faisant ainsi diminuer le contraste recherché lors du changement de coloration . L'emploi comme contenant du milieu électro-actif d'une matrice polymère autosupportée permet de simplifier la fabrication, car il permet l'empilement des différentes couches. Toutefois, il reste que sa tenue mécanique n'est pas parfaite et que, s'il est appliqué entre des substrats ayant des mini-défauts de planéité tels que des substrats souples et des verres trempés, il épousera ces défauts de planéité. Toute l'épaisseur du milieu électro-actif participant à la coloration, il se posera alors des problèmes d'homogénéité de cette coloration. On peut certes augmenter l'épaisseur de la matrice polymère autosupportée, mais ceci n'est pas non plus idéal pour les deux mêmes raisons que celles indiquées ci-dessus.It may also be noted that too much thickness of the electro-active layer is not sought, given the risk of a decrease in the value of the light transmission of the electro-active layer when no electric current is applied, thus reducing the contrast sought during the color change. The use as containing electro-active medium of a self-supporting polymer matrix makes it possible to simplify the manufacture because it allows the stacking of the different layers. However, it remains that its mechanical strength is not perfect and that, if it is applied between substrates having mini flatness defects such as flexible substrates and tempered glasses, it will meet these flatness defects. The entire thickness of the electro-active medium involved in the coloring, there will then arise problems of homogeneity of this coloration. While it is possible to increase the thickness of the autosupported polymer matrix, this is not ideal for the same two reasons as those indicated above.
La Société déposante a donc recherché à supprimer ou à diminuer au moins l'un de ces nombreux inconvénients, et en particulier elle a recherché des moyens permettant le contrôle de l'épaisseur du milieu actif autrement que par le contrôle de la distance entre les deux substrats, tout
en recherchant à simplifier le procédé de fabrication du dispositif électrocommandable .The Applicant Company has therefore sought to eliminate or reduce at least one of these numerous disadvantages, and in particular it has sought ways to control the thickness of the active medium other than by controlling the distance between the two. substrates, everything by seeking to simplify the method of manufacturing the electrically controllable device.
A cet effet, elle a découvert que le milieu électro-actif pouvait être déposé sur un substrat revêtu d'une première couche électroniquement conductrice sous la forme d'un vernis à sécher, dont on contrôle parfaitement l'épaisseur, avantageusement inférieure à celle de l'état antérieur de la technique, et qui, une fois séché, a une tenue mécanique suffisante pour permettre un dépôt direct de la seconde couche électroniquement conductrice.For this purpose, she discovered that the electro-active medium could be deposited on a substrate coated with a first electronically conductive layer in the form of a varnish to be dried, the thickness of which is perfectly controlled, advantageously less than that of the prior state of the art, and which, once dried, has sufficient mechanical strength to allow direct deposition of the second electronically conductive layer.
La présente invention a donc d'abord pour objet un dispositif électrocommandable à propriétés optiques/énergétiques variables, caractérisé par le fait qu'il comporte l'empilement suivant de couches : - un substrat à fonction verrière (Vi) ;The present invention therefore firstly relates to an electrically controllable device with variable optical / energy properties, characterized in that it comprises the following stack of layers: a substrate with a glass function (Vi);
- une première couche électroniquement conductricea first electrically conductive layer
(TCCi) avec une amenée de courant associée ;(TCCi) with an associated current supply;
- une couche de vernis électro-actif (VEA) à base d'au moins un polymère liant renfermant les constituants d'un milieu électro-actif formés par : o au moins un composé organique électro-actif (eai+) capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation ; o au moins un composé organique électro-actif (ea2) capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation ; o au moins l'un desdits composés organiques électro-actifs (ea/ & ea2) étant électrochrome pour obtenir un contraste de couleur ; et o des charges ioniques aptes à permettre, sous l'action d'un courant électrique, des réactions
d' oxydation et de réduction desdits composés organiques électro-actifs (ea/ & ea2) , lesquelles sont nécessaires pour obtenir le contraste de couleur ; et - une deuxième couche électroniquement conductrice (TCC2) avec une amenée de courant associée.a layer of electro-active varnish (VEA) based on at least one binder polymer containing the constituents of an electroactive medium formed by: at least one electroactive organic compound (eai + ) capable of being reduced and / or accepting electrons and cations acting as compensation charges; at least one electroactive organic compound (ea2) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; at least one of said electroactive organic compounds (ea / ea2) being electrochromic to obtain a color contrast; and ionic charges able to allow, under the action of an electric current, reactions oxidizing and reducing said electroactive organic compounds (ea / ea2), which are necessary to obtain the color contrast; and a second electrically conductive layer (TCC2) with an associated current supply.
Le ou les polymères constituant la base du vernis (VEA) sont notamment choisis parmi les polymères acryliques, les siloxanes et les silicones. Le ou les composés organiques électro-actifsThe polymer (s) constituting the base of the varnish (VEA) are in particular chosen from acrylic polymers, siloxanes and silicones. The electroactive organic compound (s)
(eai+) peut ou peuvent être choisis parmi les bipyridiniums ou viologènes tels que le diperchlorate de 1, l' -diéthyl- 4, 4' -bipyridinium, les pyraziniums, les pyrimidiniums, les quinoxaliniums, les pyryliums, les pyridiniums, les tétrazoliums, les verdazyls, les quinones, les quinodiméthanes, les tricyanovinylbenzènes, le tétracyanoéthylène, les polysulfures et les disulfures, ainsi que tous les dérivés polymériques électro-actifs des composés électro-actifs qui viennent d'être mentionnés ; et le ou les composés organiques électro-actifs (eβ2) est ou sont choisis parmi les métallocènes, tels que les cobaltocènes, les ferrocènes, la N, N, N' , N' -tétraméthyl phénylènediamine (TMPD) , les phénothiazines telles que la phénothiazine, les dihydrophénazines telles que la 5,10- dihydro-5, 10-diméthylphénazine, la méthylphénothiazone réduite (MPT) , le violet de méthylène bernthsen (MVB) , les verdazyls, ainsi que tous les dérivés polymériques électroactifs des composés électro-actifs qui viennent d'être mentionnés . Les charges ioniques peuvent être portées par un au moins sel ionique présent au sein de la couche de vernis, le ou les sels ioniques étant notamment choisis parmi le perchlorate de lithium, les sels
trifluorométhanesulfonates ou triflates, les sels de trifluorométhanesulfonylimide et les sels d'ammonium.(eai + ) may or may be chosen from bipyridiniums or viologenes such as 1,1'-diethyl-4,4'-bipyridinium diperchlorate, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums and tetrazoliums , verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulfides and disulphides, as well as all the electro-active polymeric derivatives of the electro-active compounds just mentioned; and the electroactive organic compound (s) (eβ2) is or are chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N ', N' -tetramethylphenylenediamine (TMPD), phenothiazines such as phenothiazine, dihydrophenazines such as 5,10-dihydro-5,10-dimethylphenazine, reduced methylphenothiazone (MPT), methylene violet bernthsen (MVB), verdazyls, and all electroactive polymeric derivatives of electroactive compounds which have just been mentioned. The ionic charges may be borne by at least one ionic salt present in the layer of varnish, the ionic salt or salts being chosen in particular from lithium perchlorate, the salts trifluoromethanesulfonates or triflates, trifluoromethanesulfonylimide salts and ammonium salts.
La couche de vernis (VEA) a notamment une épaisseur au plus égale à 100 μm. Une couche électroniquement conductrice (TCCi ;The varnish layer (VEA) has a thickness at most equal to 100 microns. An electronically conductive layer (TCCi;
TCC2) peut être une couche de type métallique, choisie notamment parmi les couches d'argent, d'or, de platine et de cuivre ; ou les couches de type oxyde conducteur transparent (TCO), telles que des couches d'oxyde d' indium dopé à l'étain (In2Oa: Sn ou ITO), d'oxyde d' indium dopé à l'antimoine (In2θ3:Sb), d'oxyde d'étain dopé au fluorTCC2) may be a layer of metal type, chosen in particular from the layers of silver, gold, platinum and copper; or transparent conductive oxide (TCO) layers, such as tin - doped indium oxide (In 2 Oa: Sn or ITO) layers, antimony - doped indium oxide (In 2 θ3: S b ), fluorine-doped tin oxide
(SnO2: F) et d'oxyde de zinc dopé à l'aluminium (ZnO: Al) ; ou les multicouches de type TCO/métal/TCO, le TCO et le métal étant notamment choisis parmi ceux énumérés ci- dessus ; ou les multicouches de type NiCr/métal/NiCr, le métal étant notamment choisi parmi ceux énumérés ci-dessus.(SnO 2 : F) and zinc oxide doped with aluminum (ZnO: Al); or the TCO / metal / TCO multilayers, the TCO and the metal being in particular chosen from those enumerated above; or type of the multilayer of the NiCr / metal / NiCr type, the metal being chosen in particular from those enumerated above.
La couche TCCi peut aussi se présenter sous la forme d'une grille ou d'une microgrille. Elle peut aussi comprendre une sous-couche organique et/ou inorganique, notamment dans le cas de substrats plastiques, comme décrit dans la demande internationale WO 2007/057605.The TCCi layer may also be in the form of a grid or a microgrid. It may also comprise an organic and / or inorganic sub-layer, particularly in the case of plastic substrates, as described in the international application WO 2007/057605.
Une couche de vernis organique et/ou une couche ou un empilement de couches inorganiques peut ou peuvent être déposés sur la seconde couche électroniquement conductrice (TCC2) afin de protéger de dispositif électrocommandable des agressions mécaniques telles que les rayures ou des agressions chimiques dues par exemple à l'oxygène ou à l'humidité de l'air ambiant. Le vernis organique de protection du TTC2 peut être à base de siloxane et la couche inorganique ou l'empilement de couches inorganiques peut être à base de SiaN4 ou de SiOx par exemple. Des empilements composites vernis organique/couche organique peuvent aussi être utilisés.
Le substrat à fonction verrière (Vi) peut être choisi parmi le verre et les polymères transparents, tels que le poly (méthacrylate de méthyle) (PMMA), le polycarbonate (PC), le poly (éthylène téréphtalate) (PET), le poly (éthylène naphtoate) (PEN) et les copolymères de cyclooléfines (COC) . Le substrat (Vi) peut donc sans inconvénient être un substrat souple, tel que le PET.An organic varnish layer and / or a layer or a stack of inorganic layers may or may be deposited on the second electronically conductive layer (TCC 2 ) in order to protect electrically controllable device from mechanical aggression such as scratching or chemical attack due to example to oxygen or the humidity of the ambient air. The organic protection varnish of the TTC 2 may be based on siloxane and the inorganic layer or the stack of inorganic layers may be based on SiaN 4 or SiO x for example. Composite organic / organic layer composite stacks can also be used. The glass-function substrate (Vi) may be chosen from glass and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), poly (ethylene terephthalate) (PET), poly (ethylene naphthoate) (PEN) and copolymers of cycloolefins (COC). The substrate (Vi) can therefore without disadvantage be a flexible substrate, such as PET.
Le substrat à fonction verrière (Vi) , disposé du côté extérieur du vitrage, peut être un verre trempé ou encore un verre feuilleté, ce dernier étant constitué par deux feuilles de verre (Via) et (Vib) séparées par une feuille intercalaire de feuilletage (I), par exemple une feuille de polyvinyl butyral (PVB) ou une feuille de copolymère éthylène-acétate de vinyle (EVA) . Le dispositif électrocommandable de l'invention peut être configuré pour former : un toit pour véhicule automobile, activable de façon autonome, ou une vitre latérale ou une lunette arrière pour véhicule automobile ou un rétroviseur ; un pare-brise ou une portion de pare-brise d'un véhicule automobile ou d'un avion ou d'un navire, un toit d'automobile ; un hublot d'avion ; un panneau d'affichage d'informations graphiques et/ou alphanumériques ; un vitrage intérieur ou extérieur pour le bâtiment ; une fenêtre de toit ; un présentoir, comptoir de magasin ; un vitrage de protection d'un objet du type tableau ; un écran anti-éblouissement d'ordinateur ; un mobilier verrier ; une paroi de séparation de deux pièces à l'intérieur d'un bâtiment.The glass-function substrate (Vi) disposed on the outside of the glazing may be a toughened glass or a laminated glass, the latter consisting of two sheets of glass (V ia ) and (V ib ) separated by an intermediate sheet laminating material (I), for example a polyvinyl butyral (PVB) sheet or an ethylene-vinyl acetate copolymer (EVA) sheet. The electrically controllable device of the invention may be configured to form: a roof for a motor vehicle, activatable autonomously, or a side window or a rear window for a motor vehicle or a rearview mirror; a windshield or a portion of a windshield of a motor vehicle or an airplane or a ship, an automobile roof; an airplane porthole; a display panel of graphical and / or alphanumeric information; indoor or outdoor glazing for the building; a roof window; a display stand, store counter; a protective glazing of an object of the table type; an anti-glare computer screen; glass furniture; a partition wall of two rooms inside a building.
Le dispositif électrocommandable de l'invention peut être monté en double vitrage, un second substrat à fonction verrière (V2) étant rapporté du côté de la seconde couche électroniquement conductrice (TCC2) avec interposition d'une lame d'un gaz, tel que l'air ou
l'argon, entre lui et ladite seconde couche électroniquement conductrice (TCC2) .The electrically controllable device of the invention can be mounted in double glazing, a second glass-function substrate (V 2 ) being attached to the side of the second electronically conductive layer (TCC 2 ) with the interposition of a blade of a gas, such as that the air or argon, between it and said second electronically conductive layer (TCC2).
La présente invention a également pour objet un procédé de fabrication d'un dispositif électrocommandable tel que défini ci-dessus, caractérisé par le fait que l'on dépose sur un substrat à fonction verrière (Vi ; Via-I-Vib) revêtu d'une première couche électroniquement conductriceThe present invention also relates to a method of manufacturing an electrically controllable device as defined above, characterized in that it is deposited on a substrate with a glass function (Vi; Vi a -I-Vi b ) coated a first electronically conductive layer
(TCCi) 1 du côté de cette dernière, une couche de vernis électro-actif (VEA) à base d'au moins un polymère liant renfermant :(TCCi) 1 on the latter side, a layer of electro-active varnish (VEA) based on at least one binder polymer containing:
- au moins un composé organique électro-actif (eai+) capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation ; - au moins un composé organique électro-actifat least one electroactive organic compound (eai + ) capable of being reduced and / or of accepting electrons and cations acting as compensation charges; at least one electroactive organic compound
(ea2) capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation ; au moins l'un desdits composés organiques électro- actifs (eai+ & ea2) étant électrochrome pour obtenir un contraste de couleur ; et(ea 2 ) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; at least one of said electroactive organic compounds (eai + & ea2) being electrochromic to obtain a color contrast; and
- des charges ioniques aptes à permettre, sous l'action d'un courant électrique, des réactions d'oxydation et de réduction desdits composés organiques électro- actifs (eai+ & ea2) , lesquelles sont nécessaires pour obtenir le contraste de couleur ; puis, après séchage du vernis (VEA) , une seconde couche électroniquement conductrice (TCC2) , puis, dans le cas où l'on souhaite réaliser un double vitrage, on rapporte un second substrat à fonction verrièreionic charges capable of allowing, under the action of an electric current, oxidation and reduction reactions of said electroactive organic compounds (eai + & ea2), which are necessary to obtain the color contrast; then, after drying of the varnish (VEA), a second electronically conductive layer (TCC2), then, in the case where it is desired to produce a double glazing, a second substrate with a glass function is reported
(V2) du côté de la seconde couche électroniquement conductrice (TCC2) avec interposition d'une lame de gaz,
tel que l'air ou l'argon, entre lui et ladite seconde couche électroniquement conductrice (TCC2) .(V 2 ) on the side of the second electronically conductive layer (TCC 2 ) with the interposition of a gas strip, such as air or argon, between it and said second electronically conductive layer (TCC2).
On peut avantageusement déposer la couche de vernis (VEA) par application par aspersion, arrosage ou ruissellement, par sérigraphie ou par technique de dépôt par rotation ou centrifugation ou par une technique de type jet d'encre.The varnish layer (VEA) can advantageously be deposited by application by spraying, watering or trickling, by screen printing or by rotational deposition or centrifugation technique or by an ink jet technique.
On peut avantageusement déposer la seconde couche électroniquement conductrice TCC2 par dépôt chimique en phase vapeur assisté plasma magnétron (PE-CVD) .It is advantageous to deposit the second electronically conductive layer TCC2 by magnetron plasma-assisted chemical vapor deposition (PE-CVD).
Pour mieux illustrer l'objet de la présente invention, on va en décrire plus en détail ci-après deux modes de réalisation particuliers, avec référence au dessin annexé . Sur ce dessin :To better illustrate the object of the present invention will be described in more detail below two particular embodiments, with reference to the accompanying drawing. On this drawing :
- la Figure 1 est une vue schématique en coupe transversale d'une partie d'un double vitrage de bâtiment incorporant le dispositif électrocommandable dans sa configuration classique ;- Figure 1 is a schematic cross-sectional view of a portion of a building double glazing incorporating the electrically controllable device in its conventional configuration;
la Figure 2 est une vue analogue à la Figure 1 mais dans une configuration de l'invention ; etFigure 2 is a view similar to Figure 1 but in a configuration of the invention; and
- la Figure 3 est une vue analogue à la Figure 2 mais montrant une variante de la configuration de l' invention .- Figure 3 is a view similar to Figure 2 but showing a variant of the configuration of the invention.
Exemple de réalisation :Example of realization:
Le verre « K-glass™ » utilisé dans ces exemples est un verre recouvert d'une couche électroconductrice de
SnO2:F (verre commercialisé sous cette dénomination par la Société « Pilkington »)The "K-glass ™" glass used in these examples is a glass covered with an electroconductive layer of SnO2: F (glass sold under this name by the company "Pilkington")
On a préparé une formulation de vernis électroactif en mélangeant 0,25 g de 5, 10-dihydro-5, 10- diméthylphénazine, 0,50 g de diperchlorate de 1, 1 ' -diéthyl-An electroactive varnish formulation was prepared by mixing 0.25 g of 5,10-dihydro-5,10-dimethylphenazine with 0.50 g of 1,1'-diethyl-diperchlorate.
4, 4 ' -bipyridinium et 0,47 g de triflate de lithium et 20ml de résine SILIKOPHENE®P50/X, disponible commercialement après de Evonik Tego Chemie GmbH, dans 20 ml de carbonate de propylène. On a agité la solution pendant 1 heure.4, 4'-bipyridinium and 0.47 g of lithium triflate and 20 ml of SILIKOPHENE®P50 / X resin, available commercially from Evonik Tego Chemie GmbH, in 20 ml of propylene carbonate. The solution was stirred for 1 hour.
On a ensuite coulé une épaisseur constante deWe then poured a constant thickness of
60μm de formulation de vernis électroactif en utilisant un filmographe sur un verre K-glass™. Le solvant est évaporé en chauffant le verre K-glass™ recouvert de la formulation de résine électroactive pendant 10 heures à 900C.60μm of electroactive lacquer formulation using a filmograph on a K-glass ™ glass. The solvent is evaporated by heating the K-glass ™ glass coated with the electroactive resin formulation for 10 hours at 90 ° C.
Avant de réaliser le dépôt d'une couche d' ITO par pulvérisation magnétron, un masquage des zones de SnO2 :F non recouvertes de vernis est réalisé sur le substrat recouvert de vernis électroactif. Une couche de 300nm d' ITO est ensuite déposée par pulvérisation magnétron sur le verre K-glass™ recouvert de vernis électroactif.
Before deposition of a layer of ITO by magnetron sputtering, a masking of the areas of SnO2: F not covered with varnish is performed on the substrate coated with electroactive varnish. A layer of 300 nm of ITO is then deposited by magnetron sputtering onto K-glass ™ glass coated with electroactive varnish.
Claims
REVENDICATIONS
1 - Dispositif électrocommandable à propriétés optiques/énergétiques variables, caractérisé par le fait caractérisé par le fait qu'il comporte l'empilement suivant de couches :1 - Electrocontrollable device with variable optical/energetic properties, characterized by the fact characterized by the fact that it comprises the following stack of layers:
- un substrat à fonction verrière (Vi) ;- a substrate with a glass function (Vi);
- une première couche électroniquement conductrice (TCCi) avec une amenée de courant associée ;- a first electronically conductive layer (TCCi) with an associated current supply;
- une couche de vernis électro-actif (VEA) à base d'au moins un polymère liant renfermant les constituants d'un milieu électro-actif formés par : o au moins un composé organique électro-actif (eai+) capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation ; o au moins un composé organique électro-actif (eβ2) capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation ; o au moins l'un desdits composés organiques électro-actifs (ea/ et ea2) étant électrochrome pour obtenir un contraste de couleur ; et o des charges ioniques aptes à permettre, sous l'action d'un courant électrique, des réactions d' oxydation et de réduction desdits composés organiques électro-actifs (ea/ & ea2) , lesquelles sont nécessaires pour obtenir le contraste de couleur ; et une deuxième couche électroniquement conductrice (TCC2) avec une amenée de courant associée.
2 - Dispositif électrocommandable selon la revendication 1, caractérisé par le fait que le ou les polymères constituant la base du vernis sont choisis parmi les polymères acryliques, les siloxanes et les silicones. 3 - Dispositif électrocommandable selon l'une des revendications 1 et 2, caractérisé par le fait que le ou les composés organiques électro-actifs (eai+) est ou sont choisis parmi les bipyridiniums ou viologènes tels que le diperchlorate de 1, l' -diéthyl-4, 4' -bipyridinium, les pyraziniums, les pyrimidiniums, les quinoxaliniums, les pyryliums, les pyridiniums, les tétrazoliums, les verdazyls, les quinones, les quinodiméthanes, les tricyanovinylbenzènes, le tétracyanoéthylène, les polysulfures et les disulfures, ainsi que tous les dérivés polymériques électro-actifs des composés électro-actifs qui viennent d'être mentionnés ; et le ou les composés organiques électro-actifs (eβ2) est ou sont choisis parmi les métallocènes, tels que les cobaltocènes, les ferrocènes, la N, N, N' , N' -tétraméthyl phénylènediamine (TMPD) , les phénothiazines telles que la phénothiazine, les dihydrophénazines telles que la 5,10- dihydro-5, 10-diméthylphénazine, la méthylphénothiazone réduite (MPT) , le violet de méthylène bernthsen (MVB) , les verdazyls, ainsi que tous les dérivés polymériques électro- actifs des composés électro-actifs qui viennent d'être mentionnés .- a layer of electro-active varnish (VEA) based on at least one binder polymer containing the constituents of an electro-active medium formed by: o at least one electro-active organic compound (eai + ) capable of reduction and/or to accept electrons and cations acting as compensation charges; o at least one electroactive organic compound (eβ2) capable of oxidizing and/or ejecting electrons and cations acting as compensation charges; o at least one of said electroactive organic compounds (ea/ and ea2) being electrochromic to obtain a color contrast; and o ionic charges capable of allowing, under the action of an electric current, oxidation and reduction reactions of said electro-active organic compounds (ea/ & ea2), which are necessary to obtain the color contrast; and a second electronically conductive layer (TCC2) with an associated current supply. 2 - Electrocontrollable device according to claim 1, characterized in that the polymer(s) constituting the base of the varnish are chosen from acrylic polymers, siloxanes and silicones. 3 - Electrocontrollable device according to one of claims 1 and 2, characterized in that the electroactive organic compound(s) (eai + ) is or are chosen from bipyridiniums or viologens such as diperchlorate of 1, - diethyl-4,4'-bipyridinium, pyraziniums, pyrimidiniums, quinoxaliniums, pyryliums, pyridiniums, tetrazoliums, verdazyls, quinones, quinodimethanes, tricyanovinylbenzenes, tetracyanoethylene, polysulfides and disulfides, as well as all the electro-active polymeric derivatives of the electro-active compounds which have just been mentioned; and the electroactive organic compound(s) (eβ2) is or are chosen from metallocenes, such as cobaltocenes, ferrocenes, N, N, N', N'-tetramethyl phenylenediamine (TMPD), phenothiazines such as phenothiazine, dihydrophenazines such as 5,10-dihydro-5,10-dimethylphenazine, reduced methylphenothiazone (MPT), methylene bernthsen violet (MVB), verdazyls, as well as all electroactive polymeric derivatives of electrocompounds -assets which have just been mentioned.
4 - Dispositif électrocommandable selon l'une des revendications 1 à 3, caractérisé par le fait que les charges ioniques sont portées par un au moins sel ionique présent au sein de la couche de vernis, le ou les sels ioniques étant notamment choisis parmi le perchlorate de lithium, les sels trifluorométhanesulfonates ou triflates,
les sels de trifluorométhanesulfonylimide et les sels d' ammonium.4 - Electrocontrollable device according to one of claims 1 to 3, characterized in that the ionic charges are carried by at least one ionic salt present within the varnish layer, the ionic salt(s) being chosen in particular from perchlorate lithium, trifluoromethanesulfonate or triflate salts, trifluoromethanesulfonylimide salts and ammonium salts.
5 - Dispositif électrocommandable selon l'une des revendications 1 à 4, caractérisé par le fait que la couche de vernis a une épaisseur au plus égale à 100 μm.5 - Electrocontrollable device according to one of claims 1 to 4, characterized in that the varnish layer has a thickness at most equal to 100 μm.
6 - Dispositif électrocommandable selon l'une des revendications 1 à 5, caractérisé par le fait qu'une couche électroniquement conductrice (TCCi ; TCC2) est une couche de type métallique, choisie notamment parmi les couches d'argent, d'or, de platine et de cuivre ; ou les couches de type oxyde conducteur transparent (TCO) , telles que des couches d'oxyde d' indium dopé à l'étain (In2Oa: Sn ou ITO), d'oxyde d' indium dopé à l'antimoine (In2θ3:Sb), d'oxyde d' étain dopé au fluor (SnO2: F) et d'oxyde de zinc dopé à l'aluminium (ZnO: Al) ; ou les multicouches de type TCO/métal/TCO, le TCO et le métal étant notamment choisis parmi ceux énumérés ci-dessus ; ou les multicouches de type NiCr/métal/NiCr, le métal étant notamment choisi parmi ceux énumérés ci-dessus. 7 - Dispositif électrocommandable selon l'une quelconque des revendications 1 à 6, caractérisé par le fait que la couche TCCi se présente sous la forme d'une grille ou d'une microgrille.6 - Electrocontrollable device according to one of claims 1 to 5, characterized in that an electronically conductive layer (TCCi; TCC2) is a metallic type layer, chosen in particular from layers of silver, gold, platinum and copper; or transparent conductive oxide (TCO) type layers, such as layers of indium oxide doped with tin (In 2 Oa: Sn or ITO), indium oxide doped with antimony (In 2 θ3:S b ), tin oxide doped with fluorine (SnO 2 : F) and zinc oxide doped with aluminum (ZnO: Al); or multilayers of the TCO/metal/TCO type, the TCO and the metal being chosen in particular from those listed above; or multilayers of the NiC r /metal/NiC r type, the metal being chosen in particular from those listed above. 7 - Electrocontrollable device according to any one of claims 1 to 6, characterized in that the TCCi layer is in the form of a grid or a microgrid.
8 - Dispositif électrocommandable selon l'une quelconque des revendications 1 à 7, caractérisé par le fait que la couche TCCi comprend une sous-couche organique et/ou inorganique, notamment dans le cas de substrats plastiques .8 - Electrocontrollable device according to any one of claims 1 to 7, characterized in that the TCCi layer comprises an organic and/or inorganic sublayer, particularly in the case of plastic substrates.
9 - Dispositif électrocommandable selon l'une quelconque des revendications 1 à 8, caractérisé par le fait qu'une couche de vernis organique et/ou une couche ou un empilement de couches inorganiques est ou sont déposés sur la seconde couche électroniquement conductrice TCC2,
ledit vernis organique de protection du TCC2 pouvant être à base de siloxane, et la couche inorganique ou l'empilement de couches inorganiques pouvant être à base de Si3θ4 ou de SiOx, des empilements composites vernis organique/couche organique pouvant également être utilisées.9 - Electrocontrollable device according to any one of claims 1 to 8, characterized in that a layer of organic varnish and/or a layer or a stack of inorganic layers is or are deposited on the second electronically conductive layer TCC 2 , said organic varnish for protecting TCC2 which may be based on siloxane, and the inorganic layer or the stack of inorganic layers which may be based on Si3θ 4 or SiO x , organic varnish/organic layer composite stacks which may also be used.
10 - Dispositif électrocommandable selon l'une des revendications 1 à 8, caractérisé par le fait que le substrat à fonction verrière (Vi) est choisi parmi le verre et les polymères transparents, tels que le poly (méthacrylate de méthyle) (PMMA), le polycarbonate (PC), le polyéthylène téréphtalate (PET), le poly (éthylène naphtoate) (PEN) et les copolymères de cyclooléfines (COC) .10 - Electrocontrollable device according to one of claims 1 to 8, characterized in that the substrate with glass function (Vi) is chosen from glass and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), poly(ethylene naphthoate) (PEN) and cycloolefin copolymers (COC).
11 - Dispositif électrocommandable selon la revendication 10, caractérisé par le fait que le substrat à fonction verrière (Vi) , disposé du côté extérieur du vitrage, est un verre trempé ou encore un verre feuilleté, ce dernier étant constitué par deux feuilles de verre (Via) et (Vib) séparées par une feuille intercalaire de feuilletage (I), par exemple une feuille de polyvinyl butyral (PVB) ou une feuille de copolymère éthylène-acétate de vinyle (EVA) .11 - Electrocontrollable device according to claim 10, characterized in that the substrate with glass function (Vi), disposed on the exterior side of the glazing, is a tempered glass or even a laminated glass, the latter being constituted by two sheets of glass ( V ia ) and (Vi b ) separated by a lamination interlayer sheet (I), for example a sheet of polyvinyl butyral (PVB) or a sheet of ethylene-vinyl acetate copolymer (EVA).
12 - Dispositif électrocommandable selon la revendication 10, caractérisé par le fait que le substrat à fonction verrière est un substrat souple. 13 - Dispositif électrocommandable selon l'une des revendications 1 à 12, caractérisé par le fait qu'il configuré pour former : un toit pour véhicule automobile, activable de façon autonome, ou une vitre latérale ou une lunette arrière pour véhicule automobile ou un rétroviseur ; un pare-brise ou une portion de pare-brise d'un véhicule automobile ou d'un avion ou d'un navire, un toit d'automobile ; un hublot d'avion ; un panneau d'affichage d'informations graphiques et/ou
alphanumériques ; un vitrage intérieur ou extérieur pour le bâtiment ; une fenêtre de toit ; un présentoir, comptoir de magasin ; un vitrage de protection d'un objet du type tableau ; un écran anti-éblouissement d'ordinateur ; un mobilier verrier ; une paroi de séparation de deux pièces à l'intérieur d'un bâtiment.12 - Electrocontrollable device according to claim 10, characterized in that the substrate with glass function is a flexible substrate. 13 - Electrocontrollable device according to one of claims 1 to 12, characterized in that it is configured to form: a roof for a motor vehicle, which can be activated autonomously, or a side window or a rear window for a motor vehicle or a rear-view mirror ; a windshield or a portion of a windshield of a motor vehicle or an airplane or a ship, an automobile roof; an airplane window; a graphic information display panel and/or alphanumeric; interior or exterior glazing for the building; a roof window; a display, store counter; protective glazing for a painting type object; an anti-glare computer screen; glass furniture; a dividing wall between two rooms inside a building.
14 - Dispositif électrocommandable selon l'une des revendications 1 à 12, caractérisé par le fait qu'il est monté en double vitrage, un second substrat à fonction verrière étant rapporté du côté de la couche de vernis avec interposition d'une lame de gaz, tel que l'air, entre lui et ladite couche de vernis.14 - Electrocontrollable device according to one of claims 1 to 12, characterized in that it is mounted in double glazing, a second substrate with glass function being attached to the side of the varnish layer with the interposition of a gas blade , such as air, between it and said layer of varnish.
15 - Procédé de fabrication d'un dispositif électrocommandable tel que défini à l'une des revendications 1 à 14, caractérisé par le fait que l'on dépose sur un substrat à fonction verrière (Vi ; Via-I-Vib) revêtu d'une première couche électroniquement conductrice (TCCi) i du côté de cette dernière, une couche de vernis électro-actif (VEA) à base d'au moins un polymère liant renfermant :15 - Method for manufacturing an electrocontrollable device as defined in one of claims 1 to 14, characterized in that it is deposited on a substrate with a glass function (Vi; Vi a -I-Vi b ) coated a first electronically conductive layer (TCCi) i on the side of the latter, a layer of electro-active varnish (VEA) based on at least one binder polymer containing:
- au moins un composé organique électro-actif (eai+) capable de se réduire et/ou d'accepter des électrons et des cations jouant le rôle de charges de compensation ; — au moins un composé organique électro-actif- at least one electro-active organic compound (eai + ) capable of reducing and/or accepting electrons and cations playing the role of compensation charges; — at least one electro-active organic compound
(eβ2) capable de s'oxyder et/ou d'éjecter des électrons et des cations jouant le rôle de charges de compensation ; au moins l'un desdits composés organiques électro- actifs (eai+ & ea2) étant électrochrome pour obtenir un contraste de couleur ; et(eβ2) capable of oxidizing and/or ejecting electrons and cations acting as compensation charges; at least one of said electroactive organic compounds (eai + & ea2) being electrochromic to obtain a color contrast; And
- des charges ioniques aptes à permettre, sous l'action d'un courant électrique, des réactions d'oxydation et
de réduction desdits composés organiques électroactifs (eai+ & ea2) , lesquelles sont nécessaires pour obtenir le contraste de couleur ; puis, après séchage du vernis (VEA) , une seconde couche électroniquement conductrice (TCC2) , puis, dans le cas où l'on souhaite réaliser un double vitrage, on rapporte un second substrat à fonction verrière- ionic charges capable of allowing, under the action of an electric current, oxidation reactions and reduction of said electroactive organic compounds (eai + & ea2), which are necessary to obtain the color contrast; then, after drying the varnish (VEA), a second electronically conductive layer (TCC2), then, in the case where double glazing is desired, a second substrate with glass function is added
(V2) du côté de la seconde couche électroniquement conductrice (TCC2) avec interposition d'une lame de gaz, tel que l'air ou l'argon, entre lui et ladite seconde couche électroniquement conductrice (TCC2) .(V 2 ) on the side of the second electronically conductive layer (TCC 2 ) with the interposition of a gas blade, such as air or argon, between it and said second electronically conductive layer (TCC 2 ).
16 - Procédé selon la revendication 15, caractérisé par le fait que l'on dépose la couche de vernis (VEA) par application par aspersion, arrosage ou ruissellement, par sérigraphie ou par technique de dépôt par rotation ou centrifugation ou par une technique de type jet d'encre ; et que l'on dépose la seconde couche électroniquement conductrice TCC2 par dépôt chimique en phase vapeur assisté plasma magnétron (PE-CVD) .
16 - Method according to claim 15, characterized in that the varnish layer (VEA) is deposited by application by sprinkling, watering or running, by screen printing or by deposition technique by rotation or centrifugation or by a technique of the type inkjet ; and that the second electronically conductive layer TCC 2 is deposited by magnetron plasma-assisted chemical vapor deposition (PE-CVD).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0858280A FR2939526B1 (en) | 2008-12-04 | 2008-12-04 | ELECTROCOMMADABLE DEVICE WITH CONTROLLED THICKNESS OF ELECTRO-ACTIVE MEDIUM AND SIMPLIFIED MANUFACTURE AND METHOD OF MANUFACTURE |
PCT/EP2009/066165 WO2010063729A1 (en) | 2008-12-04 | 2009-12-01 | Electrically controllable device with controlled thickness of the electroactive medium and simplified manufacturing, and method for making same |
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EP2374039A1 true EP2374039A1 (en) | 2011-10-12 |
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EP09796654A Withdrawn EP2374039A1 (en) | 2008-12-04 | 2009-12-01 | Electrically controllable device with controlled thickness of the electroactive medium and simplified manufacturing, and method for making same |
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US (1) | US20110216389A1 (en) |
EP (1) | EP2374039A1 (en) |
JP (1) | JP2012511166A (en) |
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WO (1) | WO2010063729A1 (en) |
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CA2077444A1 (en) * | 1990-03-06 | 1991-09-07 | Mani Shabrang | Sealed electrochromic device |
US5910854A (en) * | 1993-02-26 | 1999-06-08 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
DE60214833T2 (en) * | 2001-03-07 | 2007-09-06 | Acreo Ab | ELECTROCHROMICAL DEVICE |
ITCS20040008A1 (en) * | 2004-07-20 | 2004-10-20 | Consorzio Tebaid | ELECTRO-CHROMIC ORGANIC, SOLID, SELF-SUPPORTED MATERIAL |
-
2008
- 2008-12-04 FR FR0858280A patent/FR2939526B1/en not_active Expired - Fee Related
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- 2009-12-01 EA EA201170744A patent/EA201170744A1/en unknown
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- 2009-12-01 EP EP09796654A patent/EP2374039A1/en not_active Withdrawn
- 2009-12-01 CN CN2009801491385A patent/CN102239442A/en active Pending
- 2009-12-01 US US13/127,636 patent/US20110216389A1/en not_active Abandoned
- 2009-12-01 KR KR1020117012803A patent/KR20110100203A/en not_active Application Discontinuation
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CN102239442A (en) | 2011-11-09 |
EA201170744A1 (en) | 2011-12-30 |
JP2012511166A (en) | 2012-05-17 |
FR2939526A1 (en) | 2010-06-11 |
KR20110100203A (en) | 2011-09-09 |
WO2010063729A1 (en) | 2010-06-10 |
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