EP4370327A1 - Method for producing illuminated laminated glazing, which is transparent in a non-illuminated state - Google Patents
Method for producing illuminated laminated glazing, which is transparent in a non-illuminated stateInfo
- Publication number
- EP4370327A1 EP4370327A1 EP22744247.2A EP22744247A EP4370327A1 EP 4370327 A1 EP4370327 A1 EP 4370327A1 EP 22744247 A EP22744247 A EP 22744247A EP 4370327 A1 EP4370327 A1 EP 4370327A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- laminated glazing
- light
- glazing
- process according
- ink
- 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.)
- Pending
Links
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- 239000011521 glass Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 35
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- 238000007639 printing Methods 0.000 claims abstract description 14
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- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 20
- 239000012790 adhesive layer Substances 0.000 claims description 16
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
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- 239000000758 substrate Substances 0.000 claims description 8
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- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000007641 inkjet printing Methods 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 claims description 4
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- 239000004014 plasticizer Substances 0.000 claims description 4
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- 239000011159 matrix material Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 2
- 102000011045 Chloride Channels Human genes 0.000 claims description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000518 rheometry Methods 0.000 claims description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
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- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- -1 benzoate ester Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
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- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- LBKFHGHXATXEBY-UHFFFAOYSA-N bis(1-methylcyclohexyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OC2(C)CCCCC2)C=1C(=O)OC1(C)CCCCC1 LBKFHGHXATXEBY-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000011929 di(propylene glycol) methyl ether Substances 0.000 description 1
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- 238000010017 direct printing Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
- B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
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- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
- B32B17/10256—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques
- B32B17/10284—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons created by printing techniques on intermediate layer
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- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
- B32B17/10467—Variable transmission
- B32B17/10495—Variable transmission optoelectronic, i.e. optical valve
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10541—Functional features of the laminated safety glass or glazing comprising a light source or a light guide
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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- B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
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- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
- B41J3/407—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed for marking on special material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
- B41J3/407—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed for marking on special material
- B41J3/4073—Printing on three-dimensional objects not being in sheet or web form, e.g. spherical or cubic objects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5281—Polyurethanes or polyureas
Definitions
- This invention relates to illuminating glazing according to various known light emission methods, according to patterns of all complexity, according to different colors, among others.
- a demand for this type of glazing exists in particular in the automotive field, for example for glass roofs.
- the printed patterns thus obtained are then illuminated by activating edge lighting on the glazing, which may consist of a light-emitting diode LED bar (in English light-emitting diode - LED -) placed on the edges of the glazing, or a circular LED placed in a hole provided within the illuminating glazing.
- the printed diffusing patterns are visible to the passengers of the automobile, whether the window lighting is activated or not.
- the printed materials can be colored or translucent for example.
- edge lighting switching off or absent
- the printed patterns are visible from inside the vehicle and may hinder visibility through the glazing. This effect can be reduced by printing very fine patterns, but this greatly limits the flexibility of these patterns.
- the invention aims to solve this problem by proposing a method for obtaining a light extraction solution which is transparent in the off state.
- Transparent mineral pastes requiring a heat treatment between 550 and 800°C, deposited before forming the glass are not compatible with bending techniques, because they exhibit sticky behavior during processing. They cannot resist contact with the tools or the paired counter-glass (different sheets of glass in laminated glazing are frequently bent, in a known manner, by gravity sagging, in intimate contact with each other). others). Techniques to make these pastes non-sticky cause them to lose their transparency.
- the positioning of these mineral materials on the face of a sheet of glass intended to constitute the main interior face of the laminated glazing, not requiring the absence of stickiness of the materials, is not acceptable because transparent enamels have a low resistance to aging, and this positioning is not appreciated by consumers.
- the inner main face of the laminated glazing relates to the volume delimited by the laminated glazing, in particular the passenger compartment of a motor vehicle).
- the subject of the invention is a method for manufacturing laminated glazing comprising at least two sheets of glass bonded to one another by an intermediate adhesive layer, characterized in that it comprises, prior to the assembly of the laminated glazing, a digital printing of a face intended to be inside the laminated structure, of at least one of the two sheets of glass after their possible forming / bending, and/or of a face at least of the intermediate adhesive layer, by means of a homogeneous organic ink with a viscosity of between 1 and 50 mPa.s comprising 50 to 99% by mass of resin curable under ultraviolet radiation, and 0.05 to 20% by mass of scattering particles, then the curing of the organic ink under illumination by ultraviolet radiation.
- a curable (or crosslinkable) ink under UV light diffusing and transparent is deposited by a digital printing process.
- a digital printing technique direct printing on the substrate
- a resin curable under UV radiation is a composition of uncrosslinked monomers and/or oligomers, in an intermediate reaction/polymerization state, and optionally one or more UV curing initiators.
- the ink dries quickly (hardening under UV), compatible with the cycle times required on automotive laminated glazing production lines. This drying is no longer the bottleneck of the laminated glazing assembly. Adhesion to glass is good. No adhesion primer is required.
- the intermediate adhesive layer is made of polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), ionomer.
- PVB polyvinyl butyral
- TPU thermoplastic polyurethane
- EVA ethylene-vinyl acetate copolymer
- ionomer ionomer
- An example of a monomer resin is marketed by the Kuraray Company under the registered trademark SentryGlas®.
- the ink contains 0.01 to 20% by mass of one or more agents for modifying its rheology.
- the ink contains 0.1 to 20% by weight of thermoplastic polymer material at 1 to 20% by weight in one or more organic solvents.
- the thermoplastic material can be chosen from polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), ionomer, alone or as a mixture or copolymer of several of them.
- the thermoplastic polymer material may contain 5 to 45% by mass of plasticizer.
- plasticizer mention may be made of a benzoate ester, a phthalate and/or its derivative, an adipate and/or its derivative, a fatty acid ester, a trioctyltrimellitate, a triacetin, a glycerol, a propylene glycol, a sorbitol or a trimethylpentanedioldiisobutyrate, alone or as a mixture of several of them.
- the scattering particles have a particle size defined by D90 of less than 2 ⁇ m, preferably between 100 and 700 nm, in particular around 400 nm.
- the scattering particles are chosen from non-luminescent particles of TiC>2, SiC>2, CaCC>3, ZnO, Al2O3, ZrC>2.
- the organic ink comprises at most 5% by mass of luminescent particles, chosen from luminophores, fast-decreasing fluorescent particles or molecules coating non-luminescent particles.
- the luminescent particles are dispersed in the polymer matrix. The durability of these luminescent particles to light radiation must be high so as not to lead to an accelerated decay of the initial properties. An example of this consists of the product marketed by the BASF Company under the registered trademark TINOPAL® OB CO.
- the resin curable under ultraviolet radiation is chosen from a reaction product between a thiol and an alkene (called thiol-ene), an acrylate such as epoxy-acrylate, polyester-acrylate, urethane-acrylate, silicone-acrylate alone or as a mixture of several of them.
- thiol-ene an alkene
- an acrylate such as epoxy-acrylate, polyester-acrylate, urethane-acrylate, silicone-acrylate alone or as a mixture of several of them.
- the intermediate adhesive layer has a roughness Rz of between 5 and 25, preferably 10 and 15 ⁇ m.
- the ink is printed directly on the intermediate adhesive layer by inkjet printing with one or more passes.
- the ink is printed directly on a curved glass sheet by inkjet printing in one or more passes.
- the printheads are mounted on a multi-axis robot and the glass sheet is fixed.
- the curved sheet of glass is held by a multi-axis robot under the immobile print heads.
- Inkjet printing can be done on a three-dimensional substrate.
- first embodiment printing on the intermediate adhesive layer
- second printing on a sheet of curved glass
- the laminated glazing comprises a light source, such as a light-emitting diode LED (in English light-emitting diode - LED -), one of said two glass sheets or said intermediate adhesive layer constitutes a light guide optically coupled to the light source on the one hand, to the product of said digital printing which is capable of extracting the light thus guided on the other hand.
- the LED(s) can be in or near a (through) hole in the inner glass sheet for optical coupling by the wall delimiting the hole, or facing the edge of the glass sheet interior.
- the laminated glazing preferably comprises a light source, such as a light-emitting diode LED (in English light-emitting diode - LED -), emitting a light of length d wave at which the luminescent particles are excited and re-emit light radiation in the visible range.
- a light source such as a light-emitting diode LED (in English light-emitting diode - LED -)
- LEDs can be positioned as already indicated above.
- This excitation wavelength is for example in the UV in particular UVA, and even 365 to 400 or 390 nm.
- the laminated glazing has low solar energy transmission (in English Total Solar Transmittance) in the visible and infrared domains. In other words, the amount of solar energy transmitted by the laminated glazing is low.
- face 2 is provided with a stack of thin layers of solar control (reflecting solar radiation), such as a silver multilayer, and/or the face 4 of a low-emissivity coating in particular based on indium oxide doped with tin (in English Indium Tin Oxide - ITO - ), for example.
- a low-emissivity coating reflects infrared radiation inside a building or passenger compartment, so as to keep the heat in when the outside temperature is low.
- the laminated glazing comprises a functional film based on liquid crystals encapsulated, or dispersed in a polymer matrix (in English Polymer Dispersed Liquid Crystals - PDLC -), electrophoretic particles dispersed in a medium, particles dispersed in an electrophoretic fluid , or a Suspended Particle Device (SPD) film, or an electrochromic system.
- a functional film based on liquid crystals encapsulated, or dispersed in a polymer matrix (in English Polymer Dispersed Liquid Crystals - PDLC -), electrophoretic particles dispersed in a medium, particles dispersed in an electrophoretic fluid , or a Suspended Particle Device (SPD) film, or an electrochromic system.
- the one of said two sheets of glass intended to be more outside the volume delimited by the laminated glazing is tinted, while the other of said two sheets of glass, the inner sheet, is clear or extra-clear (in especially when it constitutes the light guide).
- the invention also relates to the use of a laminated glazing obtained by a manufacturing process described above, as glazing for land, water or air vehicles, or as glazing for buildings, in particular as automobile glazing, most particularly as a car roof.
- An organic ink with a viscosity of between 1 and 50 mPa.s is prepared by mixing
- polyvinyl butyral at 10% in an ethanol / Di(propylene glycol) methyl ether 50/50 solvent, the PVB containing 30% dimethylcyclohexyl phthalate (plasticizer), and
- T1O2 is mixed in diffusing particles whose particle size corresponds to the relationships 100 nm lower than D90 lower than 700 nm.
- a homogeneous and stable white solution is obtained over several days at rest. Good quality of the deposition is obtained on glass and on PVB with a 50 ⁇ m film puller, good adhesion even on flexible PVB, good UV curing in one passage of the conveyor.
- T1O2 we obtain a substrate provided with transparent patterns degrading the light transmission and the blur only in a very small proportion, and maintaining the clarity almost unchanged, compared to the absence of T1O2 particles.
- the use as automotive glazing, side, rear window, glass roof... is perfectly feasible in compliance with optical standards.
- the patterns formed with the T1O2 particles are able to extract the light from an LED bar at the edge of the glazing, for example, the glass sheet or the PVB layer constituting both the substrate and the light guide coupling the LED bar and the patterns.
- the invention makes it possible to obtain glazing capable of illuminating in several colors, simultaneously or sequentially.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
Abstract
The invention relates to a method for producing laminated glazing, comprising at least two sheets of glass bonded to one another by an adhesive interlayer, characterised in that it comprises, prior to the assembly of the laminated glazing, digitally printing a face intended to be on the inside of the laminated structure, at least one of the two glass sheets after the optional forming/curving thereof and/or at least one face of the adhesive interlayer by means of a homogeneous organic ink having a viscosity between 1 and 50 mPa.s comprising 50 to 99% by weight of resin curable under ultraviolet radiation and 0.05 to 20% by weight of diffusing particles, and subsequently curing, by means of UV light, the organic ink; using the laminated glazing obtained by said method as a glazing for a ground, water or air vehicle, or as a glazing for a building.
Description
Description Description
Titre de l'invention : Procédé de fabrication d’un vitrage feuilleté éclairant transparent à l’état éteintTitle of the invention: Process for manufacturing an illuminating laminated glazing transparent in the extinguished state
Cette invention a trait aux vitrages éclairants selon différents procédés d’émission de lumière connus, selon des motifs de toutes complexités, selon des couleurs différentes, entre autre. Une demande pour ce type de vitrages existe notamment dans le domaine automobile, par exemple pour les toits en verre. This invention relates to illuminating glazing according to various known light emission methods, according to patterns of all complexity, according to different colors, among others. A demand for this type of glazing exists in particular in the automotive field, for example for glass roofs.
On pourrait envisager d’imprimer sur le verre avant le bombage un émail (minéral) diffusant la lumière, ou d’imprimer une encre diffusante sur la couche adhésive intercalaire avant l’assemblage du vitrage feuilleté. Les motifs imprimés ainsi obtenus sont alors illuminés en actionnant un éclairage de bord du vitrage, pouvant consister en une barre à diode électroluminescente DEL (en anglais light-emitting diode - LED -) disposée sur les bords du vitrage, ou une DEL circulaire disposée dans un trou ménagé au sein du vitrage éclairant. One could consider printing a light-diffusing (mineral) enamel on the glass before bending, or printing a diffusing ink on the intermediate adhesive layer before assembling the laminated glazing. The printed patterns thus obtained are then illuminated by activating edge lighting on the glazing, which may consist of a light-emitting diode LED bar (in English light-emitting diode - LED -) placed on the edges of the glazing, or a circular LED placed in a hole provided within the illuminating glazing.
L’un des inconvénients de ces technologies est que les motifs diffusants imprimés sont visibles par les passagers de l’automobile, que l’éclairage du vitrage soit actionné ou pas. En effet, les matériaux imprimés peuvent être colorés ou translucides par exemple. Ainsi, même sans éclairage de bord (état éteint ou absence de celui-ci), les motifs imprimés sont visibles de l’intérieur du véhicule et peuvent gêner la visibilité à travers le vitrage. Cet effet peut être diminué en imprimant des motifs très fins mais cela limite beaucoup la flexibilité de ces motifs. L’invention vise à résoudre ce problème en proposant un procédé pour obtenir une solution d’extraction de lumière qui soit transparente à l’état éteint. One of the disadvantages of these technologies is that the printed diffusing patterns are visible to the passengers of the automobile, whether the window lighting is activated or not. Indeed, the printed materials can be colored or translucent for example. Thus, even without edge lighting (switched off or absent), the printed patterns are visible from inside the vehicle and may hinder visibility through the glazing. This effect can be reduced by printing very fine patterns, but this greatly limits the flexibility of these patterns. The invention aims to solve this problem by proposing a method for obtaining a light extraction solution which is transparent in the off state.
Selon une première voie, il peut être envisagé d’imprimer un matériau minéral. Des pâtes transparentes minérales requérant un traitement thermique entre 550 et 800 °C, déposées avant le formage du verre, ne sont pas compatibles avec les techniques de bombage, car elles présentent un comportement collant pendant la mise en œuvre. Elles ne peuvent pas résister au contact avec l’outillage ou le contre-verre appairé (différentes feuilles de verre d’un vitrage feuilleté sont fréquemment bombées, de manière connue, par affaissement par gravité, en contact intime les unes avec les
autres). Les techniques pour rendre ces pâtes non collantes leur font perdre la transparence. According to a first way, it can be envisaged to print a mineral material. Transparent mineral pastes requiring a heat treatment between 550 and 800°C, deposited before forming the glass, are not compatible with bending techniques, because they exhibit sticky behavior during processing. They cannot resist contact with the tools or the paired counter-glass (different sheets of glass in laminated glazing are frequently bent, in a known manner, by gravity sagging, in intimate contact with each other). others). Techniques to make these pastes non-sticky cause them to lose their transparency.
Le positionnement de ces matériaux minéraux sur la face d’une feuille de verre destinée à constituer la face principale intérieure du vitrage feuilleté, ne requérant pas l’absence de caractère collant des matériaux, n’est pas acceptable car les émaux transparents ont une faible résistance au vieillissement, et ce positionnement n’est pas apprécié des consommateurs. (La face principale intérieure du vitrage feuilleté est relative au volume délimité par le vitrage feuilleté, notamment habitacle de véhicule automobile). The positioning of these mineral materials on the face of a sheet of glass intended to constitute the main interior face of the laminated glazing, not requiring the absence of stickiness of the materials, is not acceptable because transparent enamels have a low resistance to aging, and this positioning is not appreciated by consumers. (The inner main face of the laminated glazing relates to the volume delimited by the laminated glazing, in particular the passenger compartment of a motor vehicle).
Selon une seconde voie, l’impression d’encre organique semble la solution la plus prometteuse pour fabriquer un revêtement extracteur de lumière qui soit transparent. Cette encre est imprimée sur la couche adhésive intercalaire car en raison de sa nature organique, elle ne résiste pas à la température de formage du verre, supérieure à 500 °C. Les encres courantes à base de polyvinylbutyral (PVB) dans un solvant requièrent une opération de séchage longue lorsqu’elles sont imprimées sur le PVB, car ce substrat en matériau polymère est incompatible avec un séchage par infrarouge (IR). According to a second way, the printing of organic ink seems the most promising solution to manufacture a light extracting coating which is transparent. This ink is printed on the interlayer adhesive layer because, due to its organic nature, it does not withstand the glass forming temperature of over 500°C. Common solvent-based polyvinyl butyral (PVB) inks require a long drying operation when printed on PVB, as this polymer material substrate is incompatible with infrared (IR) drying.
L’invention a pour but la mise à disposition d’un procédé de réalisation de tels motifs invisibles lorsque l’éclairage est à l’état éteint, ne présentant pas les inconvénients précités. A cet effet, l’invention a pour objet un procédé de fabrication d’un vitrage feuilleté comprenant au moins deux feuilles de verre collées l’une à l’autre par une couche adhésive intercalaire, caractérisé en ce qu’il comprend, préalablement à l’assemblage du vitrage feuilleté, une impression digitale d’une face destinée à être à l’intérieur de la structure feuilletée, d’au moins une des deux feuilles de verre après leur éventuel formage / bombage, et/ou d’une face au moins de la couche adhésive intercalaire, au moyen d’une encre organique homogène de viscosité comprise entre 1 et 50 mPa.s comprenant 50 à 99 % en masse de résine durcissable sous rayonnement ultraviolet, et 0,05 à 20 % en masse de particules diffusantes, puis le durcissement de l’encre organique sous illumination par un rayonnement ultraviolet.The object of the invention is to provide a method for producing such invisible patterns when the lighting is in the off state, which does not have the aforementioned drawbacks. To this end, the subject of the invention is a method for manufacturing laminated glazing comprising at least two sheets of glass bonded to one another by an intermediate adhesive layer, characterized in that it comprises, prior to the assembly of the laminated glazing, a digital printing of a face intended to be inside the laminated structure, of at least one of the two sheets of glass after their possible forming / bending, and/or of a face at least of the intermediate adhesive layer, by means of a homogeneous organic ink with a viscosity of between 1 and 50 mPa.s comprising 50 to 99% by mass of resin curable under ultraviolet radiation, and 0.05 to 20% by mass of scattering particles, then the curing of the organic ink under illumination by ultraviolet radiation.
Conformément à l’invention, une encre durcissable (ou réticulable) sous UV diffusant la lumière et transparente est déposée par un procédé d’impression digitale. Une technique d’impression digitale (impression directe sur le substrat) permet d’imprimer
l’encre sans aucun contact avec le substrat à imprimer. Sont imprimées la couche adhésive intercalaire et/ou une face interne à la structure feuilletée d’une feuille de verre bombée (après le procédé de formage). According to the invention, a curable (or crosslinkable) ink under UV light diffusing and transparent is deposited by a digital printing process. A digital printing technique (direct printing on the substrate) makes it possible to print ink without any contact with the substrate to be printed. Are printed the intermediate adhesive layer and / or an internal face to the laminated structure of a curved glass sheet (after the forming process).
Une résine durcissable sous rayonnement UV est une composition de monomères et/ou oligomères non réticulés, dans un état intermédiaire de réaction / polymérisation, et éventuellement d’un ou plusieurs initiateurs de durcissement sous UV. A resin curable under UV radiation is a composition of uncrosslinked monomers and/or oligomers, in an intermediate reaction/polymerization state, and optionally one or more UV curing initiators.
Le séchage de l’encre est rapide (durcissement sous UV), compatible avec les temps de cycle requis sur les lignes de fabrication de vitrage feuilleté automobile. Ce séchage n’est plus le goulot d’étranglement de l’assemblage du vitrage feuilleté. L’adhésion au verre est bonne. Aucun primaire d’adhésion n’est nécessaire. The ink dries quickly (hardening under UV), compatible with the cycle times required on automotive laminated glazing production lines. This drying is no longer the bottleneck of the laminated glazing assembly. Adhesion to glass is good. No adhesion primer is required.
De préférence, la couche adhésive intercalaire est en polyvinylbutyral (PVB), polyuréthane thermoplastique (TPU), copolymère éthylène-acétate de vinyle (EVA), ionomère. Un exemple de résine monomère est commercialisé par la Société Kuraray sous la marque enregistrée SentryGlas®. Preferably, the intermediate adhesive layer is made of polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), ionomer. An example of a monomer resin is marketed by the Kuraray Company under the registered trademark SentryGlas®.
De préférence, l’encre contient 0,01 à 20 % en masse d’un ou plusieurs agents de modification de sa rhéologie. Preferably, the ink contains 0.01 to 20% by mass of one or more agents for modifying its rheology.
De préférence, l’encre contient 0,1 à 20 % en masse de matériau polymère thermoplastique à 1 à 20 % en masse dans un ou plusieurs solvants organiques. Le matériau thermoplastique peut être choisi parmi les polyvinylbutyral (PVB), polyuréthane thermoplastique (TPU), copolymère éthylène-acétate de vinyle (EVA), ionomère, seul ou en mélange ou copolymère de plusieurs d’entre eux. Le matériau polymère thermoplastique peut contenir 5 à 45 % en masse de plastifiant. Comme plastifiant, on peut citer un ester de benzoate, un phtalate et/ou son dérivé, un adipate et/ou son dérivé, un ester d’acide gras, un trioctyltrimellitate, une triacetine, un glycérol, un propylèneglycol, un sorbitol ou un triméthylpentanedioldiisobutyrate, seul ou en mélange de plusieurs d’entre eux. Preferably, the ink contains 0.1 to 20% by weight of thermoplastic polymer material at 1 to 20% by weight in one or more organic solvents. The thermoplastic material can be chosen from polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), ionomer, alone or as a mixture or copolymer of several of them. The thermoplastic polymer material may contain 5 to 45% by mass of plasticizer. As plasticizer, mention may be made of a benzoate ester, a phthalate and/or its derivative, an adipate and/or its derivative, a fatty acid ester, a trioctyltrimellitate, a triacetin, a glycerol, a propylene glycol, a sorbitol or a trimethylpentanedioldiisobutyrate, alone or as a mixture of several of them.
De préférence, les particules diffusantes ont une granulométrie définie par D90 inférieur à 2 pm, de préférence compris entre 100 et 700 nm, notamment autour de 400 nm. Preferably, the scattering particles have a particle size defined by D90 of less than 2 μm, preferably between 100 and 700 nm, in particular around 400 nm.
De préférence, les particules diffusantes sont choisies parmi des particules de TiC>2, SiC>2, CaCC>3, ZnO, AI2O3, ZrC>2non luminescentes.
Dans une réalisation particulière intéressante, l’encre organique comprend au plus 5 % en masse de particules luminescentes, choisies parmi des luminophores, des particules fluorescentes à décroissance rapide ou des molécules enrobant des particules non luminescentes. Les particules luminescentes sont dispersées dans la matrice polymère. La durabilité de ces particules luminescentes au rayonnement lumineux doit être élevée pour ne pas conduire à une décroissance accélérée des propriétés initiales. Un exemple en est constitué du produit commercialisé par la Société BASF sous la marque enregistrée TINOPAL® OB CO. Preferably, the scattering particles are chosen from non-luminescent particles of TiC>2, SiC>2, CaCC>3, ZnO, Al2O3, ZrC>2. In a particular advantageous embodiment, the organic ink comprises at most 5% by mass of luminescent particles, chosen from luminophores, fast-decreasing fluorescent particles or molecules coating non-luminescent particles. The luminescent particles are dispersed in the polymer matrix. The durability of these luminescent particles to light radiation must be high so as not to lead to an accelerated decay of the initial properties. An example of this consists of the product marketed by the BASF Company under the registered trademark TINOPAL® OB CO.
De préférence, la résine durcissable sous rayonnement ultraviolet est choisie parmi un produit de réaction entre un thiol et un alcène (appelé thiol-ene), un acrylate tel qu’epoxy-acrylate, polyester-acrylate, urethane-acrylate, silicone-acrylate seul ou en mélange de plusieurs d’entre eux. Preferably, the resin curable under ultraviolet radiation is chosen from a reaction product between a thiol and an alkene (called thiol-ene), an acrylate such as epoxy-acrylate, polyester-acrylate, urethane-acrylate, silicone-acrylate alone or as a mixture of several of them.
De préférence, préalablement à l’assemblage du vitrage feuilleté, la couche adhésive intercalaire a une rugosité Rz comprise entre 5 et 25, de préférence 10 et 15 pm.Preferably, prior to assembly of the laminated glazing, the intermediate adhesive layer has a roughness Rz of between 5 and 25, preferably 10 and 15 μm.
Selon un premier mode de réalisation, l’encre est directement imprimée sur la couche adhésive intercalaire par impression à jet d’encre à une ou plusieurs passes. According to a first embodiment, the ink is printed directly on the intermediate adhesive layer by inkjet printing with one or more passes.
Selon un deuxième mode de réalisation, l’encre est directement imprimée sur une feuille de verre bombée par impression à jet d’encre à une ou plusieurs passes. Dans ce cas, trois variantes sont possibles. Conformément à la première, les têtes d’impression sont montées sur un robot multi-axe et la feuille de verre est fixe. Dans la deuxième, au contraire, la feuille de verre bombée est maintenue par un robot multi- axe sous les têtes d’impression immobiles. Dans la troisième, il y a à la fois un déplacement du substrat et un déplacement des têtes d’impression s’adaptant à la forme du vitrage. L’impression jet d’encre est réalisable sur un substrat en trois dimensions. According to a second embodiment, the ink is printed directly on a curved glass sheet by inkjet printing in one or more passes. In this case, three variants are possible. According to the first, the printheads are mounted on a multi-axis robot and the glass sheet is fixed. In the second, on the contrary, the curved sheet of glass is held by a multi-axis robot under the immobile print heads. In the third, there is both a displacement of the substrate and a displacement of the printheads adapting to the shape of the glazing. Inkjet printing can be done on a three-dimensional substrate.
La mise en oeuvre du premier mode de réalisation (impression sur la couche adhésive intercalaire) et celle du second (impression sur une feuille de verre bombée) ne s’excluent pas mutuellement, au contraire elles peuvent être réalisées toutes deux sur un vitrage feuilleté. The implementation of the first embodiment (printing on the intermediate adhesive layer) and that of the second (printing on a sheet of curved glass) are not mutually exclusive, on the contrary they can both be carried out on laminated glazing.
De préférence, le vitrage feuilleté comprend une source de lumière, telle que diode électroluminescente DEL (en anglais light-emitting diode - LED -), l’une desdites deux
feuilles de verre ou ladite couche adhésive intercalaire constitue un guide de lumière couplé optiquement à la source de lumière d’une part, au produit de ladite impression digitale qui est apte à extraire la lumière ainsi guidée d’autre part. La ou les LEDs peu(ven)t être dans ou au voisinage d’un trou (traversant) de la feuille de verre intérieure pour un couplage optique par la paroi délimitant le trou, ou bien en regard de la tranche de la feuille de verre intérieure. Preferably, the laminated glazing comprises a light source, such as a light-emitting diode LED (in English light-emitting diode - LED -), one of said two glass sheets or said intermediate adhesive layer constitutes a light guide optically coupled to the light source on the one hand, to the product of said digital printing which is capable of extracting the light thus guided on the other hand. The LED(s) can be in or near a (through) hole in the inner glass sheet for optical coupling by the wall delimiting the hole, or facing the edge of the glass sheet interior.
Lorsque l’encre organique du procédé de l’invention comprend des particules luminescentes, le vitrage feuilleté comprend de préférence une source de lumière, telle que diode électroluminescente DEL (en anglais light-emitting diode - LED -), émettant une lumière de longueur d’onde à laquelle les particules luminescentes sont excitées et ré-émettent un rayonnement lumineux dans le domaine visible. Cette ou ces LEDs peu(ven)t être positionnée(s) comme déjà indiqué précédemment. Cette longueur d’onde d’excitation est par exemple dans l’UV en particulier UVA, et même 365 à 400 ou 390 nm. On pourrait envisager des LEDs émettant à la fois à cette longueur d’onde d’excitation et dans le visible. When the organic ink of the process of the invention comprises luminescent particles, the laminated glazing preferably comprises a light source, such as a light-emitting diode LED (in English light-emitting diode - LED -), emitting a light of length d wave at which the luminescent particles are excited and re-emit light radiation in the visible range. This or these LEDs can be positioned as already indicated above. This excitation wavelength is for example in the UV in particular UVA, and even 365 to 400 or 390 nm. One could consider LEDs emitting both at this excitation wavelength and in the visible.
Dans une réalisation avantageuse, le vitrage feuilleté est à basse transmission d’énergie solaire (en anglais Total Solar Transmittance) dans les domaines visible et infra-rouge. En d’autres termes, la quantité d’énergie solaire transmise par le vitrage feuilleté est faible. A cette fin, dans le cas d’un vitrage feuilleté à deux feuilles de verre dont les faces sont numérotées de 1 à 4 à partir de l’extérieur en position de montage, la face 2 est munie d’un empilement de couches minces de contrôle solaire (réfléchissant le rayonnement solaire), tel que multicouche argent, et/ou la face 4 d’un revêtement bas-émissif notamment à base d’oxyde d’indium dopé à l’étain (en anglais Indium Tin Oxide - ITO -), par exemple. Un revêtement bas-émissif réfléchit le rayonnement infra-rouge à l’intérieur d’un bâtiment ou d’un habitacle, de manière à en garder la chaleur lorsque la température extérieure est basse. In an advantageous embodiment, the laminated glazing has low solar energy transmission (in English Total Solar Transmittance) in the visible and infrared domains. In other words, the amount of solar energy transmitted by the laminated glazing is low. To this end, in the case of laminated glazing with two sheets of glass whose faces are numbered from 1 to 4 from the outside in the mounting position, face 2 is provided with a stack of thin layers of solar control (reflecting solar radiation), such as a silver multilayer, and/or the face 4 of a low-emissivity coating in particular based on indium oxide doped with tin (in English Indium Tin Oxide - ITO - ), for example. A low-emissivity coating reflects infrared radiation inside a building or passenger compartment, so as to keep the heat in when the outside temperature is low.
De préférence, le vitrage feuilleté comprend un film fonctionnel à base de cristaux liquides encapsulés, ou dispersés dans une matrice polymère (en anglais Polymer Dispersed Liquid Crystals - PDLC -), de particules électrophorétiques dispersées dans un milieu, de particules dispersées dans un fluide électrophorétique, ou un film de dispositif de particules en suspension (en anglais Suspended Particle Device - SPD -), ou un système électrochrome.
De préférence, celle desdites deux feuilles de verre destinée à être plus à l’extérieur du volume délimité par le vitrage feuilleté est teintée, tandis que l’autre desdites deux feuilles de verre, la feuille intérieure, est claire ou extra-claire (en particulier lorsque celle-ci constitue le guide de lumière). Preferably, the laminated glazing comprises a functional film based on liquid crystals encapsulated, or dispersed in a polymer matrix (in English Polymer Dispersed Liquid Crystals - PDLC -), electrophoretic particles dispersed in a medium, particles dispersed in an electrophoretic fluid , or a Suspended Particle Device (SPD) film, or an electrochromic system. Preferably, the one of said two sheets of glass intended to be more outside the volume delimited by the laminated glazing is tinted, while the other of said two sheets of glass, the inner sheet, is clear or extra-clear (in especially when it constitutes the light guide).
L’invention a également pour objet l’utilisation d’un vitrage feuilleté obtenu par un procédé de fabrication décrit ci-dessus, comme vitrage de véhicule terrestre, aquatique ou aérien, ou comme vitrage de bâtiment, en particulier comme vitrage automobile, tout particulièrement comme toit automobile. The invention also relates to the use of a laminated glazing obtained by a manufacturing process described above, as glazing for land, water or air vehicles, or as glazing for buildings, in particular as automobile glazing, most particularly as a car roof.
L’invention est maintenant illustrée à l’aide des exemples suivants. The invention is now illustrated with the aid of the following examples.
Contre-exemple 1 Counterexample 1
On prépare une encre organique de viscosité comprise entre 1 et 50 mPa.s, en mélangeant An organic ink with a viscosity of between 1 and 50 mPa.s is prepared by mixing
- 80 % de 4-Phenoxyethyl Monomère acrylate (PEA), résine durcissable sous UV commercialisée par la Société Sartomer (Groupe Arkema) sous la référence commerciale SR 410, viscosité à 25 °C = 38 mPa.s, - 80% of 4-Phenoxyethyl Monomer acrylate (PEA), resin curable under UV marketed by Sartomer (Arkema Group) under the commercial reference SR 410, viscosity at 25°C = 38 mPa.s,
- 16 % de polyvinylbutyral (PVB) à 10 % dans un solvant éthanol / Di(propylene glycol) methyl ether 50 / 50, le PVB contenant 30 % de dimethylcyclohexyl phtalate (plastifiant), et - 16% polyvinyl butyral (PVB) at 10% in an ethanol / Di(propylene glycol) methyl ether 50/50 solvent, the PVB containing 30% dimethylcyclohexyl phthalate (plasticizer), and
4 % de 2-hydroxy-2-methyl-1-phenylpropanone (photoinitiateur) commercialisé par la Société Sartomer sous la marque enregistrée Speedcure® 73. 4% of 2-hydroxy-2-methyl-1-phenylpropanone (photoinitiator) marketed by Sartomer under the registered trademark Speedcure® 73.
Toutes les proportions sont en masse. On ne réussit pas à homogénéiser en solution le PVB. All proportions are by mass. It is not possible to homogenize the PVB in solution.
Exemple 1 Example 1
On réussit cette fois à préparer une encre organique homogène de viscosité comprise entre 1 et 50 mPa.s, en substituant à la résine durcissable sous UV du Contre-exemple 1 , une proportion identique de résine durcissable sous UV commercialisée par la Société Sartomer (Groupe Arkema) sous la référence commerciale SR 238, viscosité à 25 °C = 7 mPa.s ; il s’agit de 1 ,6-Hexanediol Di Monomère acrylate (HDDA).
Cette encre est bien homogène en solution. On observe une bonne qualité du dépôt sur verre au tire film 50 miti, ainsi qu’une bonne réticulation aux UV en un passage de convoyeur. This time, we succeeded in preparing a homogeneous organic ink with a viscosity of between 1 and 50 mPa.s, by replacing the UV-curable resin of Counterexample 1 with an identical proportion of UV-curable resin marketed by Sartomer (Groupe Arkema) under the commercial reference SR 238, viscosity at 25° C.=7 mPa.s; it is 1,6-Hexanediol Di Monomer acrylate (HDDA). This ink is very homogeneous in solution. A good quality of the deposition on glass with a 50 miti film puller is observed, as well as good UV curing in one passage of the conveyor.
A 99,8 % de cette encre, on mélange 0,2 % de T1O2 en particules diffusantes dont la granulométrie répond aux relations 100 nm inférieur à D90 inférieur à 700 nm. On obtient une solution blanche homogène et stable sur plusieurs jours au repos. On obtient une bonne qualité du dépôt sur verre et sur PVB au tire film 50 pm, une bonne adhésion même sur PVB flexible, une bonne réticulation aux UV en un passage de convoyeur. At 99.8% of this ink, 0.2% of T1O2 is mixed in diffusing particles whose particle size corresponds to the relationships 100 nm lower than D90 lower than 700 nm. A homogeneous and stable white solution is obtained over several days at rest. Good quality of the deposition is obtained on glass and on PVB with a 50 μm film puller, good adhesion even on flexible PVB, good UV curing in one passage of the conveyor.
On effectue une évaluation optique de la transparence d’une feuille de verre revêtue de l’encre transparente réticulée, avec et sans particules de PO2, en utilisant un Hazemeter modèle haze-gard plus 4725 de marque enregistrée BYK®. Celui-ci contrôle une transparence totale selon les méthodes des normes internationales ASTM D1003 - Méthode standard de test de voile et de transmission lumineuse des plastiques transparents. An optical evaluation of the transparency of a glass sheet coated with cross-linked transparent ink, with and without PO2 particles, is carried out using a Hazemeter model haze-gard plus 4725 of registered brand BYK®. This checks for total transparency according to the methods of the international standards ASTM D1003 - Standard method for the test of haze and light transmission of transparent plastics.
Sont consignées dans le tableau ci-dessous les valeurs de The table below shows the values of
- TL : transmission lumineuse (en anglais Transmittance), - TL: light transmission (Transmittance in English),
- H : flou / voile (en anglais Haze), - H: blur / veil (in English Haze),
- C : netteté / clarté (en anglais Clarity). - C: sharpness / clarity (in English Clarity).
[Tableaux 1]
[Tables 1]
Avec T1O2, on obtient un substrat muni de motifs transparents ne dégradant la transmission lumineuse et le flou que dans une très faible proportion, et maintenant la clarté quasi inchangée, par rapport à l’absence de particules de T1O2. L’utilisation comme vitrage automobile, latéral, lunette arrière, toit en verre... est parfaitement réalisable dans le respect des normes optiques. With T1O2, we obtain a substrate provided with transparent patterns degrading the light transmission and the blur only in a very small proportion, and maintaining the clarity almost unchanged, compared to the absence of T1O2 particles. The use as automotive glazing, side, rear window, glass roof... is perfectly feasible in compliance with optical standards.
Les motifs formés avec les particules de T1O2 sont aptes à extraire la lumière d’une barre de LED en bord de vitrage, par exemple, la feuille de verre ou la couche de PVB
constituant à la fois le substrat et le guide de lumière couplant la barre de LED et les motifs. En employant des particules diffusantes de diverses natures, et/ou des sources lumineuses de diverses natures, voire des particules luminescentes de diverses natures, l’invention permet d’obtenir un vitrage apte à éclairer en plusieurs couleurs, simultanément, ou séquentiellement. The patterns formed with the T1O2 particles are able to extract the light from an LED bar at the edge of the glazing, for example, the glass sheet or the PVB layer constituting both the substrate and the light guide coupling the LED bar and the patterns. By using scattering particles of various kinds, and/or light sources of various kinds, or even luminescent particles of various kinds, the invention makes it possible to obtain glazing capable of illuminating in several colors, simultaneously or sequentially.
Contre-exemple 2 Counterexample 2
On mélange 10 % de PVB dans 90 % de résine durcissable sous UV HDDA utilisée à l’exemple 1. On ne réussit pas à bien homogénéiser en solution le PVB.
10% of PVB is mixed in 90% of HDDA UV-curable resin used in Example 1. It is not possible to homogenize the PVB well in solution.
Claims
[Revendication 1] Procédé de fabrication d’un vitrage feuilleté comprenant au moins deux feuilles de verre collées l’une à l’autre par une couche adhésive intercalaire, caractérisé en ce qu’il comprend, préalablement à l’assemblage du vitrage feuilleté, une impression digitale d’une face destinée à être à l’intérieur de la structure feuilletée, d’au moins une des deux feuilles de verre après leur éventuel formage / bombage, et/ou d’une face au moins de la couche adhésive intercalaire, au moyen d’une encre organique homogène de viscosité comprise entre 1 et 50 mPa.s comprenant50 à 99 % en masse de résine durcissable sous rayonnement ultraviolet, et 0,05 à 20 % en masse de particules diffusantes, puis le durcissement de l’encre organique sous illumination par un rayonnement ultraviolet. [Claim 1] A method of manufacturing laminated glazing comprising at least two sheets of glass bonded to each other by an intermediate adhesive layer, characterized in that it comprises, prior to the assembly of the laminated glazing, digital printing of a side intended to be inside the laminated structure, of at least one of the two sheets of glass after their possible forming/bending, and/or of at least one side of the intermediate adhesive layer , by means of a homogeneous organic ink with a viscosity of between 1 and 50 mPa.s comprising 50 to 99% by mass of resin curable under ultraviolet radiation, and 0.05 to 20% by mass of scattering particles, then the hardening of the organic ink under illumination by ultraviolet radiation.
[Revendication 2] Procédé selon la revendication 1 , caractérisé en ce que la couche adhésive intercalaire est en polyvinylbutyral (PVB), polyuréthane thermoplastique (TPU), copolymère éthylène-acétate de vinyle (EVA), ionomère. [Claim 2] Process according to Claim 1, characterized in that the intermediate adhesive layer is made of polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), ionomer.
[Revendication 3] Procédé selon la revendication 1 , caractérisé en ce que l’encre contient 0,01 à 20 % en masse d’un ou plusieurs agents de modification de sa rhéologie. [Claim 3] Process according to Claim 1, characterized in that the ink contains 0.01 to 20% by mass of one or more agents for modifying its rheology.
[Revendication 4] Procédé selon la revendication 1 , caractérisé en ce que l’encre contient 0,1 à 20 % en masse de matériau polymère thermoplastique à 1 à 20 % en masse dans un ou plusieurs solvants organiques. [Claim 4] Process according to claim 1, characterized in that the ink contains 0.1 to 20% by mass of thermoplastic polymer material at 1 to 20% by mass in one or more organic solvents.
[Revendication 5] Procédé selon la revendication 4, caractérisé en ce que le matériau thermoplastique peut être choisi parmi les polyvinylbutyral (PVB), polyuréthane thermoplastique (TPU), copolymère éthylène-acétate de vinyle (EVA), ionomère, seul ou en mélange ou copolymère de plusieurs d’entre eux. [Claim 5] Process according to Claim 4, characterized in that the thermoplastic material may be chosen from polyvinyl butyral (PVB), thermoplastic polyurethane (TPU), ethylene-vinyl acetate copolymer (EVA), ionomer, alone or as a mixture or copolymer of several of them.
[Revendication 6] Procédé selon la revendication 4, caractérisé en ce que le matériau polymère thermoplastique contient 5 à 45 % en masse de plastifiant. [Claim 6] Process according to Claim 4, characterized in that the thermoplastic polymer material contains 5 to 45% by mass of plasticizer.
[Revendication 7] Procédé selon la revendication 1 , caractérisé en ce que les particules diffusantes ont une granulométrie définie par D90 inférieur à 2 pm, de préférence compris entre 100 et 700 nm, notamment autour de 400 nm.
[Claim 7] Process according to claim 1, characterized in that the scattering particles have a particle size defined by D90 of less than 2 μm, preferably between 100 and 700 nm, in particular around 400 nm.
[Revendication 8] Procédé selon la revendication 1 , caractérisé en ce que les particules diffusantes sont choisies parmi des particules de PO2, S1O2, CaCC>3, ZnO, AI2O3, ZrC>2non luminescentes. [Claim 8] Process according to claim 1, characterized in that the scattering particles are chosen from non-luminescent particles of PO2, S1O2, CaCC>3, ZnO, Al2O3, ZrC>2.
[Revendication 9] Procédé selon la revendication 1 , caractérisé en ce que l’encre organique comprend au plus 5 % en masse de particules luminescentes choisies parmi des luminophores, des particules fluorescentes à décroissance rapide ou des molécules enrobant des particules non luminescentes. [Claim 9] Process according to claim 1, characterized in that the organic ink comprises at most 5% by mass of luminescent particles chosen from phosphors, rapidly decaying fluorescent particles or molecules coating non-luminescent particles.
[Revendication 10] Procédé selon la revendication 1 , caractérisé en ce que la résine durcissable sous rayonnement ultraviolet est choisie parmi un produit de réaction entre un thiol et un alcène (appelé thiol-ene), un acrylate tel qu’epoxy- acrylate, polyester-acrylate, urethane-acrylate, silicone-acrylate seul ou en mélange de plusieurs d’entre eux. [Claim 10] Process according to claim 1, characterized in that the resin curable under ultraviolet radiation is chosen from a reaction product between a thiol and an alkene (called thiol-ene), an acrylate such as epoxy-acrylate, polyester -acrylate, urethane-acrylate, silicone-acrylate alone or as a mixture of several of them.
[Revendication 11] Procédé selon la revendication 1, caractérisé en ce que préalablement à l’assemblage du vitrage feuilleté, la couche adhésive intercalaire a une rugosité Rz comprise entre 5 et 25, de préférence 10 et 15 pm. [Claim 11] Process according to claim 1, characterized in that prior to the assembly of the laminated glazing, the intermediate adhesive layer has a roughness Rz of between 5 and 25, preferably 10 and 15 μm.
[Revendication 12] Procédé selon la revendication 1, caractérisé en ce que l’encre est directement imprimée sur la couche adhésive intercalaire par impression à jet d’encre à une ou plusieurs passes. [Claim 12] Method according to claim 1, characterized in that the ink is printed directly on the intermediate adhesive layer by single or multi-pass ink-jet printing.
[Revendication 13] Procédé selon la revendication 1, caractérisé en ce que l’encre est directement imprimée sur une feuille de verre bombée par impression à jet d’encre à une ou plusieurs passes. [Claim 13] Method according to claim 1, characterized in that the ink is printed directly on a curved glass sheet by single or multi-pass ink-jet printing.
[Revendication 14] Procédé selon la revendication 13, caractérisé en ce que les têtes d’impression sont montées sur un robot multi-axe et la feuille de verre est fixe. [Claim 14] Method according to claim 13, characterized in that the printheads are mounted on a multi-axis robot and the glass sheet is fixed.
[Revendication 15] Procédé selon la revendication 13, caractérisé en ce que la feuille de verre bombée est maintenue par un robot multi-axe sous les têtes d’impression immobiles. [Claim 15] Method according to claim 13, characterized in that the curved glass sheet is held by a multi-axis robot under the stationary print heads.
[Revendication 16] Procédé selon la revendication 13, caractérisé en ce qu’il y a à la fois un déplacement du substrat et un déplacement des têtes d’impression s’adaptant à la forme du vitrage.
[Claim 16] Method according to claim 13, characterized in that there is both a displacement of the substrate and a displacement of the printing heads adapting to the shape of the glazing.
[Revendication 17] Procédé selon la revendication 1 , caractérisé en ce que le vitrage feuilleté comprend une source de lumière, telle que diode électroluminescente DEL (en anglais light-emitting diode - LED -), l’une desdites deux feuilles de verre ou ladite couche adhésive intercalaire constitue un guide de lumière couplé optiquement à la source de lumière d’une part, au produit de ladite impression digitale qui est apte à extraire la lumière ainsi guidée d’autre part. [Claim 17] Method according to claim 1, characterized in that the laminated glazing comprises a light source, such as a light-emitting diode LED (in English light-emitting diode - LED -), one of said two sheets of glass or said intermediate adhesive layer constitutes a light guide optically coupled to the light source on the one hand, to the product of said digital printing which is able to extract the light thus guided on the other hand.
[Revendication 18] Procédé selon la revendication 9, caractérisé en ce que le vitrage feuilleté comprend une source de lumière, telle que diode électroluminescente DEL (en anglais light-emitting diode - LED -), émettant une lumière de longueur d’onde à laquelle les particules luminescentes sont excitées et ré-émettent un rayonnement lumineux dans le domaine visible.[Claim 18] Method according to claim 9, characterized in that the laminated glazing comprises a light source, such as a light-emitting diode LED (in English light-emitting diode - LED -), emitting a light of wavelength at which the luminescent particles are excited and re-emit light radiation in the visible range.
[Revendication 19] Procédé selon la revendication 1 , caractérisé en ce que le vitrage feuilleté est à basse transmission d’énergie solaire. [Claim 19] Method according to claim 1, characterized in that the laminated glazing is of low solar energy transmission.
[Revendication 20] Procédé selon la revendication 1 , caractérisé en ce que le vitrage feuilleté comprend un film fonctionnel à base de cristaux liquides encapsulés, ou dispersés dans une matrice polymère (en anglais Polymer Dispersed Liquid Crystals - PDLC -), de particules électrophorétiques dispersées dans un milieu, de particules dispersées dans un fluide électrophorétique, ou un film de dispositif de particules en suspension (en anglais Suspended Particle Device - SPD -), ou un système électrochrome. [Claim 20] Method according to claim 1, characterized in that the laminated glazing comprises a functional film based on liquid crystals encapsulated, or dispersed in a polymer matrix (in English Polymer Dispersed Liquid Crystals - PDLC -), dispersed electrophoretic particles in a medium, particles dispersed in an electrophoretic fluid, or a Suspended Particle Device (SPD) film, or an electrochromic system.
[Revendication 21] Procédé selon la revendication 1, caractérisé en ce que celle desdites deux feuilles de verre destinée à être plus à l’extérieur du volume délimité par le vitrage feuilleté est teintée, tandis que l’autre desdites deux feuilles de verre, la feuille intérieure, est claire ou extra-claire. [Claim 21] Method according to claim 1, characterized in that that of the said two sheets of glass intended to be more outside the volume delimited by the laminated glazing is tinted, while the other of the said two sheets of glass, the inner leaf, is clear or extra-clear.
[Revendication 22] Utilisation d’un vitrage feuilleté obtenu par un procédé de fabrication selon l’une des revendications précédentes, comme vitrage de véhicule terrestre, aquatique ou aérien, ou comme vitrage de bâtiment.!
[Claim 22] Use of a laminated glazing obtained by a manufacturing process according to one of the preceding claims, as glazing for land, water or air vehicles, or as glazing for buildings.!
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2107648A FR3125251A1 (en) | 2021-07-15 | 2021-07-15 | Process for manufacturing an illuminating laminated glazing transparent in the extinguished state |
| PCT/FR2022/051170 WO2023285743A1 (en) | 2021-07-15 | 2022-06-16 | Method for producing illuminated laminated glazing, which is transparent in a non-illuminated state |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4370327A1 true EP4370327A1 (en) | 2024-05-22 |
Family
ID=78086456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22744247.2A Pending EP4370327A1 (en) | 2021-07-15 | 2022-06-16 | Method for producing illuminated laminated glazing, which is transparent in a non-illuminated state |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP4370327A1 (en) |
| CN (1) | CN115812037A (en) |
| FR (1) | FR3125251A1 (en) |
| WO (1) | WO2023285743A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12090729B2 (en) | 2022-07-08 | 2024-09-17 | Agc Automotive Americas Co. | Glass assembly including an opaque boundary feature and method of manufacturing thereof |
| US12071365B2 (en) | 2022-07-08 | 2024-08-27 | Agc Automotive Americas Co. | Glass assembly including a performance-enhancing feature and method of manufacturing thereof |
| FR3145918A1 (en) | 2023-02-17 | 2024-08-23 | Saint-Gobain Glass France | Illuminated laminated glass roof OF vehicle, VEHICLE WITH SUCH Illuminated laminated glass roof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080233371A1 (en) * | 2007-03-19 | 2008-09-25 | Richard Allen Hayes | Decorative safety glass |
| FR2964447B1 (en) * | 2010-09-02 | 2012-08-24 | Saint Gobain | LUMINOUS LIGHT EMITTING LAMINATED GLAZING AND MANUFACTURE THEREOF |
| EP2711346A1 (en) * | 2012-09-25 | 2014-03-26 | Falco Technologies BVBA | Multi-layered panel and method for manufacturing a multi-layered panel |
| FR3056147B1 (en) * | 2016-09-21 | 2021-02-12 | Saint Gobain | PRINTING PROCESS ON AN EXTERNAL FACE OF A LAMINATED WINDOW |
-
2021
- 2021-07-15 FR FR2107648A patent/FR3125251A1/en active Pending
-
2022
- 2022-06-16 EP EP22744247.2A patent/EP4370327A1/en active Pending
- 2022-06-16 WO PCT/FR2022/051170 patent/WO2023285743A1/en active Application Filing
- 2022-06-16 CN CN202280004341.9A patent/CN115812037A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023285743A1 (en) | 2023-01-19 |
| FR3125251A1 (en) | 2023-01-20 |
| CN115812037A (en) | 2023-03-17 |
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