FR2973392A1 - FLUORESCENT POLYMER COMPOSITION, FILMS COMPRISING THE SAME, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS - Google Patents
FLUORESCENT POLYMER COMPOSITION, FILMS COMPRISING THE SAME, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATIONS Download PDFInfo
- Publication number
- FR2973392A1 FR2973392A1 FR1152751A FR1152751A FR2973392A1 FR 2973392 A1 FR2973392 A1 FR 2973392A1 FR 1152751 A FR1152751 A FR 1152751A FR 1152751 A FR1152751 A FR 1152751A FR 2973392 A1 FR2973392 A1 FR 2973392A1
- Authority
- FR
- France
- Prior art keywords
- polymer
- fluorescent
- composition
- group
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 10
- 229920001109 fluorescent polymer Polymers 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 150000004905 tetrazines Chemical class 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 229920000515 polycarbonate Polymers 0.000 claims description 16
- 239000004417 polycarbonate Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 230000000269 nucleophilic effect Effects 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 26
- 239000011550 stock solution Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 5
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- PJBDTFYJRYBUKR-UHFFFAOYSA-N 5,6-dichlorotetrazine Chemical compound ClC1=NN=NN=C1Cl PJBDTFYJRYBUKR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000005893 naphthalimidyl group Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- DKLWRIQKXIBVIS-UHFFFAOYSA-N 1,1-diiodooctane Chemical compound CCCCCCCC(I)I DKLWRIQKXIBVIS-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000010147 laser engraving Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 125000005545 phthalimidyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- B42D2033/04—
-
- B42D2033/30—
-
- 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
-
- 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
- C09K2211/1011—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
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
La présente invention porte sur une composition polymère comprenant un polymère et un dérivé de tétrazine bichromophorique fluorescent, sur des films polymères comprenant cette composition et sur leurs utilisations pour le marquage de produits polymères, la sécurisation de documents officiels.The present invention relates to a polymer composition comprising a polymer and a fluorescent bichromophoric tetrazine derivative, to polymeric films comprising this composition and to their uses for marking polymeric products, securing official documents.
Description
COMPOSITION POLYMERE FLUORESCENTE, FILMS COMPRENANT LADITE COMPOSITION, LEUR PROCEDE DE PREPARATION ET LEURS APPLICATIONS L'invention porte sur des compositions polymères fluorescentes, sur leur procédé de préparation et leurs utilisations comme traceur de polymères pour lutter contre la contrefaçon, comme moyen de sécurisation de documents officiels, ou en tant qu'éléments de décoration. FLUORESCENT POLYMER COMPOSITION, FILMS COMPRISING THE SAID COMPOSITION, PROCESS FOR PREPARING THEM AND THEIR APPLICATIONS The invention relates to fluorescent polymer compositions, to their method of preparation and to their use as a polymer tracer for combating counterfeiting, as a means of securing documents official, or as decorative elements.
Les colorants fluorescents sont utilisés de façon classique comme traceurs, notamment pour aider à l'identification de faux (billets, pièces d'identité, documents officiels). Pour des raisons de sécurité, il est possible de vérifier l'authenticité de documents avec plusieurs niveaux de sécurité. Un premier niveau consiste en une observation visuelle, tactile et sonore du document, un second niveau de sécurité consiste en une observation sous lumière UV, qui laisse apparaître les traceurs fluorescents notamment, un troisième niveau de sécurité consiste en des observations et analyses plus poussées faites par expertise en laboratoire. Les activités de piratage informatique telles que le vol d'identité ne concernent plus uniquement le vol de fonds. En effet, les cyber-pirates peuvent fournir à tout criminel en fuite des documents falsifiés, tels que passeport, carte d'identité, permis de conduire, etc. Il est désormais possible de falsifier tout un ensemble de papiers officiels c'est pourquoi il est important de faire très attention à la diffusion des données personnelles, que ce soit sur les réseaux sociaux ou dans la vie « réelle ». Fluorescent dyes are conventionally used as tracers, especially to help identify fake (banknotes, identity documents, official documents). For security reasons, it is possible to verify the authenticity of documents with several security levels. A first level consists of a visual, tactile and auditory observation of the document, a second level of security consists of an observation under UV light, which reveals the fluorescent tracers in particular, a third level of security consists of observations and further analyzes made by expertise in the laboratory. Computer hacking activities such as identity theft are no longer just fund theft. Indeed, cyber-hackers can provide fugitive documents to fugitive criminals, such as passports, identity cards, driving licenses, etc. It is now possible to falsify a whole set of official papers, which is why it is important to pay close attention to the dissemination of personal data, whether on social networks or in "real" life.
Les gouvernements s'attachent également à empêcher la falsification des documents, en augmentant les exigences de qualité des photographies par exemple. Ainsi, en France, le ministère de l'Intérieur durcit les règles concernant les photos d'identité, en exigeant que toutes les photos des papiers officiels, (Carte nationale d'identité, passeport, permis de conduire, titre de séjour, etc.) soient produites à l'aide d'un système photographique agréé par le ministère de l'Intérieur, ledit système devant assurer un niveau de qualité et fiabilité satisfaisant et devant permettre de satisfaire des spécifications techniques précises, comme la résistance à la température et à l'humidité, la résistance à la lumière, ou les caractéristiques de l'image. Tous ces documents officiels, doivent bénéficier d'une haute sécurité pour prévenir la falsification et doivent résister à l'usure du temps. Le support papier est maintenant avantageusement remplacé par un support carte plastique, le plus souvent au format carte de crédit. Les documents d'identité nationaux (passeports, cartes d'identité, visas, permis de conduire...) doivent non seulement être hautement sécurisés mais également facilement contrôlables. Diverses sociétés apportent des solutions d'authentification visuelle des produits, par exemple à l'aide d'hologrammes, de gravures laser qui peuvent permettre d'insérer des informations en filigrane sur le corps de cartes en polycarbonate, telles que carte d'identité, carte de santé, permis de conduire, Si ces solutions s'avèrent intéressantes, elles sont 30 parfois difficiles à mettre en oeuvre et ne doivent pas être exclusives les unes des autres. Il existe donc un réel besoin pour les autorités d'avoir à disposition des moyens simples à mettre en oeuvre et permettant une vérification facile de l'authenticité d'un document, notamment de cartes en polycarbonate. C'est à cette fin que les présents inventeurs ont trouvé qu'il était possible d'obtenir des compositions polymères transparentes à la lumière blanche, notamment sous forme de films, qui lorsqu'elles sont soumises à un rayonnement UV émettent une fluorescence jaune très caractéristique. L'invention a donc pour objet, une composition polymère comprenant un polymère et un dérivé de tétrazine bichromophorique fluorescent de formule (1) ci-dessous: N -N N =N dans laquelle: - X représente un atome d'oxygène ou de soufre; - n est un nombre entier compris entre 0 et 5, de préférence entre 0 et 3, plus préférentiellement encore égal à 2; - Y est un groupe électroattracteur choisi dans le groupe comprenant les halogènes; les groupes neutres constitués à partir d'un hétéroatome bi- ou trivalent comme l'oxygène, notamment -O-A-R où A représente une liaison simple ou un alkylidènyle en C1-C4 et R est alkyle, alcényle, alcynyle, cycloalkyle, aryle, époxyalkyle ou perfluoroalkyle; et les électroattracteurs ioniques de type « onium » notamment pyridinium, imidazolium, phosphonium et composés analogues; - Z est un absorbant UV électrodéficitaire. Governments are also working to prevent the falsification of documents by, for example, increasing the quality requirements of photographs. Thus, in France, the Ministry of the Interior hardens the rules regarding identity photos, requiring that all photos of official documents, (National identity card, passport, driving license, residence permit, etc.). ) are produced using a photographic system approved by the Ministry of the Interior, the said system being required to ensure a satisfactory level of quality and reliability and to meet specific technical specifications, such as temperature and temperature resistance. the moisture, the light resistance, or the characteristics of the image. All of these official documents must be highly secure to prevent forgery and must withstand the passage of time. The paper support is now advantageously replaced by a plastic card holder, most often in credit card format. National identity documents (passports, identity cards, visas, driving licenses ...) must not only be highly secure but also easily controllable. Various companies provide solutions for the visual authentication of products, for example using holograms, laser engravings that can be used to insert watermark information on the body of polycarbonate cards, such as identity card, If these solutions prove to be interesting, they are sometimes difficult to implement and must not be exclusive of each other. There is therefore a real need for the authorities to have available simple means to implement and allowing easy verification of the authenticity of a document, including polycarbonate cards. It is to this end that the present inventors have found that it is possible to obtain white light-transparent polymer compositions, especially in the form of films, which, when subjected to UV radiation, emit a very yellow fluorescence. feature. The subject of the invention is therefore a polymer composition comprising a polymer and a fluorescent bichromophoric tetrazine derivative of formula (1) below: ## STR1 ## in which: X represents an oxygen or sulfur atom; n is an integer between 0 and 5, preferably between 0 and 3, more preferably still equal to 2; Y is an electron-withdrawing group chosen from the group comprising halogens; neutral groups consisting of a bi- or trivalent heteroatom such as oxygen, especially -OAR where A represents a single bond or a C1-C4 alkylidenyl and R is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, epoxyalkyl or perfluoroalkyl; and ionic electroattractants of "onium" type, in particular pyridinium, imidazolium, phosphonium and similar compounds; Z is an electrodeficient UV absorbent.
Le composé de formule (1) est un composé fluorescent bichromophorique qui autorise le transfert d'énergie entre un bon absorbant UV (fraction Z) de la molécule et un accepteur qui est un fluorophore de type tétrazine. The compound of formula (1) is a fluorescent bichromophoric compound which allows the transfer of energy between a good UV absorber (fraction Z) of the molecule and an acceptor which is a tetrazine type fluorophore.
La fraction Z du composé (encore appelée "antenne") ne doit pas pouvoir s'oxyder à un potentiel inférieur à environ +1,5 V (par rapport au calomel), ce qui correspond approximativement au pouvoir oxydant (potentiel rédox) de la tétrazine à l'état oxydé. De façon préférée, cette fraction Z doit en pratique être non-oxydable (cas par exemple de la naphtalimide). Selon un mode de réalisation particulier, dans le composé de formule (1), Z est choisi dans le groupe comprenant les radicaux suivants naphtalimidyle, phtalimidyle, benzotriazolyle, benzoxazolyle, benzophénonyle, dont les représentations respectives sont données ci-après: De façon avantageuse, Z est le naphtalimidyle. Par le terme « groupe électroattracteur» au sens de la présente invention, on entend tout groupement ayant un effet inducteur attracteur d'électrons, en particulier les halogènes et les groupes neutres constitués à partir d'un hétéroatome bi- ou trivalent comme l'oxygène, notamment -O-AR où A représente une liaison simple ou un alkyldènyle en C1-C4 et R est alkyle, alcényle, alcynyle, cycloalkyle, aryle ou époxyalkyle, perfluoroalkyle, ainsi que des groupes de type « onium » notamment pyridinium, imidazolium, phosphonium et composés analogues. Par le terme « halogène » au sens de la présente invention, on entend les atomes F, Cl, Br ou I, en particulier, F et Cl. The Z fraction of the compound (also called "antenna") must not be able to oxidize at a potential lower than about +1.5 V (relative to calomel), which corresponds approximately to the oxidizing power (redox potential) of the tetrazine in the oxidized state. Preferably, this fraction Z must in practice be non-oxidizable (for example, naphthalimide). According to a particular embodiment, in the compound of formula (1), Z is chosen from the group comprising the following radicals: naphthalimidyl, phthalimidyl, benzotriazolyl, benzoxazolyl and benzophenonyl, the respective representations of which are given below: Advantageously, Z is naphthalimidyl. By the term "electron-withdrawing group" within the meaning of the present invention is meant any group having an electron-inducing inducing effect, in particular halogens and neutral groups constituted from a bi- or trivalent heteroatom such as oxygen. , especially -O-AR where A represents a single bond or a C 1 -C 4 alkyldenyl and R is alkyl, alkenyl, alkynyl, cycloalkyl, aryl or epoxyalkyl, perfluoroalkyl, as well as groups of "onium" type including pyridinium, imidazolium, phosphonium and similar compounds. For the purposes of the present invention, the term "halogen" means the atoms F, Cl, Br or I, in particular F and Cl.
Par le terme « alkyle » au sens de la présente invention, on entend tout groupement alkyle linéaire ou branché, en particulier, les groupements alkyle contenant 1 à 6 atomes de carbone, notamment les groupes méthyle, éthyle, n-propyle, isopropyle ou isobutyle. For the purposes of the present invention, the term "alkyl" means any linear or branched alkyl group, in particular alkyl groups containing 1 to 6 carbon atoms, in particular methyl, ethyl, n-propyl, isopropyl or isobutyl groups. .
Par le terme « alcényle » au sens de la présente invention, on entend tout groupement alcényle comprenant au moins une double liaison, en particulier, les groupements alcényle contenant 2 à 6 atomes de carbone, notamment les groupes éthényle ou allyle. For the purposes of the present invention, the term "alkenyl" means any alkenyl group comprising at least one double bond, in particular alkenyl groups containing 2 to 6 carbon atoms, in particular ethenyl or allyl groups.
Par le terme « alcynyle » au sens de la présente invention, on entend tout groupement alcynyle comprenant au moins une triple liaison, en particulier, les groupements alcynyle contenant 2 à 6 atomes de carbone, notamment les groupes éthynyle et propargyle. For the purposes of the present invention, the term "alkynyl" means any alkynyl group comprising at least one triple bond, in particular alkynyl groups containing 2 to 6 carbon atoms, especially ethynyl and propargyl groups.
Par le terme « cycloalkyle » au sens de la présente invention, on entend tout groupement cycloalkyle, en particulier les groupements cycloalkyle monocycliques, bicycliques ou tricycliques, chaque cycle contenant 5 ou 6 atomes de carbone notamment les groupes cyclohexyle ou adamantanyle. For the purposes of the present invention, the term "cycloalkyl" means any cycloalkyl group, in particular monocyclic, bicyclic or tricyclic cycloalkyl groups, each ring containing 5 or 6 carbon atoms, in particular cyclohexyl or adamantanyl groups.
Par les termes « aryle » au sens de la présente invention on entend tout groupement aryl, en particulier les groupements aryle monocycliques, bicycliques ou tricycliques contenant 5 ou 6 atomes de carbone, notamment les groupes benzyle ou naphtalényle. Par le terme « époxyalkyle » au sens de la présente invention, on entend tout groupement époxyalkyle, en particulier les groupements époxyalkyle contenant 2 à 6 atomes de carbone, notamment les groupes 2,3-époxypropyle ou 3,4-époxybutyle. Par le terme « alkyldènyle en C1-C4 » au sens de la présente invention, on entend tout groupement alkyl bivalent contenant 1 à 4 atomes de carbone, notamment les groupes -CH2- et - (CH2) 2-- Par le terme « attracteurs ioniques » on entend tout groupe de type « onium » notamment pyridinium, imidazolium, phosphonium et composés analogues. Selon un mode de réalisation particulier, Y est choisi dans le groupe constitué de halogène, azoture, cyano et -O-A- R où A représente une liaison simple ou un alkyldènyle en C1-C4r de préférence -CH2-, et R est alkyle, alcényle, alcynyle, cycloalkyle, aryle, époxyalkyle ou perfluoroalkyle. Selon un mode de réalisation particulier de l'invention, le dérivé de tétrazine fluorescent bichromophorique est le 2- (4-chloro-1-éthoxy-s-tétrazinyl)-N-naphtalimide (dénommé ci- après NITZ) qui présente la formule suivante: Dans la composition selon l'invention le polymère peut être de toute nature. Pour que l'effet de fluorescence soit le plus marqué, le polymère est avantageusement un polymère transparent lorsqu'il est mis en forme. A titre d'exemples de polymères, on peut citer un polycarbonate, un polystyrène, un polyéthylène, un polyéthylène téréphtalate, un polyacrylate, un polyméthacrylate, poly(chlorure de vinyle), polyamides, polyaramides, etc. Selon un mode de réalisation particulier, le polymère est un polycarbonate. De préférence ce polycarbonate est un polycarbonate classiquement utilisé dans la préparation de support de type cartes (cartes bancaires, cartes d'identité, cartes de séjour, etc.). Selon un mode de réalisation, la composition de l'invention comprend un solvant. La composition est liquide, le solvant permet la dissolution, de préférence à la température ambiante, à la fois du polymère et du dérivé de tétrazine bichromophorique. Le solvant est un solvant non nucléophile. On peut citer comme solvant les cétones, les sulfoxydes, les nitriles, les esters, les hétérocycles azotés, les éthers, les solvants chlorés, et leurs mélanges. Plus particulièrement, le solvant peut être choisi parmi, l'acétone, la butanone, le 7 diméthylsulfoxyde, le DMF, l'acétonitrile, l'acétate d'éthyle, le diéthyléther, le THF, la diglyme, la triglyme, le chloroforme, le dichlorométhane, le dichloroéthane, le dichlorobenzène, et leurs mélanges. For the purposes of the present invention, the term "aryl" means any aryl group, in particular monocyclic, bicyclic or tricyclic aryl groups containing 5 or 6 carbon atoms, in particular benzyl or naphthalenyl groups. For the purposes of the present invention, the term "epoxyalkyl" means any epoxyalkyl group, in particular epoxyalkyl groups containing 2 to 6 carbon atoms, in particular 2,3-epoxypropyl or 3,4-epoxybutyl groups. For the purposes of the present invention, the term "C 1 -C 4 alkyldenyl" means any divalent alkyl group containing 1 to 4 carbon atoms, in particular the groups -CH 2 - and - (CH 2) 2 - By the term "attractors" "ionic" means any group of "onium" type including pyridinium, imidazolium, phosphonium and similar compounds. According to a particular embodiment, Y is chosen from the group consisting of halogen, azide, cyano and -OA-R where A represents a single bond or a C 1 -C 4 alkyl-lower alkyl, preferably -CH 2 -, and R is alkyl, alkenyl alkynyl, cycloalkyl, aryl, epoxyalkyl or perfluoroalkyl. According to a particular embodiment of the invention, the bichromophoric fluorescent tetrazine derivative is 2- (4-chloro-1-ethoxy-s-tetrazinyl) -N-naphthalimide (hereinafter referred to as NITZ) which has the following formula In the composition according to the invention the polymer can be of any kind. In order for the fluorescence effect to be most pronounced, the polymer is advantageously a transparent polymer when it is shaped. Examples of polymers that may be mentioned are polycarbonate, polystyrene, polyethylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamides, polyaramids, etc. According to a particular embodiment, the polymer is a polycarbonate. Preferably this polycarbonate is a polycarbonate conventionally used in the preparation of card-type support (bank cards, identity cards, residence cards, etc.). According to one embodiment, the composition of the invention comprises a solvent. The composition is liquid, the solvent allows the dissolution, preferably at room temperature, of both the polymer and the tetrazine dichromophoric derivative. The solvent is a non-nucleophilic solvent. Mention may be made, as a solvent, of ketones, sulfoxides, nitriles, esters, nitrogenous heterocycles, ethers, chlorinated solvents, and mixtures thereof. More particularly, the solvent may be selected from acetone, butanone, dimethylsulfoxide, DMF, acetonitrile, ethyl acetate, diethyl ether, THF, diglyme, triglyme, chloroform, dichloromethane, dichloroethane, dichlorobenzene, and mixtures thereof.
Selon un mode de réalisation particulier, le solvant est choisi dans le groupe comprenant le dichlorométhane, le dichloroéthane, le dichlorobenzène, et leurs mélanges. Un solvant particulièrement adapté lorsque le polymère est le polycarbonate, est le dichlorométhane. According to a particular embodiment, the solvent is selected from the group comprising dichloromethane, dichloroethane, dichlorobenzene, and mixtures thereof. A particularly suitable solvent when the polymer is polycarbonate is dichloromethane.
Ainsi, selon un mode de réalisation particulier, la composition selon l'invention comprend un polycarbonate, la NITZ de formule et du dichlorométhane. La composition selon l'invention peut en outre comprendre des additifs, notamment des agents stabilisants tels que des antioxydants classiques, des plastifiants tels que les phtalates ou le diiodooctane, etc. Thus, according to one particular embodiment, the composition according to the invention comprises a polycarbonate, the NITZ of formula and dichloromethane. The composition according to the invention may further comprise additives, especially stabilizing agents such as conventional antioxidants, plasticizers such as phthalates or diiodooctane, etc.
La quantité de dérivé de tétrazine fluorescent présente dans la composition selon l'invention est celle nécessaire à l'obtention d'une fluorescence lors de l'observation sous rayonnement UV. Des quantités de l'ordre de 0,05 à 5% en poids du poids total de la composition permettent d'obtenir cette fluorescence, de façon préférée on utilise de 0,1 à 0,5% et plus particulièrement environ 0,2% en poids de dérivé de tétrazine par rapport au poids total de la composition polymère. L'invention porte également sur la composition polymère fluorescente telle que définie précédemment, mise en forme. The amount of fluorescent tetrazine derivative present in the composition according to the invention is that required to obtain a fluorescence during the observation under UV radiation. Amounts of the order of 0.05 to 5% by weight of the total weight of the composition make it possible to obtain this fluorescence, preferably from 0.1 to 0.5% and more particularly about 0.2%. by weight of tetrazine derivative relative to the total weight of the polymer composition. The invention also relates to the fluorescent polymer composition as defined above, shaped.
Le dérivé de tétrazine fluorescent bichromophorique mis en oeuvre dans l'invention est stable thermiquement, ce qui permet de l'incorporer au polymère par des procédés de mélange ou de mise en forme nécessitant une montée en température, tels que l'extrusion ou le laminage. On peut ainsi obtenir la composition de l'invention sous forme de granulés extrudés prêts à l'emploi. Selon un mode de réalisation particulier, cette composition est mise sous la forme d'un film. L'invention a également pour objet ledit film polymère fluorescent. The bichromophoric fluorescent tetrazine derivative used in the invention is thermally stable, which makes it possible to incorporate it into the polymer by mixing or shaping processes requiring a rise in temperature, such as extrusion or rolling. . It is thus possible to obtain the composition of the invention in the form of ready-to-use extruded granules. According to a particular embodiment, this composition is in the form of a film. The subject of the invention is also said fluorescent polymer film.
Le film selon l'invention peut être obtenu par différents procédés connus de l'homme du métier pour la préparation de films polymères. Des exemples de tels procédés sont le laminage, le calandrage, l'extrusion, les procédés au rouleau d'étalement ("doctor blading"). Lorsque la composition est liquide, les procédés d'application peuvent être choisis parmi l'application d'un film par pulvérisation, l'application au pinceau, ou à la tournette. Ces nouveaux films polymères peuvent constituer le corps de cartes en polycarbonate pour des documents officiels de type cartes d'identité, cartes santé, permis de conduire, certificats d'immatriculation, cartes d'électeur, cartes de séjour, etc. La technologie utilisée est très simple à mettre en oeuvre et permet de déjouer la falsification tout en facilitant la vérification d'authenticité des documents par les autorités. L'invention a également pour objet un procédé de sécurisation de documents comprenant la formation d'un film 5 polymère fluorescent tel que défini précédemment. Un tel film peut être appliqué sur des documents déjà existants par lamination à chaud ou à froid. Selon un mode de réalisation particulier, le film polymère constitue le coeur du support de type carte, et 10 d'autres films polymères, éventuellement également fluorescents, sont déposés de part et d'autre de celui-ci. L'invention concerne aussi l'utilisation d'une composition polymère fluorescente ou d'un film polymère tels que définis ci-dessus, pour la sécurisation de documents, 15 notamment de cartes, badges, etc. Elle concerne également l'utilisation de ces compositions ou films comme traceurs permettant d'identifier rapidement l'origine du matériau polymère utilisé et ainsi de contrôler l'authenticité du produit incorporant ledit 20 polymère. Ainsi, l'invention a un intérêt tout particulier pour la lutte contre la contrefaçon d'objets incorporant des matériaux polymère (montres, jouets, récipients pour cosmétiques, etc.). L'invention a donc également pour objet un procédé de 25 traçage de matériau polymère comprenant la préparation d'une composition polymère telle que décrite précédemment, puis la mise en forme de cette composition polymère, de préférence sous forme de films. En effet, l'observation à la lumière UV du produit final obtenu fera apparaître une fluorescence jaune caractéristique de la composition polymère de base utilisée. Les compositions et films selon l'invention peuvent également servir d'éléments de décoration. The film according to the invention can be obtained by various methods known to those skilled in the art for the preparation of polymer films. Examples of such processes are rolling, calendering, extrusion, doctor blading processes. When the composition is liquid, the methods of application may be selected from the application of a film by spraying, brushing, or spinning. These new polymer films can constitute the body of polycarbonate cards for official documents such as identity cards, health cards, driving licenses, registration certificates, voter cards, residence cards, etc. The technology used is very simple to implement and makes it possible to thwart the falsification while facilitating the verification of authenticity of the documents by the authorities. The invention also relates to a method for securing documents comprising the formation of a fluorescent polymer film as defined above. Such a film can be applied to existing documents by hot or cold lamination. According to a particular embodiment, the polymer film constitutes the core of the card-type support, and other polymer films, possibly also fluorescent, are deposited on either side thereof. The invention also relates to the use of a fluorescent polymer composition or a polymer film as defined above, for securing documents, in particular cards, badges, etc. It also relates to the use of these compositions or films as tracers making it possible to rapidly identify the origin of the polymer material used and thus to check the authenticity of the product incorporating said polymer. Thus, the invention has a particular interest in the fight against counterfeit objects incorporating polymeric materials (watches, toys, cosmetic containers, etc.). The invention therefore also relates to a process for tracing polymeric material comprising the preparation of a polymer composition as described above, and then shaping this polymer composition, preferably in the form of films. Indeed, the observation with UV light of the final product obtained will reveal a yellow fluorescence characteristic of the basic polymer composition used. The compositions and films according to the invention can also serve as decorative elements.
L'invention est décrite plus en détail ci-après, à l'aide des exemples suivants qui sont nullement limitatifs mais sont donnés à titre d'illustration uniquement. The invention is described in more detail below, with the aid of the following examples which are in no way limiting but are given by way of illustration only.
EXEMPLES: Le polymère utilisé dans les exemples est un polycarbonate commercialisé par la Société Aldrich sous la marque Aldrich-Chemie. Il présente un poids moléculaire M.w 64000 g/mol, et est préparé à partir d'un monomère de poids moléculaire Mw: 284,35 g/mol Exemple 1: Préparation de NITZ 1) Synthèses a) (2-hydroxyéthyl)-N-naphtalimide Du naphtalimide (0.2g, lmmol) est mis à réagir dans du DMF (15 ml) avec du bromoéthanol en présence de carbonate de potassium pendant 10h. La solution résultante est reprise dans de l'eau et extraite par de l'acétate d'éthyle. Une chromatographe sur colonne (DCM) permet d'isoler le produit. (rendement 73%, 1HNMR (CDC13) : 3.98 (dd, 2H, J1=5.5Hz, J2=5Hz), 4.47 (t, 2H, J=5Hz), 7.76 (t, 2H, J =7.5Hz), 8.23 ((d, 2H, J =7.5Hz), 8.62 (d, 2H, J =7.5Hz) b) Fluorophore NITZ La réaction de la dichlorotétrazine et du (2- hydroxyéthyl)-N-naphthalimide a été réalisée dans des conditions standard (leq. dichlorotétrazine, leq. alcool, 2 eq. collidine dans le DCM, RT, 2h) pour fournir le NITZ avec 56% de rendement. (rendement 56%, 1H NMR (CDC13) : 4.75 (t, 2H, J=5Hz), 5.06 (t, 2H, J=5Hz), 7.75 (t, 2H, J =7.5Hz), 8.23 ((d, 2H, J =7.5Hz), 8.56 (d, 2H, J =7.5Hz). 13C :38.06, 67.62 (aliphatiques), 122.28, 127.14, 128.88, 131.75, 132.26, 134.54 (coeur naphtalène), 163.65, 164.51, 166.65 (imide et tétrazine). EXAMPLES: The polymer used in the examples is a polycarbonate marketed by Aldrich under the trademark Aldrich-Chemie. It has a molecular weight of Mw 64,000 g / mol, and is prepared from a monomer of molecular weight Mw: 284.35 g / mol. Example 1: Preparation of NITZ 1) Syntheses a) (2-hydroxyethyl) -N- naphthalimide Naphthalimide (0.2 g, 1 mmol) is reacted in DMF (15 ml) with bromoethanol in the presence of potassium carbonate for 10 h. The resulting solution is taken up in water and extracted with ethyl acetate. A column chromatograph (DCM) isolates the product. (73% yield, 1HNMR (CDCl3): 3.98 (dd, 2H, J1 = 5.5Hz, J2 = 5Hz), 4.47 (t, 2H, J = 5Hz), 7.76 (t, 2H, J = 7.5Hz), 8.23 ((d, 2H, J = 7.5Hz), 8.62 (d, 2H, J = 7.5Hz) b) NITZ Fluorophore The reaction of dichlorotetrazine and (2-hydroxyethyl) -N-naphthalimide was carried out under standard conditions (dichlorotetrazine, leq alcohol, 2 eq collidine in DCM, RT, 2h) to provide NITZ with 56% yield (56% yield, 1H NMR (CDCl3): 4.75 (t, 2H, J = 5Hz), 5.06 (t, 2H, J = 5Hz), 7.75 (t, 2H, J = 7.5Hz), 8.23 ((d, 2H, J = 7.5Hz), 8.56 (d, 2H, J = 7.5Hz) 13C: 38.06, 67.62 (aliphatic), 122.28, 127.14, 128.88, 131.75, 132.26, 134.54 (naphthalene core), 163.65, 164.51, 166.65 (imide and tetrazine).
M+ = 355, 357 (calc. 355, 357) M + = 355, 357 (calc 355, 357)
Exemple 2: On a préparé une solution mère de la façon suivante. 5g de polycarbonate et 2mg de NITZ préparée selon l'exemple 1 sont introduits dans 100mL de CH2C12 en une heure sous vive agitation. La concentration en NITZ est de 0,4 mg/g. La solution est rose. Example 2: A stock solution was prepared as follows. 5 g of polycarbonate and 2 mg of NITZ prepared according to Example 1 are introduced into 100 ml of CH 2 Cl 2 in one hour with vigorous stirring. The NITZ concentration is 0.4 mg / g. The solution is pink.
La solution mère est diluée avec CH2C12 pour obtenir: "Solution 2": 10 mL de la solution mère sont complétés à 100 mL. La solution est légèrement rose. "Solution 3" : 10 mL de la solution mère sont complétés à 100 25 mL . La solution est presque incolore The stock solution is diluted with CH2Cl2 to obtain: "Solution 2": 10 mL of the stock solution are made up to 100 mL. The solution is slightly pink. "Solution 3": 10 mL of the stock solution is made up to 100 mL. The solution is almost colorless
Des dépôts de ces trois solutions (solution mère, "Solution 2" et "Solution 3") sont réalisés sous forme de 30 gouttes que l'on laisse sécher et des films d'épaisseur variable sont obtenus. On obtient des films présentant des zones transparentes et des zones translucides. Ces inhomogénéités de surface traduisent l'inhomogénéité de l'évaporation du solvant. Deposits of these three solutions (stock solution, "Solution 2" and "Solution 3") are made in the form of 30 drops which are allowed to dry and films of variable thickness are obtained. Films with transparent areas and translucent areas are obtained. These surface inhomogeneities reflect the inhomogeneity of the evaporation of the solvent.
Par observation à la lumière UV, les zones transparentes apparaissent fluorescentes de couleur jaune. By observation with UV light, the transparent areas appear fluorescent yellow.
Exemple 3 On prépare diverses solutions comme dans l'exemple 2: Solution mère : 20 mg de NITZ sont dissous dans 10 mL de CH2C12. Example 3 Various solutions are prepared as in Example 2: Stock solution: 20 mg of NITZ are dissolved in 10 ml of CH2Cl2.
"Solution 2" : 1 mL de la solution mère est complétée à 10 mL avec CH2C12. "Solution 2": 1 mL of the stock solution is made up to 10 mL with CH2Cl2.
"Solution polymère 1": 5 g de polycarbonate sont dissous dans 50 mL de CH2C12et 1 mL de solution mère est ajoutée. La concentration en NITZ est de 0,4 mg/g. La solution est rose. "Polymer solution 1": 5 g of polycarbonate are dissolved in 50 mL of CH 2 Cl 2 and 1 mL of stock solution is added. The NITZ concentration is 0.4 mg / g. The solution is pink.
"Solution Polymère 2": 5 g de polycarbonate sont dissous dans 50 mL de CH2C12 et 1 mL de "solution 2" est ajoutée. La concentration en NITZ est de 0,04 mg/g. La solution est presque incolore. "Polymer Solution 2": 5 g of polycarbonate are dissolved in 50 ml of CH 2 Cl 2 and 1 ml of "solution 2" is added. The concentration of NITZ is 0.04 mg / g. The solution is almost colorless.
"Solution Polymère 3" : 5 g de Polycarbonate sont dissous dans 50 mL de CH2C12. 5 mL de solution mère est ajoutée. La concentration en NITZ est de 2 mg/g. La solution est franchement rose."Polymer Solution 3": 5 g of Polycarbonate are dissolved in 50 ml of CH2Cl2. 5 mL of stock solution is added. The concentration of NITZ is 2 mg / g. The solution is frankly pink.
20 25 30 Des films polymères sont réalisés à partir des solutions polymères ("solution polymère 1", "solution polymère 2" et "solution polymère 3") par application au moyen d'une tournette (spin-coating) sur des supports en verre. Les supports en verre sont mouillés par la solution polymère, puis on lance la tournette à 300 tpm pendant 30 s. Pour obtenir des dépôts épais on effectue plusieurs dépôts successifs de polymères. Pour chaque solution polymère, 2 films ont été réalisés avec 3 dépôts successifs et avec 10 depôts successifs Tous les films obtenus sont transparents lorsqu'ils sont observés à la lumière blanche. Sous lumière UV (365nm) ils sont fluorescents de couleur jaune. Les films ainsi préparés ont été chauffés à 200 °C sur plaque chauffante. Après refroidissement, ils étaient transparents sous lumière blanche et fluorescents de couleur jaune par observation sous lumière UV (365 nm). Polymeric films are made from the polymer solutions ("Polymer solution 1", "Polymer solution 2" and "Polymer solution 3") by spin-coating on glass supports. . The glass supports are wetted with the polymer solution, then the spin is started at 300 rpm for 30 s. To obtain thick deposits several successive deposits of polymers are made. For each polymer solution, 2 films were made with 3 successive deposits and with 10 successive deposits. All the films obtained are transparent when they are observed with white light. Under UV light (365nm) they are fluorescent yellow. The films thus prepared were heated to 200 ° C on a hot plate. After cooling, they were transparent under white light and fluorescent yellow by observation under UV light (365 nm).
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| FR1154792A FR2973388B1 (en) | 2011-03-31 | 2011-05-31 | FLUORESCENT BICHROMOPHORIC TETRAZINE DERIVATIVES, FLUORESCENT POLYMER COMPOSITION CONTAINING SAME, PROCESS FOR PREPARING SAME AND APPLICATIONS THEREOF |
| PCT/FR2012/050703 WO2012131278A1 (en) | 2011-03-31 | 2012-03-30 | Fluorescent polymer composition, fluorescent bichromophoric tetrazine derivatives, method for preparing same, and uses thereof |
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| CN111333641B (en) * | 2018-12-18 | 2022-05-31 | 中国科学院大连化学物理研究所 | Enhanced fluorescent probe for tetrazine bio-orthogonal labeling and synthesis thereof |
| WO2022077052A1 (en) * | 2020-10-12 | 2022-04-21 | The University Of Sydney | Probe compounds for mitochondial membrane imaging |
| CN114671851B (en) * | 2020-12-24 | 2024-03-26 | 中国医学科学院药物研究所 | Naphthalimide-tetrazine compound and preparation method and application thereof |
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| US4756557A (en) * | 1984-12-21 | 1988-07-12 | G.A.O. Gesellschaft Fuer Automation Und Organisation Mbh | Security document having a security thread embedded therein and methods for producing and testing the authenticity of the security document |
| WO2002046528A1 (en) * | 2000-12-05 | 2002-06-13 | Spectra Systems Corporation | Fluorescent micro-particles embedded in a pigmented fluorescent coating for optical document security |
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| US4756557A (en) * | 1984-12-21 | 1988-07-12 | G.A.O. Gesellschaft Fuer Automation Und Organisation Mbh | Security document having a security thread embedded therein and methods for producing and testing the authenticity of the security document |
| WO2002046528A1 (en) * | 2000-12-05 | 2002-06-13 | Spectra Systems Corporation | Fluorescent micro-particles embedded in a pigmented fluorescent coating for optical document security |
Non-Patent Citations (4)
| Title |
|---|
| E. CUELLAR, G. CASTRO: "Photochemical and nonphotochemical hole burning in dimethyl-s-tetrazine in a polyvinyl carbazole film", CHEMICAL PHYSICS, vol. 54, 1981, pages 217 - 225, XP002657293 * |
| G. CLAVIER, P. AUDEBERT: "s-Tetrazines as building blocks for new functional molecules and molecular materials", CHEM. REV., vol. 110, 22 March 2010 (2010-03-22), pages 3299 - 3314, XP002657292 * |
| YUNA KIM ET.AL.: "New tetrazine-based fluororelectrochromic window; modulation of the fluorescence through applied potential", CHEM. COMMUN., 2006, pages 3612 - 3614, XP002657294 * |
| YUNA KIM ET.AL.: "Tetrazine-based electrofluorochromic windows: modulation of the fluorescence through applied potential", JOURNAL OF ELECTROANALYTICAL CHEMISTRY, vol. 632, 2009, pages 201 - 205, XP002657295 * |
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