Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
  • B42D25/378—Special inks
  • B42D25/387—Special inks absorbing or reflecting ultraviolet light
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/351—Translucent or partly translucent parts, e.g. windows
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
  • B42D25/364—Liquid crystals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
  • B42D25/373—Metallic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
  • B42D25/378—Special inks
  • B42D25/391—Special inks absorbing or reflecting polarised light
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/40—Manufacture
  • B42D25/45—Associating two or more layers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/022—Boron compounds without C-boron linkages
• • 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
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/18—Metal complexes
  • C09K2211/186—Metal complexes of the light metals other than alkali metals and alkaline earth metals, i.e. Be, Al or Mg
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/18—Metal complexes
  • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

Definitions

• the present invention relates to the field of securing and authenticating products, particularly documents.
• It relates more particularly to the securing and authentication of identity, fiduciary or administrative documents or brand labels.
• the support may be of different natures, take different forms and may comprise a polymer or a mixture of polymers. This support may for example consist entirely or partly of a polymeric material.
• documents examples include identity documents such as passports, identity cards, driving licenses or health cards, but also fiduciary documents such as banknotes and checks or administrative documents such as registration certificates.
• the documents can therefore be in the form of paper, booklet or in the form of a card and the information can be there as well printed and / or etched on the surface when it comes to paper or card as in the leaflets when it comes to booklet.
• the documents are secured by security elements that can be classified according to three levels of security according to the means implemented for the detection.
• the level 1 security elements are elements that can be detected by at least one of the five senses or through a contrasting background.
• optical variability devices such as iridescent prints, holograms, optically variable inks, markers, variable laser images (Changeable Laser Image) or laser images. multiples (Multiple Laser Image).
• Level 2 security elements are detectable elements using simple equipment such as an Ultra-Violet lamp, a convex lens or a flash light from a mobile phone. This level includes detectable elements such as micro-prints, fluorescent inks, and fluorescent fibers or platelets.
• level 3 security elements are detectable elements using sophisticated equipment such as a spectrofluorometer or an electron microscope.
• sophisticated equipment such as a spectrofluorometer or an electron microscope.
• nano-engraved pigments, biometric chips and fluorescent markers not detectable to the naked eye (English: taggants).
• the subject of the invention is an optical marking device comprising at least a first layer and a second layer arranged at least partially facing one another, at least one of said first and second layers comprises an optically variable element having a color change between a first color and a second color, said first and second colors being contrasted with respect to a color of the other layer so that when the optically variable element has said first color the first layer is visible and when the optically variable element has said second color, the second layer is visible or when the optically variable element has said first color, the second layer is visible and when the optically variable element has said second color. color, the first layer is visible.
• the device makes it possible to control the authenticity of products, such as documents, in particular identity, fiduciary or administrative documents, but also such as drug packaging (in particular blisters) or luxury goods (identification of Mark).
• the device comprises a pattern provided with said optically variable element.
• the device comprises a substrate on which at least one of said first and second layers rests.
• the two layers are in contact with one another.
• At least one of the two layers is at least partially reflective in the visible light spectrum and / or has shades of gray. According to another characteristic of the invention, at least one of the two layers (2, 3) is at least partially diffusing in the spectrum visible light.
• the optically variable element comprises one or more fluorescent compound (s).
• the optically variable element comprises one or more compound (s) of the 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene family.
• the compound (s) 4-bora-3a, 4a-diaza-s-indacene (s) used in the present invention can be chosen from those of the formula I ci- below:
• R 1 is C 1 to C 6 alkyl, C 5 to C 6 cycloalkyl, C 5 to C 6 heteroalkyl, phenyl, said phenyl group being optionally substituted with one or more groups selected from among
• R 2 and R 2 ' are independently selected from hydrogen and C 1 to C 2 alkyl
• R 3 and R 3 ' are independently selected from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups selected from alkyl C1 to C4, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups selected from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group;
• R 4 and R 4 ' are independently selected from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups selected from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted with one or more groups chosen from aryl, C1-C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by an alkyl group;
• R 5 is C 1 -C 4 alkyl or C 2 -C 4 alkenyl.
• R 6 and R 6 are independently selected from halogen, C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy, C 1 -C 4 alkyl, C 2 -C 4 alkenyl or aryl, said aryl being optionally substituted with one or more selected moieties ) from C1 to C2, hydroxy, R 5 COO-, and halogen.
• the compound (s) of the 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene family are chosen from those of formula II:
• R 1 is C 1 to C 6 alkyl, C 5 to C 6 cycloalkyl, heteroalkyl to
• phenyl said phenyl group being optionally substituted by one or more groups selected (s) from C1 to C2, hydroxy, R 5 COO and halogen;
• R 2 and R 2 are independently selected from hydrogen and C 1 to C 2 alkyl;
• R 3 and R 3 are independently selected from hydrogen and C 1 -C 3 alkyl
• R 4 and R 4 ' are independently selected from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups selected from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted with one or more groups selected from aryl, C1-C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group; ;
• the optically variable element comprises one or more compound (s) of the family of difluoroborane bisketonate (BF2bdks).
• the compound (s) of the family of difluoroborane b-diketonate (BF2bdks) are chosen from those of the formula III:
• L 1 is an unsaturated or non-existent aliphatic chain
• L 2 is an unsaturated or non-existent aliphatic chain
• R 1 is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group
• R 2 is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group
• R 3 is selected from hydrogen, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.
• the device comprises a polymer for incorporating the optically variable element.
• the polymer is chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamides, polyaramids, vinyl ethylene acetate (EVA), polyurethane, thermoplastic polyurethane (TPU), cyanoacrilate, rosin resins, pine resins, photopolymerizable resins or mixtures thereof.
• one of said first and second colors of the layer comprising the optically variable element is the complementary color of the color of the other layer.
• the two layers comprise an optically variable element having a color change, the two optically variable elements being at least partially superimposed and configured so that only the first layer is visible when a first stimulation is applied to the device and only the second layer is visible when a second stimulation is applied to the device.
• the device comprises an element configured to polarize a light passing through said optical marking device.
• At least one of said first and second layers comprises a mixture of an optically variable element having a color change between a first color and a second color and a dye.
• the dye is a fluorophore.
• the invention also relates to an identity document, fiduciary, administrative or a label comprising at least one optical marking device as described above.
• FIG. 1 illustrates a schematic sectional view of an optical marking device according to the present invention
• FIG. 2 to 4 illustrate top views respectively of a first layer, a second layer and a device according to a first embodiment of the invention
• FIG. 5 to 7 illustrate top views respectively of a first layer, a second layer and a device according to a second embodiment of the invention
• FIG. 8 to 1 1 show top views respectively of a first layer, a second layer and a device according to a third embodiment of the invention.
• FIG. 12 to 15 illustrate a top view of a pattern of one of the layers of the device according to a fourth embodiment of the invention.
• the invention relates to an optical marking device for a product, such as a document.
• the optical marking device is referenced 1 in the figures.
• the term document refers to a set formed by a medium and information.
• the support can be of different natures, take different forms and can include a polymer or a mixture of polymers. This support may for example consist entirely or partly of a polymeric material.
• documents examples include identity documents such as passports, identity cards, driving licenses or health cards, but also fiduciary documents such as banknotes and checks or administrative documents such as registration certificates.
• the documents can be in the form of paper, booklet or in the form of a card and the information can be printed and / or engraved on the surface when it comes to paper or card the leaflets when it comes to booklet.
• the device 1 comprises at least a first layer and a second layer, called optical marking layers.
• the device 1 comprises two optical marking layers, referenced 2 and 3.
• the invention is not limited to this configuration and it is possible to provide a multilayer having more than two layers.
• the layers 2 and 3 are exactly superimposed on each other in direct contact with one another, which is particularly advantageous.
• the layers 2 and 3 overlap only partially and / or that they are not in direct contact but instead spaced apart from each other, for example by other layers of the device 1. At least one of the two layers 2, 3 comprises an optically variable element.
• each of the two layers 2, 3 comprises an optically variable element referenced respectively 4, 5.
• the layer 2 comprises an optically variable element referenced 4.
• each of the two layers 2, 3 comprises an optically variable element, referenced respectively 4, 5.
• Each optically variable element has a color change between a first color and a second color. color, as will be described later.
• the optical marking device 1 is configured so that, when the optically variable element has the first color, the first layer is visible and when the optically variable element has said second color, the second layer is visible or when the element optically variable presents the first color, the second layer is visible and when the optically variable element has said second color, the first layer is visible, as will be detailed in connection with each embodiment of the invention.
• At least one of the two layers comprises a pattern at least partially superimposed with the optically variable element.
• the pattern may preferably be a symbol, a drawing, a photograph, or a fixed or variable mention which participates in identifying the product equipped with the device 1.
• the pattern may for example be printed with an ink or varnish or laser engraved, as will be detailed later.
• the device 1 comprises a substrate 11 for supporting the optical marking layers 2, 3.
• the substrate 1 1 is for example a transparent polymer layer.
• the substrate 11 is a layer of polypropylene, polycarbonate, or polyethylene of controlled thickness (for example between 10 ⁇ m to 800 ⁇ m, preferably a thickness ranging from 50 ⁇ m to 600 ⁇ m for polycarbonate, 10 ⁇ m to 600 pm, and preferably From 30 ⁇ m to 150 ⁇ m for polypropylene and from 5 ⁇ m to 500 ⁇ m, preferably 10 ⁇ m for PET) transparent.
• controlled thickness for example between 10 ⁇ m to 800 ⁇ m, preferably a thickness ranging from 50 ⁇ m to 600 ⁇ m for polycarbonate, 10 ⁇ m to 600 pm, and preferably From 30 ⁇ m to 150 ⁇ m for polypropylene and from 5 ⁇ m to 500 ⁇ m, preferably 10 ⁇ m for PET
• optically variable element any physicochemical element which exhibits a color changeover between a first color and a second color as a function of a physicochemical stimulus.
• the physico-chemical stimulus also called stimulation, can be a light irradiation, a change of temperature or pressure or a modification of an observation condition (such as the angle of incidence of the observation of the element)
• the optically variable element comprises a given concentration of an active substance comprising one or more fluorescent compound (s), particularly of the 4,4-difluoro-4-bora-3a family. , 4a-diaza-s-indacene (family called BDPY) or family of difluoroborane b-diketonate (BF2bdks), detailed later.
• fluorescent compound particularly of the 4,4-difluoro-4-bora-3a family.
• 4a-diaza-s-indacene family called BDPY
• BF2bdks difluoroborane b-diketonate
• the invention is not limited to this type of optically variable element.
• thermo-chromium a liquid crystal ink or an optically variable ink of the type known under the name "OVI” (registered trademark by the company "SICPA”) .
• OPI optically variable ink
• the layer 2 or 3 comprising the optically variable element also comprises a polymer in which the compound (s) is (are) incorporated into a polymer, and in particular a polymer matrix constituting the document or the product in question.
• the active substance can be mixed with one or more types of inks.
• the 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene compounds are fluorescent dyes whose first synthesis was published in 1968 (A. Treibs et al., Justus Liebigs Ann.Chem 1968, 718 , 208). Since then, several other syntheses have been published (for example: Chem Eur, J., 2009, 15, 5823, J. Phys Chem, 2009, 113, 1 1844, Chem Eur, J., 201 1, 17, 3069;
• the fluorescent dyes according to the invention are generally stable up to 300 ° C.
• these fluorescent dyes can easily be incorporated into polymer matrices in the molten state and, against all odds, the performances in terms of absorption and fluorescence emission are not altered by the incorporation into a polymer matrix.
• the 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene compounds all have a visible absorption band and the color perceived with the naked eye corresponds to the complementary color of the absorbed color.
• an absorbent compound at 480-490 nm which corresponds to a green / blue color, will appear with the naked eye in orange / red tones.
• the compounds of the 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene family according to the invention all have excitation bands in the Ultra-Violet (UV ) and emission bands in the visible. They can therefore be excited through in particular, a UV lamp emitting between 100 nm and 400 nm and the fluorescence can be detected with the naked eye, which makes it possible to obtain level 2 security elements.
• UV Ultra-Violet
• the emission wavelength can be determined using a spectrofluorometer or low-resolution single-grating fluorimeter (detection by photodiode or photomultiplier tube), which confers on the security elements according to the present invention a level 3 of security.
• the compound (s) 4-bora-3a, 4a-diaza-s-indacene (s) used in the present invention may be chosen from those of formula I below:
• R 1 is C 1 to C 6 alkyl, C 5 to C 6 cycloalkyl, C 5 to C 6 heteroalkyl, phenyl, said phenyl group being optionally substituted by one or more groups selected from C 1 to C 2 alkyl, hydroxy, R 5 COO and halogen;
• R 2 and R 2 ' are independently selected from hydrogen and C 1 to C 2 alkyl
• R 3 and R 3 ' are independently selected from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups selected from alkyl C1 to C4, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups selected from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group;
• R 4 and R 4 ' are independently selected from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups selected from C1 to C3 alky
• R 5 is C 1 -C 4 alkyl or C 2 -C 4 alkenyl.
• R 6 and R 6 are independently selected from halogen, C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy, C 1 -C 4 alkyl, C 2 -C 4 alkenyl or aryl, said aryl being optionally substituted with one or more selected moieties ) from C1 to C2, hydroxy, R 5 COO-, and halogen.
• Preferred compounds of formula I are those in which one or more of R 1 , R 2 , R 2 , R 3 , R 3 , R 4 , R 4 ', R 5, R 6 and R 6' are defined as follows:
• R 1 is phenyl substituted with one or more groups selected from methyl, fluoro, hydroxy, acetyl and methacrylate, preferably from methyl, fluoro, hydroxy and acetyl and more preferably from methyl or fluoro;
• R 2 and R 2 are independently selected from hydrogen and methyl
• R 3 and R 3 ' are independently selected from hydrogen, C 1 -C 3 alkyl, vinyl, aryl, heteroaryl, adamantyl, said vinyl and aryl being optionally substituted by one or more groups selected from phenyl, C 1 -C 2 alkyl said phenyl being optionally substituted by one or more groups selected from C 1 to C 2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably hydrogen, methyl, ethyl, n-propyl, vinyl, aryl, heteroaryl, adamantyl, said vinyl and aryl being optionally substituted with one or more groups selected from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted by one or more groups selected from C1-C 2 alkyl, hydroxy, bromo, nitro, dimethylamine, more preferably, R 3 and R 3 are independently selected from ethyl, n-propyl, methyl, vinyl, phen
• R 4 and R 4 are independently selected from methyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted by one or more groups selected from phenyl, C 1 -C 2 alkyl, said phenyl being optionally substituted by one or more groups chosen from C 1 to C 2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably R 4 and R 4 are independently selected from methyl, vinyl, phenyl, phenantryl, naphthyl, pyrenyl, thiophenyl, benzofuranyl, said vinyl, aryl and naphthyl being optionally substituted with one or more methyl, hydroxy, bromo, nitro and dimethylamino;
• R 5 is methyl or ethenyl.
• R 6 and R 6 are independently selected from fluoro, C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy, C 1 -C 4 alkyl, C 2 -C 4 alkenyl or aryl, said aryl being optionally substituted with one or more selected groups (s); ) from C1 to C2, hydroxy, R 5 COO- and halogen, preferably R6 and R6 'are fluoro.
• the 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene compound (s) used in the present invention may be chosen from those of the present invention.
• R 1 is C 1 to C 6 alkyl, C 5 to C 6 cycloalkyl, C 5 to C 6 heteroalkyl, phenyl, said phenyl group being optionally substituted with one or more groups selected from among
• R 2 and R 2 ' are independently selected from hydrogen and C 1 to C 2 alkyl
• R 3 and R 3 ' are independently selected from hydrogen and C 1 to C 3 alkyl
• R 4 and R 4 ' are independently selected from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups selected from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted with one or more groups selected from aryl, C1-C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group; ;
• R 5 is C 1 -C 4 alkyl or C 2 -C 4 alkenyl.
• Preferred compounds of formula II are those wherein one or more of R 1 , R 2 , R 2 , R 3 , R 3 , R 4 , R 4 and R 5 are defined as follows:
• R 1 is phenyl substituted with one or more groups selected from methyl, fluoro, hydroxy, acetyl and methacrylate, preferably from methyl, fluoro, hydroxy and acetyl and more preferably from methyl or fluoro;
• R 2 and R 2 are independently selected from hydrogen and methyl;
• R 3 and R 3 ' are independently selected from hydrogen, methyl, ethyl, n-propyl and preferably ethyl;
• R 4 and R 4 are independently selected from methyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted by one or more groups selected from phenyl, C 1 -C 2 alkyl, said phenyl being optionally substituted by one or more groups selected from C 1 to C 2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably R 4 and R 4 are independently selected from methyl, vinyl, phenyl, phenanthracenyl, naphthalenyl, pyrenyl, thiphenyl, benzofuranyl, said vinyl, aryl and naphthalenyl being optionally substituted by one or more methyl, hydrocyclo, bromo, nitro and dimethylamino;
• R 5 is methyl or ethenyl.
• halogen refers to fluoro, chloro, bromo or iodo. Preferred halogen groups are fluoro and bromo, fluoro being particularly preferred.
• alkyl refers to a hydrocarbon radical of formula
• alkyl groups are linear or branched C1-C6 alkyl groups.
• alkenyl denotes a linear or branched unsaturated alkyl group comprising one or more carbon-carbon double bonds. Suitable alkenyl groups comprise from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms and more preferably still 2 or 3 carbon atoms.
• Non-limiting examples of alkenyl groups are ethenyl (vinyl), 2-propenyl (allyl), 2-butenyl and 3-butenyl, with ethenyl and 2-propenyl being preferred.
• cycloalkyl (e) refers to a saturated mono-, di- or tri-cyclic hydrocarbon radical having 3 to 12 carbon atoms, especially 5 to 10 carbon atoms. more particularly 6 to 10 carbon atoms.
• Suitable cycloalkyl radicals include, but are not limited to, cyclopentyl, cyclohexyl, norbornyl, adamantyl, especially cyclohexyl and adamantyl.
• Preferred cycloalkyl groups include cyclohexyl, adamant-1-yl and adamant-2-yl.
• aryl refers to a polyunsaturated, aromatic, monocyclic (e.g., phenyl) or polycyclic hydrocarbon radical (e.g., naphthyl, anthracenyl, phenantracenyl, pyrenyl).
• Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenantracenyl, pyrenyl.
• heteroaryl refers to an aromatic ring having from 5 to 12 carbon atoms in which at least one carbon atom is replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen atoms and sulfur may optionally be oxidized and which nitrogen atom may optionally be quaternized, or a ring system containing 2 to 3 fused rings each containing typically 5 or 6 atoms and of which at least one ring is aromatic, at least one carbon atom of the at least one aromatic ring being replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen and sulfur atoms may optionally be oxidized and which nitrogen atom may possibly be quaternized.
• heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyridinyl and benzofuranyl.
• the compounds used in the present invention may be synthesized according to methods known to those skilled in the art. In particular, he may refer to the publication of A. Loudet et al. (Chem Rev. 2007, 107, 4891-4932).
• the optically variable element comprises a fluorescent composition
• a fluorescent composition comprising a polymer matrix incorporating a compound of the family of difluoroborane b-diketonate (BF 2 bdk) chosen from the compounds of formula III below:
• L 1 is an unsaturated or non-existent aliphatic chain
• L 2 is an unsaturated or non-existent aliphatic chain
• R 1 is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group
• R 2 is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group
• R 3 is chosen from hydrogen, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group.
• Preferred difluoroborane b-diketonate family compounds of formula I are those wherein one or more of L 1 , L 2 , R 1 , R 2 , and R 3 are defined as follows: L 1 is an unsaturated aliphatic chain, preferably C 2 to C 8 or non-existent,
• L 2 is an unsaturated, preferably C 2 -C 8 or non-existent aliphatic chain
• R 1 is an unsubstituted or substituted aryl group, preferably an unsubstituted or substituted aryl group with at least one electron donor or electron withdrawing group
• R 2 is an unsubstituted or substituted aryl group, preferably an aryl group unsubstituted or substituted by at least one electron donor or electron withdrawing group, and
• R 3 is chosen from hydrogen and a substituted or unsubstituted aryl group.
• L 2 is an unsaturated C 2 to C 4 aliphatic chain or nonexistent
• R 1 is an aryl group unsubstituted or substituted by at least one group selected from hydroxy, alkoxy, alkyl, aryl, dialkylamino, thioalkoxy, halogen
• R 2 is an aryl group unsubstituted or substituted by at least one group selected from hydroxy, alkoxy , alkyl, aryl, dialkylamino, thioalkoxy, halogen
• R 3 is selected from hydrogen and an unsubstituted aryl group.
• Preferred difluoroborane b-diketonate family compounds of formula I are those wherein one or more of L 1 , L 2 , R 1 , R 2 , and R 3 are defined as follows:
• L 1 is a C2 to C4 unsaturated aliphatic chain or nonexistent
• L 2 is an unsaturated C 2 to C 4 aliphatic chain or nonexistent
• R 1 is an aryl group which is unsubstituted or substituted with at least one group selected from hydroxy, C 1 -C 4 alkoxy, C 1 -C 8 alkyl, aryl, C 1 -C 4 dialkylamino, C 1 -C 4 thioalkoxy, halogen, preferably fluorine
• R 2 is an aryl group which is unsubstituted or substituted by at least one group selected from hydroxy, C 1 -C 4 alkoxy, C 1 -C 8 alkyl, aryl, C 1 -C 4 dialkylamino, C 1 -C 4 thioalkoxy, halogen, preferably fluorine;
• R 1 is an aryl group which is unsubstituted or substituted with at least one group selected from hydroxy, C 1 -C 4 alkoxy, C 1 -C 8 alkyl, aryl,
• R 3 is a hydrogen atom.
• Preferred difluoroborane b-diketonate family compounds of formula I are those wherein one or more of L 1 , L 2 , R 1 , R 2 , and R 3 are defined as follows:
• L 1 is an unsaturated aliphatic chain C2 or nonexistent
• L 2 is an unsaturated C 2 or non-existent aliphatic chain
• R 1 is an aryl group, preferably phenyl, biphenyl or naphthyl, unsubstituted or substituted by at least one group selected from hydroxy, C 1 -C 4 alkoxy, preferably methoxy, alkyl C1 to C8, preferably tert-butyl, aryl, C1 to C4 alkylamino, preferably dimethylamino,
• R 2 is an aryl group, preferably phenyl, biphenyl or naphthyl, unsubstituted or substituted with at least one group selected from hydroxy, (C 1 -C 4) alkoxy, preferably methoxy, (C 1 -C 8) alkyl, preferably tert-butyl, aryl, C1 to C4 alkylamino, preferably dimethylamino, and R 3 is a hydrogen atom.
• Preferred compounds of the family of b-diketonate difluoroborane are those of formula III 2 below:
• R 1 , R 2 and R 3 are as defined in formula I.
• Preferred compounds of the family of b-diketonate difluoroborane are those of formula III 3 below:
• L 1 , R 1 , R 2 and R 3 are as defined in formula III.
• Preferred compounds of the family of difluoroborane b-diketonate are those of formula III 4 below:
• L 2 , R 1 , R 2 and R 3 are as defined in formula III.
• alkyl denotes a hydrocarbon radical of formula CnH2n + 1, linear or branched, in which n is an integer greater than or equal to 1.
• the preferred alkyl groups are linear or branched C1 to C6 alkyl groups.
• alkenyl denotes a linear or branched unsaturated alkyl group comprising one or more carbon-carbon double bonds. Suitable alkenyl groups comprise from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms and more preferably still 2 or 3 carbon atoms. Non-limiting examples of alkenyl groups are ethenyl (vinyl), 2-propenyl (allyl), 2-butenyl and 3-butenyl, with ethenyl and 2-propenyl being preferred.
• cycloalkyl (e) refers to a saturated mono-, di- or tri-cyclic hydrocarbon radical having 3 to 12 carbon atoms, especially 5 to 10 carbon atoms. more particularly 6 to 10 carbon atoms.
• Suitable cycloalkyl radicals include, but are not limited to, cyclopentyl, cyclohexyl, norbornyl, adamantyl, especially cyclohexyl and adamantyl.
• Preferred cycloalkyl groups include cyclohexyl, adamant-1-yl and adamant-2-yl.
• aryl refers to a polyunsaturated, aromatic, monocyclic (e.g., phenyl) or polycyclic hydrocarbon radical (e.g., naphthyl, anthracenyl, phenantracenyl, c).
• Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenantracenyl, pyrenyl.
• heteroaryl refers to an aromatic ring having from 5 to 12 carbon atoms in which at least one carbon atom is replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen atoms and sulfur may optionally be oxidized and which nitrogen atom may optionally be quaternized, or a ring system containing 2 to 3 fused rings each typically containing 5 or 6 atoms and wherein at least one ring is aromatic, at least one carbon atom of the at least one aromatic ring being replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen and sulfur may optionally be oxidized and which nitrogen atom may optionally be quaternized.
• heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyridinyl and benzofuranyl.
• halogen refers to fluoro, chloro, bromo or iodo. Preferred halogen groups are fluoro and bromo, fluoro being particularly preferred.
• alkoxy refers to an alkyl group bonded to an oxygen atom.
• alkenyloxy refers to an alkenyl group bonded to an oxygen atom.
• the layer 2, 3 comprising the optically variable element is deposited on a light background, the intrinsic color (that is to say the color complementary to the color absorbed by the fluorescent compound (s)) is observed. ).
• the physicochemical stimulus consists of placing the device 1 on a light background then dark, or a contrario on a dark background then clear.
• the incorporation can be done in all types of polymer such as polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamides, polyaramids, vinyl ethylene acetate (EVA), polyurethane, thermoplastic polyurethane (TPU), cyanoacrilate, rosin resins, pine resins, photopolymerizable resins or mixtures thereof.
• the incorporation can take place in a polymer chosen from polycarbonate, thermoplastic polyurethane and photopolymerizable resins, preferably from polycarbonate and polycarbonate.
• thermoplastic polyurethane more preferably the polymer is polycarbonate.
• the amount of fluorescent dye to be incorporated is that necessary to detect the absorbance and fluorescence properties.
• the fluorescent dyes according to the invention have the advantage of allowing a detection of the properties even when they are incorporated within the polymer in very small quantities.
• amounts of fluorescent dyes ranging from 0.0001% to 5% by weight relative to the total weight of the polymer are sufficient for detection, preferably amounts ranging from 0.001% to 2% by weight relative to the total weight of the polymer. polymer and even more preferably, amounts ranging from 0.01% to 1%, by weight relative to the total weight of the polymer.
• the quantities of fluorescent dye (s) will be adapted by those skilled in the art depending on the shaping of the polymer and the desired visual effect.
• Each layer comprising an optically variable element is advantageously prepared by techniques known to those skilled in the art, such as, for example, rolling, extrusion, calendering, or calendering extrusion. These techniques will be chosen according to the polymer used. By way of example, if the polymer is a polycarbonate or a thermoplastic polyurethane, the principle of extrusion calendering will be preferred.
• a set of layers in the sense of the present invention may for example be obtained by rolling two or more polymer layers incorporating one or more fluorescent dyes.
• the layer 2, 3 has in particular a thickness ranging from 10 ⁇ m to 800 ⁇ m, preferably a thickness ranging from 50 ⁇ m to 600 ⁇ m, for polycarbonate, 10 ⁇ m up to 600 ⁇ m, and, preferably, from 30 ⁇ m to 150 ⁇ m. for polypropylene and from 5 ⁇ m to 500 ⁇ m, preferably 10 ⁇ m for PET, to which is added an ink thickness of 0.1 ⁇ m up to 200 ⁇ m, preferably from 1 ⁇ m to 100 ⁇ m.
• the layer has a thickness less than 0.100 mm, it is also called film and will find a particular application in the case of flat products, particularly documents and more particularly identity, fiduciary or administrative documents and may be applied to at least a portion of one of the faces of the product.
• the optical marking device 1 comprises a first optical marking layer and a second optical marking layer 3.
• the layer 3 is superimposed on the layer 2.
• Each of the layers 2, 3 comprises an optically variable element 4, 5.
• the first layer 2 comprises a pattern 9 of the shape of a disc.
• the disk 9 integrates the optically variable element 4 of the layer 2.
• the second layer 3 comprises a pattern 10 of the shape of a triangle.
• the triangle 10 integrates the optically variable element 5 of the layer 2.
• Pattern 10 covers pattern 9.
• the patterns 9, 10 are in the center of their respective layer 2, 3.
• the invention is not limited to this configuration and the patterns may instead be eccentric.
• Each of the optically variable elements 4, 5 comprises one or more fluorescent compound (s) as previously described, preferably incorporated into a polymer.
• a first half 2-1 of the first layer 2 comprising a first half 9-1 of the disc 9 is illustrated on a light background.
• a second half 2-2 of the first layer 2 comprising a second half 9-2 of the disc 9 is illustrated on a dark background.
• a first half 3-1 of the second layer 3 comprising a first half 10-1 of the triangle 10 is illustrated on a light background.
• a second half 3-2 of the second layer 3 comprising a second half 10-2 of the triangle 10 is illustrated on a dark background.
• the intrinsic colors of the layers 2, 3 and advantageously their luminous intensity are chosen so that, on a light background, it is the pattern 10 of the second layer 3 which is visible whereas, on a dark background, it is the pattern 9 of the first layer 2 which is visible.
• the first half 9-1 is pink in color (shown in dashed lines), which, as already indicated, corresponds to the intrinsic color of layer 2.
• the second half 9-2 is green (represented by hatching), which, as already indicated, corresponds to the fluorescence color of layer 2.
• the first half 10-1 is blue (shown in parallel dotted lines), which, as already indicated, corresponds to the intrinsic color of the layer 3.
• the second half 10-2 is red (represented in parallel dotted lines, in a direction different from that of the half 10-1), which, as already indicated, corresponds to the fluorescence color of the layer 3.
• a first half 1 -1 of the device 1 is placed on the light background while a second half 1 -2 of the device 1 is placed on the dark background.
• the optical effect obtained is enabled by the concentration in the second layer 3 of the active substance of the ink or varnish used to make the pattern and chosen to minimize its visibility on a light background, as well as by the choice of the active substance in the pattern of the first layer 2, the fluorescence color of which is contrasted with that of the layer 3, advantageously being complementary in color (in subtractive synthesis) to that of the second layer 3.
• the intrinsic colors of the first layer layer 2 and the second layer layer 3 are chosen so that only layer 2 is visible on a white background.
• Fluorescence colors are chosen so that only layer 3 is visible (dark background).
• the fluorescence color of the first layer is complementary to that of the second layer, as already noted.
• the layer 3 filters all the wavelengths of radiation below its color.
• the optical marking device 1 comprises a first optical marking layer 2 and a second optical marking layer 3.
• the layer 3 is superimposed on the layer 2. Only the first layer 2 comprises an optically variable element 4.
• the first layer 2 is identical to the first layer 2 detailed in relation to the first variant embodiment.
• the second layer 3 is devoid of optically variable element.
• the second layer 3 has a color, obtained by all techniques known to those skilled in the art (dyeing in the mass, varnishing for example).
• the color is for example red.
• a first half 1 -1 of the device 1 is placed on the bright background while a second half 1 -2 of the device 1 is placed on the dark background.
• the first layer 2 is visible and we observe the green 9-2 semicircle on dark red background.
• the passage of the white background or dark background is in this case the physical stimulus for the color change of the marking device 1.
• the optical effect obtained is enabled by the concentration of the active substance of the ink or varnish used to make the pattern 9 of the first layer 2 chosen to minimize its visibility on a light background and by the choice of color of the second layer 3 whose color is contrasted with the fluorescence color, and preferably of a color corresponding to the complementary color of the fluorescence used in the first layer 2.
• the marking device 1 comprises a first layer 2 and a second layer 3.
• the second layer 3 is identical to the second layer 3 detailed in relation to the first embodiment.
• the first layer 2 comprises, in a manner similar to the first variant embodiment, a pattern 9 comprising an optically variable element.
• the first layer 2 or the second layer 3 is at least partially reflective in the visible light spectrum.
• the layer 2 can be a layer of polymer (polycarbonate, polypropylene, PET) metallized or a metal layer directly.
• Layer 2 may also include micro-mirrors.
• the device 1 also comprises the substrate 1 1 which is metallized, or the layer 2 is coated with an ink layer having metallic reflections.
• the stimulus is the observation angle tilt of the device 1, as a function of the light environment (that is to say, clear or dark environment).
• the light environment that is to say, clear or dark environment.
• the second layer 3 has the intrinsic color.
• the second layer 3 has the fluorescence color.
• the first layer 2 comprises shades of gray.
• the optical effect obtained is enabled by the concentration of active substance to achieve the pattern of the second layer 3 to minimize its visibility under normal observation, by the choice of the color of the first layer 2 which is contrasted with the complementary color of the fluorescence of the active substance of the second layer 3, and preferably the complementary color, as well as the tilt angle according to a gray level of the reflecting surface (the more the surface will be reflective (low level of gray), the smaller the tilt angle and vice versa).
• the optical effect of color switching can be obtained when at least one of the layers 2, 3 has optical diffusion properties.
• the layer 2, 3 having diffusing properties is for example matt.
• the optical marking device 1 comprises a polarizing film, not shown.
• the polarizing film may be formed by the layer 2 or the substrate 1 1 for example.
• the substrate 1 1 is not necessarily transparent, unlike the variants described above.
• the polarization of the light makes it possible to view one of the layers 2 and then the other layer 3.
• each of the layers incorporating an optically variable element or at least one of the layers integrating an element optically variable may comprise a dye mixed with the optically variable element.
• coloring means any molecule capable of tinting, regardless of its size, its preparation and the conditions under which the molecule acquires the ability to tint.
• the dye may be solubilized or dispersed (such as a pigment for example).
• the dye may be goniochromic, photochromic, thermochromic, or even piezochrome.
• the round unit 9 comprises a mixture of the active substance based on a "4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene compound (s)" of the BDPY family, and dye.
• the dye has a minimum of transparency.
• the dye does not exhibit fluorescence properties and has the effect of modifying the intrinsic color (on a bright background) without changing the fluorescence color.
• This effect is obtained by adding the color of the dye and the intrinsic color of the active substance.
• the pattern 9 with the active and dye-free substance has an intrinsic blue color and a red fluorescence color
• the pattern 9 comprising mixing a yellow dye and the active substance has a green intrinsic color , the fluorescence color remaining red.
• Figure 12 is illustrated the pattern 9 with the active substance and without dye on a light background: it is the blue color that appears (hatched).
• Figure 13 is illustrated the pattern 9 with the active substance and without dye on dark background: it is the red color that appears (in opposite hatches).
• Figure 14 is illustrated the pattern 9 comprising the mixture of the active substance and yellow dye on a light background: it is the green color that appears (in pea).
• Figure 15 is illustrated the pattern 9 comprising the mixture of the active substance and the yellow dye on a dark background: it is the red color that appears (hatches identical to those of Figure 13).
• addition of the colors (on a bright background) of the intrinsic color and color of the dye can completely obscure the intrinsic color.
• the pattern 9 with the active and dye-free substance has an intrinsic pink color and a red fluorescence color
• the pattern 9 comprising mixing a blue dye and the active substance has an intrinsic blue color , the fluorescence color remaining red. This occurs when the color of the added non-fluorescent dye covers, at least with the naked eye, the intrinsic color of the active substance.
• the dye is a fluorophore that does not belong to the BDPY family and has fluorescence excitation and emission bands different from those of the active substance. Then, it is possible to modify the color emitted under ultraviolet radiation by the pattern comprising the mixture of the active substance and the fluorescent dye.
• the dark background color is not modified since the addition of the fluorescence of the added dye is visible only under UV. Under UV illumination, there are phenomena of mixing the fluorescence color of the active substance BDPY and the color of the added fluorophore dye.
• the fluorophore dye makes it possible to modify the intrinsic color as well as the fluorescence color. This is possible in the case of a mixture of several compounds of the BDPY family
• the invention also relates to an identity document, fiduciary, administrative or a label, comprising at least one optical marking device 1.
• the document may be an identity card, a passport, a license, a certificate, a diploma, a checkbook, a register, a stamp, a seal, a visa, a bank card, a bank note.
• the reason may be a national symbol, or a company or national symbol, a logo associated with a trademark, or a fixed or variable mention, or a nominal value.
• the marking device 1 occupies all or part of the document. Advantages
• the marking device has the advantage of effectively securing a document using, in particular, physico-chemical stimuli, such as a clear-bottom passage and then dark background, or change of viewing angle.
• Any agent will be able to carry out a simple and fast verification of the document, since it is not necessary that it is provided with expensive accessory and that a single gesture is enough for the verification.
• the family of fluorescent 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene compounds and / or the family of difluoroborane b-diketonate (BF2bdks) provide a simple process for producing the marking device 1 since they are easily incorporated in a polymer, and have good thermal stability, which also makes possible all the steps necessary for the manufacture of the document in which one or more marking device (s) 1 are integrated. It is added that the embodiments described are combinable to the extent that they are not incompatible.

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