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
  • G02F1/153—Constructional details
  • G02F1/155—Electrodes
• • 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
  • G02F1/1503—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

Definitions

• the present invention relates to an electrically controllable device with variable optical / energy properties, comprising the following stack of layers:
• TCCi electronically conductive layer
• EA electro-active system
• 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 (ea2) capable of oxidizing and / or ejecting electrons and cations acting as compensation charges; at least one of said electroactive organic compounds (eai + and ea2) being electrochromic to obtain a color contrast; and
• Transparent Conductive Coating an example of which is a transparent conductive oxide TCO ("Transparent Conductive Oxide”.
• 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 two electro-active materials are electrochromic materials, these may be identical or different. In the case where one of the electro-active materials is electrochromic and the other is not, the latter will act as a counterelectrode not participating in the coloring and discoloration of the system.
• 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-dimethylphenazine) or non-electrochromic being for example a ferrocene)
• the redox reactions which are established under the action of the electric current are as follows:
• each current supply consists of a thin conductive strip applied along a border of the associated electrically conductive layer, the two strips being located along two opposite edges of the electrically controllable device.
• FIG. 1 to 3 of the accompanying drawing schematically illustrate a rear view mirror according to this state of the art.
• This rearview mirror comprises two glass plates V1, V2, arranged face to face, one being offset downwards to meet mounting objectives in the rear view mirror.
• the internal faces of each of these plates Vi, V 2 are coated with an electronically conductive layer, respectively TCCi, TCC 2 , consisting in particular of a TCO (abbreviation of "transparent conductive oxide").
• TCCi electronically conductive layer
• TCC 2 transparent conductive oxide
• EA electroactive medium
• TCC 1 , TCC 2 are produced by foils respectively 1, 2, each constituted by an L-shaped metal strip, one of the branches of which is applied to the edge of the coated glass Vi, V 2 and whose other branch is applied against the TCC1, TCC2 layer portion, protruding from the "reservoir” portion.
• the foils 1, 2 are applied respectively along the upper edge and along the lower edge of the mirror.
• the eli + compound will be chosen from 1,1'-diethyl-4,4'-bipyridinium diperchlorate (electrochromic) and, as compound ea 2 , 5,10-dihydro-5,10 dimethylphenazine (electrochrome) or ferrocene (non-electrochromic or counter-electrode not involved in the coloring process of the system).
• the active medium in which the species eai + and ea2 ⁇ are found
• the species eai + are reduced.
• species eal the latter being distributed uniformly in the vicinity of the surface of the electrically conductive layer connected to the sign pole - of the electrical supply, that is to say to the cathode of the glazing
• the ea2 species oxidize in ea2 + exp, the latter being distributed uniformly in the vicinity of the surface of the electronically conductive layer connected to the + sign pole of the power supply, that is to say to the anode of the glazing, the panel then appearing in a uniform color corresponding to the uniform mixture of species eai and ea2 + .
• This phenomenon of segregation is due to the preferential reduction of species eai + in species eai towards the zone of greater electrical intensity of the cathode, and, conversely, the preferential oxidation of the species ea2 into species ea2 + towards the zone of greater electrical intensity of the anode, these two zones of greater electrical intensity being those of the foils .
• Figure 7 of the accompanying drawing the upper part shows schematically a cross section of the known electrically controllable device and its lower part, a front view of the panel tensioned, illustrates this phenomenon of segregation typical of devices of the prior art with two zones: on one side of the species eai colored and on the other, species ea2 + stained with another color.
• Figure 1 thus shows the zones of accumulation of eai and ea2 + during a tensioning of the electrically controllable device, and, consequently, the appearance of a color mainly due to the species eai towards the cathode (on the right on the front view), this color gradually deteriorating a new color mainly due to the species ea2 + towards the anode (left on the front view).
• the phenomenon of segregation is moreover all the more important that the panel of the electrically controllable device is larger, and currently prevents the commercial use of large electrically controllable devices, such as electrically controllable glazing for the building.
• EP-A-113 313 discloses an electrochromic mirror comprising a transparent conductive substrate, a reflective conductive substrate and an ion conducting layer disposed between the two, at least one of said substrates being provided on the peripheral portion of its conductive surface with a highly conductive layer having a resistance lower than the surface resistance of said conductive surface.
• US-A-5,293,546 discloses a working electrode which comprises an electrically conductive metal grid or bus having a metal oxide coating.
• the grid is arranged under the oxide coating.
• the Applicant Company has therefore sought an effective means to avoid the segregation of phases described above both in the colored state, during the discoloration or bleached regardless of the duration during which the glazing was maintained at the colored state by the application of an electric current.
• the Applicant Company has also sought, for such electrically controllable devices, in particular those of large size, a good light transmission in the colored state, a good contrast and a good cell coloring speed.
• the present invention therefore relates to an electrically controllable device with variable optical / energy properties, comprising the stack of layers as defined at the very beginning of this description, characterized in that each current supply is constituted by a continuous conductive strip applied. on the associated electrically conductive layer, said conductive strip being disposed all around or substantially all around said layer (TCCi; TCC2) so as to reinforce its conductivity and being connected to the power supply by one of from its ends.
• the two continuous conductive strips are located with an offset in relation to each other, which is preferably less than or equal to 2 cm. This arrangement makes it possible to avoid short circuit phenomena between two conductive strips.
• conductive strips of a thickness substantially greater than or equal to 50 microns it is preferable to use conductive strips of a thickness substantially greater than or equal to 50 microns.
• the electro-active system preferably has a thickness of the order of 100 microns. Therefore, such conductive strips associated with electronically conductive layers vis-à-vis must be shifted so as not to touch each other, so that the potential difference between two conductive strips does not cause a short circuit.
• the conductive strip may be a metal, an alloy or an electrically conductive composite. This conductive strip may in particular be deposited directly on the substrates or the spacers using, for example, a screen printing technique with a metal paste, or welded to the substrates or spacers or else glued by means of an electrically conductive adhesive.
• a conductive strip is applied, in particular by gluing or welding, along a first edge of said layer (TCCi; TCC2), and , at its end opposite the beginning of the strip, is folded on itself at 90 ° to come to apply along the edge of the layer (TCCi; TCC2) perpendicular to the aforementioned border, then again 90 ° to come to apply along the edge opposite to the latter, and finally 90 ° to come to apply in the vicinity of the remaining edge stopping near the beginning of the strip, the latter exceeding the stack of layers forming the electrically controllable device to form a connection with a power supply.
• each conductive strip can be applied, by one of its faces, to the associated layer (TCCi; TCC2), and by its other face against said spacer frame.
• a continuous peripheral conductive strip is deposited by screen printing on each of the electronically conductive layers (TCCi; TCC2), a foil being applied to the beginning of said strip so as to exceed the stack of layers forming the electrically controllable device to form a connection with a power supply.
• a grid pattern fed by the associated conductive strip may be formed on the surface of at least one electronically conductive layer (TCCi; TCC 2 ).
• the substrates with glass function can be chosen from glass and transparent polymers, such as poly (methyl methacrylate) (PMMA), polycarbonate (PC), poly (ethylene terephthalate) (PET), poly (ethylene naphthoate ) (PEN) and cyclosporin copolymers (COC).
• PMMA poly (methyl methacrylate)
• PC polycarbonate
• PET poly (ethylene terephthalate)
• PEN poly (ethylene naphthoate )
• COC cyclosporin copolymers
• Electronically conductive layers are metal type layers, such as silver, gold, platinum and copper layers; or transparent conductive oxide (TCO) type layers, such as tin - doped indium oxide (In 2 Os: Sn or ITO) oxide layers, antimony doped indium oxide (In 2 ⁇ 3: S b ), fluorine doped tin oxide (SnO 2 : F) and zinc oxide doped with aluminum (ZnOiAl); or TCO / metal / TCO multilayers, the TCO and the metal being in particular chosen from those enumerated above; or NiC r / metal / NiC r multilayers, the metal being in particular chosen from those enumerated above.
• TCO transparent conductive oxide
• the TCCi and TCC 2 layers can also be in the form of a grid or a microgrid. They may also comprise an organic and / or inorganic sub-layer, particularly in the case of substrates plastics, as described in international application WO 2007/057605.
• the electro-active system (EA) can comprise a self-supporting polymer matrix in which the electroactive organic compound (s) (eai + & ea2) and the ionic charges are inserted, said polymer matrix enclosing it.
• the electro-active system may comprise a solution or a gel containing the electroactive organic compounds (eai + & ea 2 ).
• the electro-active system may be a self-supported and plasticized polymer film containing electroactive organic compounds The electroactive organic compound (s)
• (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) (EA 2 ) is or are selected from metallocenes, such as cobaltocenes, ferrocenes, N, N, N ', N' -tetramethyl phenylenediamine (TMPD), phenothiazines such as phenothiazine, dihydrophen
• the ionic salt (s) may be chosen from lithium perchlorate, trifluoromethanesulfonate or triflate salts, trifluoromethanesulfonylimide salts and ammonium salts; the acid or acids are chosen from sulfuric acid (H 2 SO 4 ), triflic acid (CF 3 SO 3 H), phosphoric acid (H 3 PO 4 ) and polyphosphoric acid (H n + 2 P n O 3n + i); the solvent or solvents are chosen from dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, propylene carbonate, ethylene carbonate, N-methyl-2-pyrrolidone (1-methyl-2-pyrrolidinone), gamma-butyrolactone, ethylene glycols, alcohols, ketones, nitriles and water, the ionic liquid or liquids are chosen from imidazolium salts, such as 1-ethyl-3-methylimidazolium te
• the autosupported polymer matrix may consist of at least one polymer layer in which said liquid has penetrated to the core.
• the polymer constituting at least one layer may be a homo- or copolymer in the form of a non-porous film capable of swelling in said liquid, or in the form of a porous film, said porous film optionally being capable of swelling in the liquid having ionic charges and whose porosity after swelling is chosen to allow percolation of the ionic charges in the thickness of the liquid-impregnated film.
• the polymeric material constituting at least one layer may also be chosen from:
• the homo- or copolymers which do not comprise ionic charges are borne by at least one aforementioned electroactive organic compound and / or by at least one solubilized ionic or acidic salt and / or by at least one liquid ionic or molten salt;
• - homo- or copolymers containing ionic charges in which case additional charges to enhance the rate of percolation can be carried by at least one electroactive organic compound and / or at least one solubilized ionic salt or acid and / or at least one ionic liquid or molten salt; and mixtures of at least one homopolymer or copolymer not bearing ionic charges and at least one homo - or copolymer having ionic charges, in which case additional charges for increasing the rate of percolation may be carried by minus an electroactive organic compound mentioned above and / or by at least one ionic salt or solubilized acid and / or by at least one ionic liquid or molten salt.
• the polymer matrix may consist of a film based on a homo- or copolymer comprising ionic charges, able to give by itself a film essentially capable of providing the desired percolation rate for the electro-active system or a higher percolation rate than this and a homo or copolymer with or without ionic charges, able to give itself a film that does not necessarily ensure the desired rate of percolation but essentially able to ensure the mechanical strength, the contents of each of these two homo- or copolymers being adjusted to ensure both the desired percolation rate and the mechanical strength of the resulting self-supporting organic active medium.
• the polymer or polymers of the polymer matrix not comprising ionic charges can be chosen from copolymers of ethylene, vinyl acetate and possibly at least one other comonomer, such as ethylene-vinyl acetate copolymers.
• EVA ethylene-vinyl acetate copolymers.
• PU polyurethane
• PVB polyvinyl butyral
• PI polyimides
• PA polyamides
• PS polyvinylidene fluoride
• PVDF polyvinylidene fluoride
• PEEK polyether ether ketones
• POE copolymers of epichlorohydrin and poly (methyl methacrylate) (PMMA); and the polymer (s) of the polymer matrix carrying ionic charges or polyelectrolytes are chosen from sulphonated polymers which have been exchanged for H + ions of SO 3 H groups by the ions of the desired ionic charges, this ion exchange having taken place before and / or simultaneously with the swelling of the polyelectrolyte in the liquid comprising ionic charges, the sulphonated polymers being chosen in particular from sulfonated tetrafluoroethylene copolymers, sulphonated polystyrenes (PSS), sulphonated polystyrene copolymers, poly (2-acrylamido), 2-methyl-1-propanesulfonic acid (PAMPS), sulfonated polyetheretherketones (PEEK) and sulfonated polyimides.
• the electrically controllable device of the present invention is in particular configured to form: a roof for a motor vehicle, activatable independently, 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.
• FIG. 1 is a schematic front view of a rear view mirror according to the prior art
• Figure 4 is a schematic sectional view of a glazing according to the invention.
• FIG. 5 is a view corresponding to Figure 4 showing an alternative embodiment of the glazing
• FIG. 6 is a sectional view along VI-VI of Figure 5;
• FIG. 6A shows two views schematizing a section of that of FIG. 6, making it possible to record the zones A, B and C on a glazing unit of the prior art (diagram on the right) and a glazing unit according to the invention (left diagram);
• FIG. 7, 8 and 8A are schematic views illustrating the development of coloring
• FIG. 8A further illustrating the so-called halo phenomenon, according to which, thanks to the bands disposed on the two conductive layers and over their entire periphery, a homogeneous distribution of eal and ea2 + species around the entire periphery is obtained;
• FIGS. 9 to 12 each represent the chromatic coordinates of Examples 1 (comparative), 2, 4 (comparative) and 5 in the CIELAB color space; measurements made on zones A and / or B and / or C, such as shown in Figure 6A.
• FIGS. 4 to 6 it can be seen that two variants of a glazing unit according to the invention have been shown, this one comprising two opposite glass sheets, Vi, V 2 , each coated with their layers respectively TTC1 and TTC 2 separated by a spacer frame 3 in double-sided adhesive with a polyester core and closed by an outer encapsulation seal J.
• the frame 3 and the two coated glass sheets delimit the internal receiving space of the medium EA.
• a current conducting conductive strip which has a length 1 along a border as in the case of the prior art of FIGS. 1 to 3, but extending by three successive lengths respectively la, Ib and Ic and 2a, 2b and 2c, each in the vicinity of one of the remaining three borders.
• the aforementioned thin strips are folded on themselves each time by 90 ° at the corners. They are opposite the spacer frame 3, facing each other in the variant of FIG. slightly displaced from each other in the variant of Figures 5 and 6.
• the assembly of the glazing and the encapsulation of the EA medium is done in a conventional manner, the current supply strips having previously been welded or glued on the periphery of the corresponding coated glass sheet.
• PVDF Poly (vinylidene fluoride)
• PET polyethylene terephthalate
• the "K-glass TM” glass used in these Examples is a glass covered with an electroconductive layer of SnO 2 IF (glass marketed under this name by the company "Pilkington”).
• SnO 2 IF glass marketed under this name by the company "Pilkington”
• the polyvinylidene fluoride powder manufactured by the company "Arkema” under the name “Kynarflex® 2821” was used.
• Electroactive system PVDF + 5, 10-dihydro-5,10-dimethylphenazine + 1,1'-diethyl-4,4'-bipyridinium diperchlorate + Lithium triflate + propylene carbonate SnO 2 layer glass: F Welded current supply strip on K-glass over the entire length of one of the four sides of each K-glass to reproduce the configuration of the prior art
• a self-supporting PVDF film was made by mixing 6.5 g of PVDF powder, 13.0 g of dibutyl phthalate, 0.5 g of nanoporous silica and 25 g of acetone. The formulation was stirred for two hours and cast on a glass plate. After evaporation of the solvent, the PVDF film was removed from the glass plate under a trickle of water. The film thus obtained has a thickness of about 200 microns.
• An electroactive solution was prepared by mixing 0.25 g of 5,10-dihydro-5,10-dimethylphenazine, 0.50 g of 1,1'-diethyl-4,4'-bipyridinium diperchlorate and 47 g of lithium triflate in 20 ml of propylene carbonate. The solution was stirred for 1 hour.
• the PVDF film about 200 microns thick, was immersed for 5 minutes in diethyl ether (to solubilize dibutyl phthalate) and then for 5 minutes in the electroactive solution before being deposited on a glass plate.
• diethyl ether to solubilize dibutyl phthalate
• electroactive solution before being deposited on a glass plate.
• K-glass A second "K-glass” plate was deposited on the electrolyte-impregnated film, a PET frame was used as a spacer around the electro-active medium and clamps were used to ensure a good contact between the glass and the film.
• the electrochromic device thus manufactured has an active surface area of 8 ⁇ 8 cm 2 and its performance is reported in Table 1 below:
• SnO 2 layer glass F Electroactive system of Example 1 SnO 2 layer glass: F
• An electrochromic device having an active surface area of 8 ⁇ 8 cm 2 was manufactured as described in Example 1 and the performance of which is given in Table 2 below:
• Electro-active system PVDF + ferrocene + diperchlorate
• An electrochromic device having an active surface area of 8 ⁇ 8 cm 2 was manufactured as described in Example 1 and the performance of which is given in Table 6 below:
• SnO2 layer glass F Supply strip of the welded current on the K-glass over the entire periphery of each K-glass according to the mode of the invention
• Electroactive system PVDF + ferrocene + 5, 10-dihydro-5, 10-dimethylphenazine + 1,1'-diethyl-4,4'-bipyridinium diperchlorate + lithium triflate + propylene carbonate
• An electroactive solution was prepared by mixing 0.11 g of ferrocene, 0.15 g of 5,10-dihydro-5,10-dimethylphenazine and 0.50 g of 1,1'-diethyl-4,4-diperchlorate. bipyridinium and 0.47 g of lithium triflate in 20 ml of propylene carbonate. The solution was stirred for 1 hour.
• SnO2 layer glass F Electroactive PVDF 5, 10-dihydro-5, 10-dimethylphenazine + 1,1'-diethyl-4,4'-bipyridinium diperchlorate + lithium triflate + propylene carbonate
• An electroactive solution was prepared by mixing 0.12 g of 5,10-dihydro-5,10-dimethylphenazine with 0.25 g of 1,1'-diethyl-4,4'-bipyridinium diperchlorate and 0.47 g. g of lithium triflate in 20 ml of propylene carbonate. The solution was stirred for 1 hour.
• An electrochromic device having an active surface area of 8 ⁇ 8 cm 2 was manufactured as described in Example 1 and the performance of which is given in Table 12 below:
• IEC 60050 International Electrotechnical Vocabulary - Details for IEV number 511-23-21 Second - quarter - second - quarter report 4 of 10
• the ITO layer glass welded on the entire length of one of the four sides of each ITO layer glass to reproduce the configuration of the prior art

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• Physics & Mathematics (AREA)
• Nonlinear Science (AREA)
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• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
• Photoreceptors In Electrophotography (AREA)
• Devices For Indicating Variable Information By Combining Individual Elements (AREA)
• Control Of Indicators Other Than Cathode Ray Tubes (AREA)

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• 2008
  • 2008-12-05 FR FR0858289A patent/FR2939527B1/fr not_active Expired - Fee Related
• 2009
  • 2009-12-01 EA EA201170757A patent/EA201170757A1/ru unknown
  • 2009-12-01 US US13/130,538 patent/US20110222138A1/en not_active Abandoned
  • 2009-12-01 CN CN2009801491370A patent/CN102239443A/zh active Pending
  • 2009-12-01 EP EP09803740A patent/EP2374040A1/de not_active Withdrawn
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  • 2009-12-01 KR KR1020117012798A patent/KR20110100202A/ko not_active Application Discontinuation
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