Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/06—Veined printings; Fluorescent printings; Stereoscopic images; Imitated patterns, e.g. tissues, textiles
• • 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
  • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
  • B42D25/23—Identity cards
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/62—Benzothiazoles
  • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
  • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0025—Crystal modifications; Special X-ray patterns
  • C09B67/003—Crystal modifications; Special X-ray patterns of diketopyrrolopyrrole
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
  • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B69/00—Dyes not provided for by a single group of this subclass
  • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
  • C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
• • 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
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • 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
• • 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
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
• • 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
• • 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, e.g. electroluminescent, chemiluminescent materials
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
• • 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, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials 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
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1007—Non-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B

Definitions

• the present invention relates to the field of securing and authenticating products. More particularly, the invention relates to a fluorescent composition for securing and authenticating products such as identity, fiduciary and administrative documents.
• various companies provide visual authentication solutions, for example using holograms or laser engravings, which can allow the insertion of information about a plastic card body such as an identity card, health card or driver's license.
• Document EP0708935 A1 describes for example a set of holographic protection layers.
• This assembly consists of a support film having at least one layer formed by a protective varnish, a reflective or transparent layer bearing a diffracting microstructure, and finally, an adhesive layer.
• a protective varnish a protective varnish
• a reflective or transparent layer bearing a diffracting microstructure
• an adhesive layer a layer formed by a protective varnish
• a reflective or transparent layer bearing a diffracting microstructure a reflective or transparent layer bearing a diffracting microstructure
• an adhesive layer Once the set of layers has been transferred to a document, the latter is secured.
• this system was then improved by means of perforations making it more difficult the separation of the different layers.
• the set of layers, even perforated consists of a multitude of parts that it is necessary to assemble which represents additional constraints in terms of time and cost.
• Document FR 16 50164 of which the Applicant is the holder, describes the use of a compound of the family of 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacenes for the preparation of an element for securing a product, in particular a document, said securing element comprising a polymer and the compound being incorporated into said polymer.
• the use of the compounds described only allows fluorescence emissions to be obtained within the range from 500 nm to infrared, and thus does not cover the entire range of the visible spectrum.
• Application US 2008/0081913 A1 describes compounds of benzoxazole and benzothiazole type exhibiting fluorescent properties and having utility in particular as authentication compounds in data storage media and data storage substrates.
• level 1 security elements are elements that can be detected by at least one of the five senses or through a contrasting background.
• 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 ("Optical Variable Ink”), markers, variable laser images ("Changeable Laser Image”) or again the multiple laser images (“Multiple Laser Image”).
• the level 2 security elements are elements that can be detected by means of simple equipment such as an Ultra-Violet lamp, a convex lens or even a flash light from a mobile phone. Detectable elements such as micro-prints, fluorescent inks, as well as fluorescent fibers or plates are found in this level.
• the level 3 security elements are elements detectable by means of sophisticated equipment such as for example a spectrofluorimeter or an electron microscope. In this category are found in particular nano-engraved pigments, biometric chips as well as fluorescent markers not detectable with the naked eye (in English: taggants).
• a secure product incorporates several security elements of different levels.
• the present relates to a fluorescent composition
• X is selected from NH, O and S;
• Z is selected from OH, NHR 5 and N (R 5 ) 2;
• R is selected from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH 2 , -NHR 4 , -N (R 4 ) 2 , -N + (R 4 ) 3 , -NHCOR 4 , -CHO, - C (0) 0H, -C (0) 0R 4 , -CFs, C1-C6-alkoxy, aryloxy, -SH, -SOsH, -SR 4 ;
• R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR 4 , -N (R 4 ) 2, -N + (R 4 ) 3, -NHCOR 4 , -CHO, -C (0) 0H, -C (0) 0R 4 , -CFs, C1 -C6-alkoxy, aryloxy, -SH, -SOsH, - SR 4 ;
• R 4 is selected from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;
• R 5 is chosen from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1 -C6-alkyloxycarbonyl, C1 -C6-alkylaminocarbonyl, C1 -C6-alkylaminothionyl, di-C1-C6-alkylaminothionyl , arylaminocarbonyl, arylaminothionyl, arylsulfonyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted with C1-C6-alkyl, C1- C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C
• a method for securing a product comprising a step of preparing a fluorescent composition as defined above and a step of securing by applying said fluorescent composition to at least one part of the product to be secured.
• R 1 , and R 2 and R 3 are independently selected from hydrogen, C1 -C6-alkyl, C3- C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR 4 , -N (R 4 ) 2, - N + (R 4 ) 3 , -NHCOR 4 , -CHO, -C (0) 0H, -C (0) 0R 4 , -CFS, C1 -C6-alkoxy, aryloxy, -SH, -SOsH , -SR 4 ; R 4 is selected from C1 -C6-alkyl, C1 -C6-cycloalkyl and aryl;
• R 5 is chosen from C1-C6-alkyl, hydroxy-C1 -C6-alkyl, C1 -C6-alkyloxycarbonyl, di-C1 -C6-alkylaminothionyl, C1 -C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5 , 6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1 -C6-alkyl, C1 -C6-alkoxy, trifluoro-C1 -C6-alkyl, C1 -C6-alkylamino or hydroxy-C1 -C6- alkylamino; and with the condition that:
• R 1 , R 2 and R 3 are not all three hydrogen when R 5 is cinnamoyl, or benzoyl optionally substituted with methyl, methoxy, chloro or trifluoromethyl; R 1 is not methyl when R 5 is benzoyl;
• R 2 is not methyl when R 5 is benzoyl
• R 3 is not methyl, methoxy or chloro when R 5 is benzoyl.
• a first object of the invention relates to a fluorescent composition
• a fluorescent composition comprising a polymer matrix incorporating a compound of formula I:
• X is selected from NH, O and S; preferably X is S;
• Z is selected from OH, NHR 5 and N (R 5 ) 2; preferably Z is NHR 5 or N (R 5 ) 2; more preferably Z is NHR 5 ;
• R is chosen from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, C (0) 0H, -C (0) 0R 4 , -CF3, aryloxy, -SH, -SO3H, -SR 4 ; preferably R is chosen from hydrogen, C1-C4-alkyl, halogen, -NO2, -NH2, -NHR 4 , -N (R 4 ) 2, C1-C4-alkoxy; more preferably R is chosen from hydrogen, C1-C2-alkyl, halogen, C1-C4-alkoxy; more preferably, R is hydrogen;
• R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR 4 , -N (R 4 ) 2, -N + (R 4 ) 3, -NHCOR 4 , -CHO, -C (0) 0H, -C (0) 0R 4 , -CFs, C1-C6-alkoxy, aryloxy, -SH, -SOsH, - SR 4 ; preferably R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; more preferably R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably
• R 4 is selected from alkyl, cycloalkyl and aryl; preferably R 4 is chosen from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;
• R 5 is chosen from C1 -C6-alkyl, hydroxy-C1 -C6-alkyl, halogen, aryl, acyl, C1 -C6-alkyloxycarbonyl, C1 -C6-alkylaminocarbonyl, C1 -C6-alkylaminothionyl, di-C1 -C6-alkylaminothionyl , arylaminocarbonyl, arylaminothionyl, arylsulfonyl, C1 -C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1 -C6-alkyl, C1 - C6-alkoxy, trifluoro-C1 -C6-alkyl, C1 -C6-alky
• the polymer matrix of the fluorescent composition according to the invention can be obtained from an amorphous or semi-crystalline polymer chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride), polyamides, polyaramides, vinyl ethylene acetate, polyurethane, thermoplastic polyurethane, cyanoacrylate, rosin resins, pine resins, light-curing resins, acrylic and theirs mixtures.
• an amorphous or semi-crystalline polymer chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride), polyamides, polyaramides, vinyl ethylene acetate, polyurethane, thermoplastic polyurethane, cyanoacrylate, rosin resins, pine resins, light-curing resins, acrylic and theirs mixtures.
• the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polyethylene, thermoplastic polyurethane, acrylic and photopolymerizable resins and their mixtures, and more preferably polymer matrix is a polycarbonate or polypropylene matrix.
• the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride) , polyamides, polyaramides, polyurethane, thermoplastic polyurethane (TPU), cyanoacrylate, rosin resins, pine resins, light-curing resins, acrylic and their mixtures.
• the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, thermoplastic polyurethane, photopolymerizable resins, acrylic, and mixtures thereof. More particularly, the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polyethylene, polypropylene, polyethylene terephthalate and their mixtures. More particularly still, the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polypropylene, polyethylene terephthalate and mixtures thereof. Still more particularly, the polymer matrix of the fluorescent composition can be obtained from polycarbonate or polyethylene terephthalate.
• the polymer matrix is a semi-crystalline polymer matrix.
• the polymer matrix does not contain an anti-UV additive in order thus to allow optimum maintenance of the fluorescence properties.
• polymer matrix incorporating a compound of formula I is meant within the meaning of the present invention that the compound of formula I is intimately integrated into the polymer matrix so as to form a mixture.
• the compound of formula I is intimately integrated into the polymer matrix so as to form a homogeneous mixture exhibiting no dispersion.
• the integration of the compound into the polymer matrix can for example be carried out hot. In this scenario, the polymer matrix is heated to its melting point, then the compound of formula I is added to the melt before the whole is mixed.
• the integration of the compound into the polymer matrix can be carried out by melt, extrusion, calendering extrusion, extrusion spinning, plastic injection or dyeing.
• the inventors have found that the compounds of formula I according to the invention can be incorporated into polymer matrices without altering either the performance of the matrix, or especially that of the incorporated compounds.
• the compounds incorporated into the polymer matrix of the fluorescent composition are the compounds of formula I in which X is S.
• the compounds incorporated into the polymer matrix of the fluorescent composition are those of formula la:
• Preferred compounds of formula la are those in which R, R 1 , R 2 , R 3 and / or Z are defined as follows: Z is NHR 5 or N (R 5 ) 2 ;
• R is selected from hydrogen, C1-C4-alkyl, halogen, -NO2 and C1-C4-alkoxy; preferably R is hydrogen;
• R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; preferably R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, Cl, F and -NO2; even more preferably R 1 , R 2 and R 3 are independently chosen from hydrogen, methyl, methoxy, Cl, F and - NO2; R 5 is chosen from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1 -C6-alkyloxycarbonyl, di-C1 -C6-alkylaminothionyl, arylaminocarbonyl,
• R 5 is chosen from benzoyl, 3,5-bis (trifluomethyl) benzoyl, 4- (butylamino) -2, 3,5,6-tetrafluorobenzoyl and cinnamoyl.
• the compounds incorporated into the polymer matrix of the fluorescent composition are those of formula Ib: [0032] [Chem. 4] wherein R, R 1 , R 2 , R 3 and R 5 are as defined in formula I.
• R is chosen from hydrogen, C1-C4-alkyl, halogen, -NO2 and C1-C4-alkoxy; preferably R is hydrogen;
• R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; preferably R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably R 1 , R 2 and R 3 are independently selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, Cl, F and -NO2; even more preferably R 1 , R 2 and R 3 are independently chosen from hydrogen, methyl, methoxy, Cl, F and - NO2;
• R 5 is selected from cinnamoyl, benzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted with C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; preferably R 5 is chosen from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, trifluoro-C1-C4-alkyl, C1-C4-alkylamino or hydroxy-C1-C4-alkylamino; more preferably R 5 is chosen from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted by methyl, methoxy, trifluor
• the compounds incorporated into the polymer matrix of the fluorescent composition are those of formula le:
• the compounds incorporated into the polymer matrix of the fluorescent composition are the compounds of formula I wherein Z is NHR 5 or N (R 5 ) 2, preferably Z is NHR 5 . In one embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are the compounds of formula I in which R is hydrogen.
• Compounds of formula I incorporated into the polymer matrix of the fluorescent composition more particularly preferred of the invention are the compounds 3, 4, 5, 8, 9, 10, 11, 12, 13, 14, 16, 27, 29 and 35 listed in Table 1 above.
• the polymer matrix incorporates an amount of compound of formula I necessary for the detection of the properties of absorbances and fluorescences.
• the compounds of formula I according to the invention have the advantage of allowing detection of said properties, even when they are incorporated in small amounts within the polymer matrix.
• the amounts of compounds of formula I ranging from 0.005% to 20% by weight relative to the total weight of the polymer matrix are sufficient for detection, preferably amounts ranging from 0.01% to 15% by weight relative to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix.
• the amount of compound of formula I incorporated into the polymer matrix of the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10%, between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.
• the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above.
• the fluorescent composition consists essentially of a polymer matrix integrating a compound of formula I as defined above.
• the expression “essentially constituted” is understood to mean, within the meaning of the present invention, that the composition fluorescent consists of more than 96%, 97%, 98%, or even more than 99% of a polymer matrix integrating a compound of formula I.
• the fluorescent composition further comprises a second compound of formula I as defined above, or one of its sub-formulas la, Ib and le.
• the amounts of second compound of formula I are from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably amounts ranging from 0.01% to 15% by weight relative to to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix.
• the amount of the second compound of formula I incorporated into the polymer matrix of the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10% , between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.
• the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above and a second compound of formula I as defined above.
• the fluorescent composition also comprises a difracting network or a reasoning network.
• the fluorescent composition according to the invention comprising a polymer matrix in which are integrated two different compounds of formula I, or one of its sub-formulas la, Ib and le, as defined above allows to obtain fluorescent compositions with particularly advantageous properties.
• the fluorescent composition also comprises a compounds of the family of 4-bora-3a, 4a-diaza-s-indacene, also called "BODIPY", said BODIPY being incorporated into the matrix polymer.
• BODIPY can be compounds of formula III below:
• R 1 is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted by one or more groups chosen from C1 to C2 alkyl, hydroxy, R 5 COO - and halogen; preferably R 1 is phenyl optionally substituted with one or more groups chosen from C1 to C2 alkyl; more preferably R 1 is phenyl substituted with one or more groups chosen from C1 to C2 alkyl; more preferably R 1 is phenyl substituted with several groups chosen from C1 to C2 alkyl; more preferably R 1 is phenyl substituted with several methyl groups; more preferably R 1 is 2,4,6-trimethylphenyl;
• R 2 and R 2 ' are independently selected from hydrogen and C1 to C2 alkyl; preferably R 2 and R 2 ' are hydrogen;
• 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 chosen from C1 to C4 alkyl, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to alkyl C2, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted with a C1 to C2 alkyl group; preferably R 3 and R 3 ' are hydrogen;
• R 4 and R 4 ' are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups chosen from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group ; preferably R 4 and R 4 ' are aryl optionally substituted with one or more groups chosen from C1 to C3 alkyl; more preferably R 4 and R 4 ' are phenyl optionally substituted with one or more groups chosen from C1 to C2 alkyl; more preferably R 4 and R 4 ' are phenyl substituted with one or more groups chosen
• R 5 is C1 to C4 alkyl or C2 to C4 alkenyl.
• R 6 and R 6 ' are independently selected from halogens, C1 to C4 alkoxy, C2 to C4 alkenyloxy, C1 to C4 alkyl, C2 to C4 alkenyl, CN or aryl, said aryl being optionally substituted with one or more groups selected from C1 to C2 alkyl, hydroxy, R 5 COO- and halogen; preferably R 6 and R 6 ' are independently chosen from halogens; more preferably R 6 and R 6 ' are fluorine atoms.
• the amounts of compound of formula III are from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably amounts ranging from 0.01% to 15% by weight relative to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix.
• the amount of compound of formula III incorporated into the polymer matrix of the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10%, between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.
• the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above and a second compound of formula III as defined above.
• the fluorescent composition also comprises a difracting network or a reasoning network.
• the fluorescent composition according to this second variant comprising a polymer matrix in which are integrated a compound of formula I as defined above and a compound of formula III as defined above makes it possible to obtain fluorescent compositions with particularly advantageous properties. .
• the fluorescent composition thus obtained exhibits a color on a white background and a color visible, for example on a black background and under flash light from a mobile telephone obtained from the compound of formula III.
• the composition Under UV irradiation (level 2), the composition exhibits a third color resulting from the mixture of the emissions of the compounds of formula I and of formula III.
• the fluorescent composition further comprises a fluorescent compound whose response under UV radiation is controlled, which absorbs ultraviolet electromagnetic radiation, in particular between 300 and 400 nm, of wavelength and then re-emits this energy by fluorescence in the visible range, and in particular between 400 and 500 nm.
• the amounts of fluorescent compound whose response under UV radiation is controlled are from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably amounts ranging from 0.01% to 15 % by weight relative to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix.
• the amount of fluorescent compound whose response under UV radiation is controlled in the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10% , between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.
• the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above and a fluorescent compound whose response under UV radiation is controlled.
• the fluorescent composition also comprises a difracting network or a reasoning network.
• the fluorescent composition according to this second variant comprising a polymer matrix in which are integrated a compound of formula I as defined above and a fluorescent compound whose response under UV radiation is controlled makes it possible to obtain fluorescent compositions with particularly advantageous properties. .
• a second object of the invention relates to the use of a fluorescent composition according to the invention for securing a product.
• a product within the meaning of the present invention can be any type of product suitable for receiving said fluorescent composition.
• the product can thus be a solid or a liquid. It may for example be plastic objects such as parts or packaging, luxury products such as leather goods, cosmetics, paintings or even documents. Preferably, the products are documents.
• the term document refers in particular to an assembly formed by a support and an item of information.
• the support can be of different natures, take different forms, and can optionally comprise a polymer or a mixture of polymers. This support can for example be made entirely or in part of a polymer material.
• identity documents such as passports, identity cards, driving licenses or health cards, but also fiduciary documents such as banknotes and checks, or even administrative documents such as registration certificates.
• the documents can therefore be in the form of paper, a booklet or even a map, and the information can also be printed and / or engraved on it.
• the fluorescent composition is integrated into the product or into the product to be secured at any time during its design.
• the fluorescent composition can equally well be used for securing the product during its manufacture, as well as being applied or integrated subsequently into the latter.
• the fluorescent composition can be applied a posteriori to all or part of the document. This point is developed further in the description.
• the products are secured by the use of a fluorescent composition
• a fluorescent composition comprising a polymer matrix incorporating a compound of formula I described above, a mixture of two compounds of formula I, or a mixture of a compound of formula I and of a compound of formula III, and can be authenticated by virtue of the properties and effects conferred by the fluorescent composition.
• the secure products in accordance with the invention can be authenticated by virtue of the unique combination of the absorbed wavelength and of the specific fluorescence of the fluorescent composition.
• Authentication within the meaning of the present invention is understood to mean the verification of the authenticity of a product by the detection of the fluorescent composition or of the security means incorporated therein.
• the compounds of formula III contained in the fluorescent composition may exhibit an absorption band in the visible range. and the color perceived with the naked eye will correspond to the color complementary to the color absorbed. For example, a compound absorbing around 500-520 nm, which corresponds to a green / blue color, will appear to the naked eye in orange / red tones. This property thus makes it possible to obtain level 1 security.
• the compounds of formula I according to the invention all have excitation bands in Ultra-Violet (UV). They can therefore be excited by means in particular of a UV or LED lamp emitting between 100 nm and 400 nm, which makes it possible to obtain level 2 security. This property makes it possible to obtain an activation / deactivation effect (on / off) which therefore corresponds to the visualization of a color change following a stimulation of the fluorescence of the fluorescent composition, in particular by a light source of the LED or UV type.
• UV Ultra-Violet
• the emission wavelength can be determined using a low resolution spectrofluorimeter or fluorimeter with a single grating (detection by photodiode or photomultiplier tube), which gives security elements according to the present invention a level 3 security.
• the products and in particular the secure documents according to the present invention will be, thanks to the association of absorption and fluorescence properties, detectable on levels 2 and 3 in the case of the use of a composition. comprising a compound of formula I or a mixture of two compounds of formula I, and on the 3 levels of security in the case of the use of a composition comprising a compound of formula I and a compound of formula III.
• the fluorescent composition according to the present invention can be in several forms which are adapted by a person skilled in the art depending on the product to be secured.
• the fluorescent composition may be in the form of a layer, a set of layers, or a film.
• the fluorescent composition is used in the form of a layer or of a set of layers prepared by techniques known to those skilled in the art such as, for example, lamination, extrusion, calendering, or extrusion calendering. These techniques will be chosen according to the polymer matrix used.
• the matrix is made of polycarbonate or thermoplastic polyurethane, shaping by calendering extrusion is preferred.
• the matrix is made of polypropylene, the principle of inflation extrusion is preferred, in particular the principle of inflation extrusion with bi-stretching.
• a set of layers within the meaning of the present invention can for example be obtained by laminating two or more layers of polymer matrix each incorporating one or more fluorescent compositions.
• a layer or set of layers finds a particularly advantageous application in the securing of documents, and more particularly identity, fiduciary or administrative documents.
• the layer or the set of layers is in the form of a card. Examples of cards are in particular professional cards, bank cards, or any other type of polymer matrix card.
• the fluorescent composition according to the invention constitutes the support of the document as such.
• the cards could for example be obtained by laminating several layers of polymer, at least one of which is the fluorescent composition according to the present invention.
• the layer or the set of layers is transparent which makes it possible to obtain, in addition to the above effects described, the following effects:
• this effect corresponds to the observation of a color complementary to the absorbed color which is different on the edges of the layer or of the set of layers, from that observed on the faces. Under UV irradiation, this constitutes level 2 safety.
• the layer or the set of layers is transparent.
• switch-color this effect corresponds to a change of color during the superposition of the layer or the whole of layers on a contrasting background (dark background type, in particular black, or light background, in particular white. We can thus observe the color complementary to the color absorbed on a light background and the fluorescence color on a dark background. This constitutes a level 1 security.
• this effect corresponds to the observation of a color complementary to the absorbed color which is different on the edges of the layer or of the set of layers, from that observed on the faces. This constitutes level 1 security.
• this effect linked to the presence of the compound of formula III, corresponds, when the fluorescence is stimulated by an LED or UV light and observed on a light background, in particular white, to the visualization both of the fluorescence color at the level of the layer and of the projection of the color complementary to the color absorbed on the light background. This constitutes level 2 security.
• a layer has in particular a thickness ranging from 0.050 mm to 0.800 mm, preferably a thickness ranging from 0.200 mm to 0.600 mm, such as for example a thickness of approximately 0.400 mm.
• a thickness ranging from 0.200 mm to 0.600 mm such as for example a thickness of approximately 0.400 mm.
• the layer has a thickness of less than 0.100 mm, it is also called a film.
• the fluorescent composition used for securing a product comprises only a polymer matrix integrating a compound of formula I as defined above.
• the fluorescent composition used for securing a product essentially consists of a polymer matrix integrating a compound of formula I as defined above.
• the expression “essentially constituted” is understood to mean that the fluorescent composition consists of more than 96%, 97%, 98%, or even more than 99% of a polymer matrix incorporating a polymer matrix. compound of formula I.
• the fluorescent composition used for securing a product consists of approximately 50% of a polymer matrix integrating a compound of formula I as defined above.
• the fluorescent composition used for securing a product comprises only a polymer matrix integrating a mixture of two different compounds of formula I as defined above.
• the fluorescent composition thus obtained exhibits a color resulting from the mixture of the colors of each of the two compounds of formula I and which is visible only under UV irradiation (level 2).
• the fluorescent composition used for securing a product comprises only a polymer matrix integrating a compound of formula I and a compound of formula III as defined above.
• the fluorescent composition thus obtained has three colors, a first which is visible on a white background (level 1), a second which is visible for example on a black background or under flash light from a mobile phone (level 1) , and a third under UV irradiation (level 2).
• composition comprising a mixture of compound of formula I and of a compound of formula III makes it possible to complexify level 2.
• the fluorescent composition is used in the form of a fluorescent ink.
• the fluorescent ink is an ink suitable for printing, in particular for screen printing, offset printing, flexography, heliography, jet printing. ink, digital printing, intaglio printing and 3D printing, preferably for offset printing, and inkjet printing.
• the inventors have advantageously observed that the fluorescent inks according to the invention could be used in printing without causing clogging of the print heads.
• the fluorescent composition is used in the form of an aqueous ink.
• the fluorescent composition is used in the form of a fluorescent varnish.
• the fluorescent composition is used in the form of a film, that is to say a layer having a thickness less than 0.100 mm, in particular ranging from 0.050 mm to 0.100 mm, which is used to laminate both sides of a document, including an identity, fiduciary or administrative document.
• a film is applied only to one of the two sides of a document, in particular of an identity document.
• such a film is applied only to a part of one of the two sides of a document, in particular of an identity document.
• such a film is applied only to a part of each of the two sides of a document, in particular of an identity document.
• the fluorescent composition is put in the form of a fiber.
• This shaping can be done by the techniques conventionally used to obtain fibers, said fibers can equally well be woven fibers or non-woven fibers.
• the fibers are preferably obtained by the melt spinning technique, via an extrusion-spinning process.
• the manufacture of fibers by the melt spinning method involves first melting the mixture of polymer and fluorescent compound in an extruder. The molten material is then sent under pressure through a die made up of a multitude of heads. On leaving the die, the filaments are cooled by air, stretched then wound on a support. Generally, a size product can be applied to the lower part of the spinning stack.
• the compound of formula I, the mixture of two compounds of formula I or the mixture of a compound of formula I and of a compound of formula III can be integrated into a polymer matrix without having recourse to extrusion, in particular by wire impregnation.
• the shape of the fluorescent fiber obtained according to the extrusion-spinning processes can in particular be determined by the shape of the heads of the die.
• the fiber can in particular have a cylindrical, three-lobed, octalobed, hollow or multiple hollow shape.
• Changing the shape of the fibers can be beneficial in that it allows visual effects to be changed on a macroscopic scale. Indeed, the discontinuity of a section or the refractive index of light within the fiber can modify the transmission of light and therefore, the effects observed at the macroscopic scale.
• fluorescent compositions are used to secure the same product, the fluorescent compositions being different from each other at least by the nature of the compound of formula I, of the mixture of two compounds of formula I or the mixture of a compound of formula I and a compound of formula III, integrated into the polymer matrix.
• This embodiment advantageously makes it possible to better secure the product in question.
• the polymer matrix is a photopolymerizable resin and the fluorescent composition also comprises a polar solvent to facilitate integration between the resin and the compound of formula I, the mixture of two compounds of formula I or the mixture of a compound of formula I and a compound of formula III.
• the fluorescent composition obtained thus finds a very particular application in certain 3D printing techniques, for example for the manufacture of holograms, said holograms then exhibiting a greater level of security.
• a third object of the invention relates to a method for securing a product comprising the following steps of: - preparation of a fluorescent composition as defined above,
• the first step therefore consists in obtaining a fluorescent composition as defined above.
• the first step of the securing process consists in preparing a fluorescent composition comprising only a polymer matrix integrating a compound of formula I as defined above.
• the first step of the securing process consists in preparing a fluorescent composition essentially consisting of a polymer matrix incorporating a compound of formula I as defined above.
• the expression “essentially constituted” is understood to mean that the fluorescent composition consists of more than 96%, 97%, 98%, or even more than 99% of a polymer matrix incorporating a polymer matrix. compound of formula I.
• the first step of the securing process consists in preparing a fluorescent composition comprising only a polymer matrix integrating two different compounds of formula I as defined above.
• the first step of the securing process consists in preparing a fluorescent composition comprising only a polymer matrix integrating a compound of formula I as defined above and a compound of formula III as defined above. above.
• the fluorescent composition is a fluorescent ink.
• the fluorescent ink is obtained from an ink known to those skilled in the art, said inks comprising a polymer matrix, in which is incorporated a compound of formula I, a mixture of two different compounds of formula I, or a mixture of a compound of formula I and a compound of formula III, so as to obtain the ink fluorescent.
• the securing step is advantageously carried out by printing fluorescent ink on the product to be secured, such as for example a document.
• the fluorescent composition is a fluorescent varnish.
• the securing step can for example be carried out by coating or varnishing said fluorescent varnish on the product to be secured.
• step of securing all or part of the product to be secured is adapted by those skilled in the art depending on the product to be secured but also on the form of said composition.
• the securing step consists of integrating the fluorescent composition into the product to be secured.
• the securing step can equally well be carried out during the manufacture of the product, as well as be carried out afterwards to the latter.
• the securing step can be performed on the finished product.
• this step can be repeated several times on the same product in order to increase the level of security of the product.
• the securing step can be carried out according to techniques known to those skilled in the art, for example by lamination, by printing, by weaving, by varnishing, by lacquering, by gluing, by coating or even by impregnation.
• the fluorescent composition according to the invention comprising a compound of formula I and a compound of formula III is applied by coating on a reflecting surface or a metallized surface.
• the product is then secured by applying the assembly consisting of the reflective or metallized layer coated with the fluorescent composition.
• the metallized surfaces are layers known to those skilled in the art, it may be, for example, an aluminum metal layer.
• the fluorescence properties of the fluorescent composition interact with the appearance.
• reflective layer of the reflective layer and this achieves specific visual effects for securing a product.
• a reflecting surface enhances the light intensity compared to a non-reflecting surface.
• the securing method according to the invention can also include a step of shaping the fluorescent composition before the securing step.
• the shaping step can be carried out according to techniques known to those skilled in the art which make it possible, for example, to obtain a layer, a set of layers, a film or fibers. This formatting step can thus facilitate the subsequent securing step by application.
• the first step of the process consists in preparing several fluorescent compositions which differ by the nature of the compound of formula I integrated into the polymer matrix.
• the securing step consists in applying simultaneously or in a delayed manner the compositions prepared and thus increasing the level of security conferred on the product.
• the method according to the invention can be used to secure any type of product suitable for receiving said fluorescent composition.
• it can be plastic objects such as coins or packaging, luxury products such as leather goods, or even documents.
• the products secured according to the method described are documents.
• the product to be secured is a document such as an identity, fiduciary or administrative document.
• the application of the fluorescent security composition can be carried out on at least part of one face of the product.
• the fluorescent security composition is put in the form of a film before being hot or cold laminated on all the faces of the document.
• the film is applied only to one of the sides of a document.
• the film is only applied to a part of one of the two sides of a document and in yet another variant, the film is only applied to a part of each of the sides. of a document.
• the polymer matrix of the fluorescent composition also incorporates a compound of formula II defined above.
• Another subject of the invention relates to a compound of formula II: [0118] [Chem. 2] in which,
• R 1 , and R 2 and R 3 are independently selected from hydrogen, C1-C6-alkyl, C3- C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR 4 , -N (R 4 ) 2, - N + (R 4 ) s, -NHCOR 4 , -CHO, -C (0) 0H, -C (0) 0R 4 , -CFs, C1 -C6-alkoxy, aryloxy, -SH,
• R 1 , and R 2 and R 3 are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; preferably R 1 , and R 2 and R 3 are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably R 1 , and R 2 and R 3 are independently chosen from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, chloro, fluoro and -NO2; more preferably R 1 , and R 2 and R 3 are independently chosen from hydrogen, methyl, methoxy, chloro, fluoro and -NO2; even more preferably R 1 , and R 2 and R 3 are independently chosen from hydrogen, methyl, methoxy, chloro and fluoro; R 4 is selected from C1 -C6-alkyl, C1 -C6-cycloalkyl
• R 5 is chosen from C1-C6-alkyl, hydroxy-C1-C6-alkyl, C1-C6-alkyloxycarbonyl, di-C1-C6-alkylaminothionyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5 , 6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; preferably R 5 is chosen from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2, 3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C6-al
• R 1 , R 2 and R 3 are not all three hydrogen when R 5 is cinnamoyl, or benzoyl optionally substituted with methyl, methoxy, chloro or trifluoromethyl;
• R 1 is not methyl when R 5 is benzoyl
• R 2 is not methyl when R 5 is benzoyl
• R 3 is not methyl, methoxy or chloro when R 5 is benzoyl.
• the compounds of formula II are those of formula IIa:
• Preferred compounds of formula IIa are those in which R 1 is methoxy or chloro.
• the compounds of formula II are those of formula IIb:
• R 2 and R 5 are as defined in formula II.
• Preferred compounds of formula IIa are those in which R 2 is chosen from methyl, methoxy, fluoro and NO2.
• the compounds of formula II are those of formula Ile:
• Preferred compounds of formula III are those in which R 3 is chloro.
• alkyl alone or as part of another group, denotes a hydrocarbon radical of formula CnPLn + i in which n is an integer greater than or equal to 1.
• Preferred alkyl groups are linear or branched C1 to C6 alkyl groups.
• alkenyl denotes an unsaturated, linear or branched alkyl group comprising one or more carbon-carbon double bonds.
• Appropriate 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) denotes a saturated mono-, di- or tri-cyclic hydrocarbon radical having 3 to 12 carbon atoms, in particular 5 to 10. carbon atoms, more particularly 6 to 10 carbon atoms.
• Suitable cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, especially adamant-1-yl and adamant-2-yl, 1-decalinyl.
• Preferred cycloalkyl groups include cyclopropyl, cyclohexyl, and cycloheptyl.
• a particularly preferred cycloalkyl group is cyclohexyl.
• aryl (e) denotes a polyunsaturated aromatic hydrocarbon radical having a single ring (phenyl) or several aromatic rings condensed together (for example naphthyl) typically containing 5 to 12 atoms, preferably 6 to 10, in which at least one of the rings is aromatic.
• Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenantracenyl, pyrenyl.
• a particularly preferred aryl group is phenyl.
• heteroaryl (e) designates, without being limited thereto, aromatic rings or ring systems containing one to two rings condensed between them, typically containing 5 to 12 atoms, in which at least one of the rings is aromatic, and in which one or more carbon atoms in one or more of these rings are replaced by oxygen, nitrogen and / or sulfur atoms, the heteroatoms of nitrogen and sulfur can optionally be oxidized and the nitrogen heteroatoms can optionally be quaternized.
• Preferred but non-limiting heteroaryl groups are pyridinyl, pyrrolyl, furanyl, thiophenyl. Particularly preferred heteroaryl groups are thiophenyl and pyridinyl.
• halo alone or as part of another group, denotes fluoro, chloro, bromo, or iodo. Preferred halo groups are chloro and fluoro, fluoro being particularly preferred.
• haloalkyl (e) denotes an alkyl radical as defined above in which one or more hydrogen atoms are replaced by a halo group such as as defined above.
• the haloalkyl radicals according to the present invention can be linear or branched, and comprise, without being limited thereto , radicals of formula C n F2n + i in which n is an integer greater than or equal to 1, preferably an integer between 1 and 10.
• Preferred haloalkyl radicals include trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, nonafluoro-n-butyl, 1,1,1 -trifluor-n-butyl, 1, 1, 1-trifluoro-n-pentyl and 1, 1, 1-trifluoro-n-hexyl, trifluoromethyl being particularly preferred.
• the reactions were monitored by thin layer chromatography (TLC) carried out on ready-to-use aluminum sheets and covered with silica gel and a UV254 fluorescence indicator (Kieselgel® 60 0.2mm thick Merck F254) or equivalent.
• TLC thin layer chromatography
• the NMR analyzes were carried out on a Bruker 300 MHz, 400 MHz or 600 MHz spectrometer. The spectra are recorded in solution in deuterated chloroform (CDCl3). Chemical shifts are given in ppm, followed for proton spectra of multiplicity, where s, si, d, t, q, dd, td and m denote singlets, broad singlets, doublets, triplets, quadruplets, doublets of doublets, triplets of doublets and multiplets (or unresolved massive). The multiplicities are followed, where appropriate, by the value of the coupling constants noted and expressed in Hertz (Hz).
• the HRMS analyzes were carried out in positive electrospray ionization mode (ESI +).
• Solvents, reagents and starting materials have been purchased from well known chemical suppliers such as Sigma Aldrich, Acros Organics, Fluorochem, Eurisotop, VWR International, Sopachem and Polymer. Solvents, unless otherwise specified, were purified by distillation before use. Reagents and starting materials, unless otherwise indicated, were used without additional purifications.
• Step 1 The same procedure as that described above for the preparation of compound 3 was used with 1.06 g of 2- (1, 3-benzothiazol-2-yl) - 4-methylaniline, 1.8 mL of pyridine, 9 mL of THF and 0.7 mL of pentafluorobenzoyl chloride to give the intermediate compound (1.51 g).
• Step 2 The same procedure as that described above for the preparation of compound 5 was used with 1.55 g of 2- (1, 3-benzo [d] thiazol-2-yl) -4-methylaniline, 0.95 g of potassium carbonate, 6 mL of DMF and 0.5 mL of butylamine to give compound 9 (1.33 g).
• Step 1 The same procedure as that described above for the preparation of compound 3 was used with 1.32 g of 2- (1, 3-benzothiazol-2-yl) - 4-methoxyaniline, 2.1 mL of pyridine, 12 mL of THF and 0.8 mL of pentafluorobenzoyl chloride to give the intermediate compound (1.63 g).
• Step 2 The same procedure as that described above for the preparation of compound 5 was used with 1.63 g of 2- (1, 3-benzo [d] thiazol-2-yl) -4-methoxyaniline, 1.0 g of potassium carbonate, 6 mL of DMF and 0.52 mL of butylamine to give compound 13 (1.43 g).
• Step 1 The same procedure as that described above for the preparation of compound 3 was used with 2.00 g of 2- (1, 3-benzothiazol-2-yl) - 5-chloroaniline, 3.1 mL of pyridine, 10 mL of THF and 3.3 mL of pentafluorobenzoyl chloride to give the intermediate compound (1.45 g).
• Step 2 The same procedure as previously described for the preparation of compound 5 was used with 1.45 g of 2- (1, 3-benzo [d] thiazol-2-yl) -5-chloroaniline, 0.88 g of potassium carbonate, 5 mL of DMF and 0.46 mL of butylamine to give compound 29 (0.93 g).
• Step 1 The same procedure as that described above for the preparation of compound 3 was used with 2.00 g of 2- (1, 3-benzothiazol-2-yl) - 5-chloroaniline, 3.1 mL of pyridine, 10 mL of THF and 3.3 mL of pentafluorobenzoyl to give the intermediate compound (1.45 g).
• Step 2 The same procedure as that described above for the preparation of compound 5 was used with 1.0 g of 2- (1, 3-benzo [d] thiazol-2-yl) -5-chloroaniline, 0.66 g of potassium carbonate, 4 mL of DMF and 0.43 mL of aminoethanol to give compound 35 (0.75 g).
• Example 1 Preparation of a fluorescent composition in the form of a layer and its use for securing
• PC Makralon 2456 polycarbonate
• PC Makralon 2456 polycarbonate
• the extrusion is carried out on a twin-screw extruder (Brabender) with a screw rotation speed of 50 revolutions / min, a hopper flow rate of 3.8 kg / h and the following temperature profile
• the fluorescent composition On leaving the calender, the fluorescent composition is then in the form of a layer 100 mm thick. After adjusting the calender, the test was repeated so as to obtain a second layer 400 mm thick from the fluorescent composition. The secure layers thus obtained are then used as document support, said document thus being secure.
• Example 2 Preparation of a fluorescent composition in the form of a varnish and its use for securing.
• the measured varnish deposit has a thickness of 5 ⁇ m in accordance with a solvent-based varnish at 33% dry extract.
• the assembly consisting of the polyethylene terephthalate film coated with the fluorescent varnish forms a fluorescent layer.
• the fluorescent layer thus obtained is a secure layer.
• a UV lamp 365 nm
• a purple fluorescence appears to the naked eye.
• Visual and spectrophotometric analysis of the secure layer shows that the incorporation of the fluorescent dye into the polycarbonate does not affect its performance in terms of fluorescence absorption and emission.
• Example 3 Preparation of a fluorescent composition in ink form comprising a compound of formula I according to the invention and a compound of formula III.
• Compound 27 is in the form of a white powder, absorbs at 365 nm, has fluorescence emission at 522 nm.
• compound 36 of formula below [0200] [Chem. 13] Compound 36 is in the form of an orange powder, absorbs at 547 nm, has fluorescence emission at 568 nm.
• Preparation of the fluorescent composition in ink form 400 mg of compound 27 are uniformly dissolved in 100 g of transparent virgin screen printing ink of the Mara® Gloss GO type distributed by the Marabu company, compatible with printing on a plastic surface. in polycarbonate. 100 mg of compound 36 are uniformly dissolved in 100 g of the same transparent virgin screen printing ink. The ink containing the compound 27 and the ink containing the compound 36 are then mixed in a ratio of 1: 1 by weight.
• the fluorescent composition thus formulated is printed on a transparent polycarbonate card.
• Results The fluorescent composition printed perfectly.
• the pattern thus printed has a pink color visible by transparency when said card is placed on a white background, and an orange color visible by transparency when said card is placed on a black background.
• Example 4 Preparation of a fluorescent composition in ink form comprising a compound of formula I according to the invention
• the compound of family I used is compound 3 of formula below:
• Compound 3 is in the form of a white powder, absorbs at 365 nm, has fluorescence emission at 513 nm.
• the fluorescent composition thus formulated is printed on a transparent polycarbonate card using a 90 mesh screen printing frame.
• the pattern thus printed is invisible under ambient lighting and has an intense yellow fluorescence under UV lighting (365 nm).
• the optical properties of the dye are transposed between the pure dye and the screen printed layer.
• Example 5 Preparation of a fluorescent composition in ink form comprising a compound of formula I according to the invention
• the compound of formula I used is compound 13 of formula below: [0212] [Chem. 10] [0213] Compound 13 is in the form of a white powder, absorbs at 365 nm, has fluorescence emission at 605 nm.
• the fluorescent composition thus formulated is printed on a transparent polycarbonate card using a 90 mesh screen printing frame.
• the pattern thus printed is invisible under ambient lighting and has a red fluorescence under UV lighting (365 nm).
• the optical properties of the dye are transposed between the pure dye and the screen printed layer.
• 400 mg of compound 3 are uniformly dissolved in 100 g of transparent virgin screen printing ink of the Mara® Gloss GO type distributed by the Marabu company, which is compatible with printing on a polycarbonate plastic surface. 400 mg of compound 13 are uniformly dissolved in 100 g of the same transparent virgin screen printing ink.
• Results The fluorescent composition printed perfectly.
• the pattern thus printed is invisible under ambient lighting and has an intense orange fluorescence under UV lighting (365 nm).
• the color thus obtained refers to the mixture of the respective fluorescence colors of the two dyes.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Textile Engineering (AREA)
• Vascular Medicine (AREA)
• Plural Heterocyclic Compounds (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Luminescent Compositions (AREA)
• Credit Cards Or The Like (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2020
  • 2020-06-10 FR FR2006079A patent/FR3111354B1/fr active Active
• 2021
  • 2021-06-10 AU AU2021286927A patent/AU2021286927A1/en active Pending
  • 2021-06-10 US US18/009,171 patent/US20230235190A1/en active Pending
  • 2021-06-10 JP JP2022576175A patent/JP2023531167A/ja active Pending
  • 2021-06-10 CA CA3185150A patent/CA3185150A1/fr active Pending
  • 2021-06-10 BR BR112022025158A patent/BR112022025158A2/pt unknown
  • 2021-06-10 CN CN202180041852.3A patent/CN115768631A/zh active Pending
  • 2021-06-10 EP EP21736639.2A patent/EP4164891A1/de active Pending
  • 2021-06-10 KR KR1020227043352A patent/KR20230031208A/ko active Search and Examination
  • 2021-06-10 WO PCT/FR2021/051044 patent/WO2021250358A1/fr unknown
  • 2021-06-10 MX MX2022015817A patent/MX2022015817A/es unknown

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