EP4267588A1 - Mechanochromic and mechanofluorochromic compound, composition, and fiduciary document using same - Google Patents

Mechanochromic and mechanofluorochromic compound, composition, and fiduciary document using same

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Publication number
EP4267588A1
EP4267588A1 EP21820271.1A EP21820271A EP4267588A1 EP 4267588 A1 EP4267588 A1 EP 4267588A1 EP 21820271 A EP21820271 A EP 21820271A EP 4267588 A1 EP4267588 A1 EP 4267588A1
Authority
EP
European Patent Office
Prior art keywords
compound
ink
document
color
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21820271.1A
Other languages
German (de)
French (fr)
Inventor
Ella Dermilly
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oberthur Fiduciaire SAS
Original Assignee
Oberthur Fiduciaire SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Oberthur Fiduciaire SAS filed Critical Oberthur Fiduciaire SAS
Publication of EP4267588A1 publication Critical patent/EP4267588A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • 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
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • 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
    • 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
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials

Definitions

  • TITLE Mechanochromic and mechanofluorochromic compound, composition and fiduciary document which make use of it
  • the present invention relates to a compound which has not only mechanochromism properties, but also mechanofluorochromism properties. It also relates to a fiduciary composition which contains it and to a security document which is coated with it and/or contains it.
  • the present invention finds an application, in particular in the field of the fiduciary industry and more particularly in the manufacture of security documents.
  • security document is understood to mean a document, for example made of paper or plastic, which includes within it and/or is coated with means making it possible to secure its manufacture, so as to make its reproduction fraudulent impossible, or at the very least particularly complex, and to ensure its authentication.
  • the article "Thermo- and mechanical-grinding-triggered color and luminescence switches of the diimine-platinum(ii) complex with 4-bromo-2,2'-bipyridine” (Jun Ni et al., Dalton Trans., 2014, 43, 352-360) describes a platinum complex showing a color change in daylight and under UV when ground in a mortar. Initially, the complex is yellow-green fluorescent and becomes fluorescent red. This color change is reversible by exposure to a solvent.
  • Document CN 108947933 describes a diethyl terephthalate compound which exhibits mechanochromism properties.
  • Document CN 109053779 describes a mechanochromic difluoroboron material and a process for its preparation.
  • WO2019/202280 describes a device comprising at least two layers arranged facing each other. These layers include an optically variable element exhibiting a color change between two sufficiently contrasting colors with respect to the second layer.
  • the optically variable element consists of a compound from the family of BODIPY (Boron-dipyrromethene) and a compound from the family of B-difluoroborane diketonate (BF2dbks).
  • a described compound, identified as “compounds” is yellow in visible light. It does not change color in the visible, even under stress. It is fluorescent green under UV and becomes fluorescent yellow under UV when scratched.
  • photochromes as mechanochromic components requires the application of a very high mechanical stress to obtain a color change, which damages the host polymeric material in an irreversible way.
  • FR2969034, FR2969152 and FR2999764 describe molecules of the difluoroborated beta-diketone family with mechanofluorochromism properties for the authentication of banknotes.
  • the compounds described above from the difluoroborated beta-diketone family have mechanofluorochromism properties only, which implies that the color change following stress is only visible under ultraviolet radiation.
  • the aim of the present invention is to respond to these difficulties and to propose a security element combining the first and second level functionalities in the same molecule.
  • a first object of the invention relates to a compound that is both mechanochromic and mechanofluorochromic, which corresponds to the following formula (F): formula (F) in which:
  • R 1 is chosen from:
  • R 1 is - -CFhh.
  • the present applicant has found that the molecule above has not only mechanochromism properties but also mechanofluorochromism properties. Expressed otherwise, the change in color resulting from mechanical stress, in particular friction, scratching or rubbing, is visible in the visible spectrum and also under ultraviolet irradiation.
  • said ink is a liquid ink, in particular with a viscosity of between 0.01 and 1 Pa.s at 25° C., or a greasy ink, in particular with a viscosity greater than or equal to 5 Pa.s at 25° C.;
  • the said ink is an ink for printing using one of the following techniques: offset, intaglio, typography, flexography, rotogravure, inkjet and screen printing;
  • said ink is an ink drying by ultraviolet rays or oxidative drying, that is to say by contact with the surrounding oxygen;
  • said compound (F) is present at a level of 1 to 30% by weight.
  • the present invention also relates to a security document such as a banknote or a passport, characterized in that it comprises within it and/or on the surface a compound (F) described above.
  • the compound is incorporated into an ink.
  • this compound is dispersed in the mass of the document.
  • said compound is affixed to the surface of said thread.
  • the document incorporates at least one film, in particular a foil, a lamination strip or a patch
  • said compound is affixed to the surface of said film, in particular of said foil, of said lamination strip or of said patch.
  • Another aspect of the invention relates to a method for authenticating a document as described above, said document comprising at least a first region coated with said compound, as well as to the minus one additional region which is coated with an imprint of the same color as said compound when subjected to mechanical excitation, but which is free of said compound, which comprises the following steps:
  • FIG. 1 is a partial top view of a banknote, one area of which has been covered with a flat area of ink incorporating the compound according to the invention, in a first state in which said area is not subjected to no mechanical stress;
  • Figure 2 is a view similar to Figure 1, in which said area has been subjected to mechanical stress, for example by partial scraping of its surface, and then has been exposed to ultraviolet radiation;
  • FIG. 3 is a top view of an alternative embodiment of the ticket of the previous figures, in which said zone incorporates a polarizer.
  • the present invention relates primarily to a compound F as defined above.
  • Step 1 A solution of acyl chloride (3.92g, 0.05moles) in 10ml of dichloromethane is added dropwise to a solution containing 12.3g of triphenylamine (0.05moles) and 6.81g of ZnCl2 (0.05moles) in 10ml of dichloromethane. The whole is heated under reflux overnight.
  • reaction medium After cooling, the reaction medium is poured into 150 ml of 2M HCl solution. After separation of the phases, the organic phase is washed with water until neutral pH. After evaporation of the solvent, the product is purified by hot recrystallization from ethanol to give a white powder (8.61 g, 60%).
  • a concentrated paste is first produced from 60% by weight of an offset matrix bearing the reference 9C0000S available from the company SICPA and 40% by weight of pigment obtained previously, ground in a disc mill.
  • the final ink is prepared by mixing 50% by weight of the paste paste previously obtained and 50% by weight of "transparent white 9C0000S” (Sicpa company), to which 3 drops of siccative are added.
  • a strip of vellum paper is then printed on an IGT model AIC2-5 type device.
  • This change is reversible at room temperature in about an hour or in a few seconds if the ink is subjected to a heat source such as a hair dryer.
  • This ink can be either a liquid ink or a greasy ink, i.e. a viscous ink that does not flow.
  • it may be an ink for printing using one of the following techniques: offset, intaglio, letterpress, flexography, rotogravure, inkjet and screen printing.
  • This ink can be an ink drying by ultraviolet rays or oxidative drying, that is to say by contact with the surrounding oxygen.
  • the above ink is suitable for printing on the surface of a security document such as a banknote, it is also suitable for coating a security element such as a thread or a film, in particular a foil , a lamination strip or a patch, in particular made of plastic material, which it is proposed to position at least partially on the surface of a ticket.
  • a security element such as a thread or a film, in particular a foil , a lamination strip or a patch, in particular made of plastic material, which it is proposed to position at least partially on the surface of a ticket.
  • the aforementioned compound also lends itself to direct introduction into a security document, for example into paper pulp when it it is a ticket or in a plastic material when it is a card, for example identity.
  • FIG. 1 and 2 is shown schematically, front view, a security document which consists of a banknote 1. It could however be another type of security document such as a visa or a passport. It is therefore a simple example of an embodiment.
  • the aforementioned ink is affixed to the fiduciary paper constituting the banknote 1 according to one of the methods known to those skilled in the art.
  • zone 4 In the initial state, that is to say in the absence of any mechanical stress or energy input, the entire zone 4 has the same orange color Ci.
  • zone 4 takes on a fluorescent orange colour. This is the situation in Figure 1.
  • zone 4 When at least part of zone 4 is subjected to scratching or rubbing, for example with the edge of a coin, then this changes from the initial orange color Ci to the red color C2.
  • This method simple to implement and accessible to anyone, provides first-level security that guarantees the authenticity of the cut.
  • the security element therefore allows double authentication, and in particular two authentications at different security levels.
  • the ticket includes an area 4 made in the form of a solid area.
  • Region 40 is coated, as in the previous case, with an ink incorporating the aforementioned compound F. It adjoins a second region 41 which is coated with an impression of red color, of a shade identical to that identified C2, but devoid of compound F.
  • region 40 As soon as part of region 40 is mechanically excited, it changes to the color red, according to a hue that can be immediately compared to that of region 41 .
  • the banknote can be considered authentic.
  • the colors are different (or if the requested area does not change color), then there is a serious doubt about the authenticity, so the document must be investigated further.
  • regions 40 and 41 can take a form other than that shown here. They can for example be graphically worked to be intimately nested.
  • Step 1
  • bromooctadodecane 33.34g 0.10mole
  • methyl paraben 15g, 0.10mole
  • potassium carbonate 14.99g, 0.11mole
  • Step 3 In a three-necked flask under argon, the diketone which was obtained in step 2 is dissolved in 120 ml of toluene, then BF3.OEt2 (2.71 ml, 0.022 mol) is added. The whole is heated to 60° C. with stirring overnight.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Saccharide Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

In particular, the invention relates to a mechanochromic and mechanofluorochromic compound, which has the formula (F) in which: R 1 is selected from: - a linear or branched C1-C4 alkyl chain, and preferably tertiobutyl; a C1-C22 alkoxy chain; a C1-C4 dialkylamino group, and preferably dimethylamino; and at least one heteroatom.

Description

DESCRIPTION DESCRIPTION
TITRE : Composé mécanochromique et mécanofluorochromique, composition et document fiduciaire qui en font usage TITLE: Mechanochromic and mechanofluorochromic compound, composition and fiduciary document which make use of it
DOMAINE TECHNIQUE GENERAL GENERAL TECHNICAL AREA
La présente invention se rapporte à un composé qui possède non seulement des propriétés de mécanochromisme, mais également des propriétés de mécanofluorochromisme. Elle se rapporte également à une composition fiduciaire qui le contient et à un document de sécurité qui en est revêtu et/ou le contient. The present invention relates to a compound which has not only mechanochromism properties, but also mechanofluorochromism properties. It also relates to a fiduciary composition which contains it and to a security document which is coated with it and/or contains it.
ETAT DE LA TECHNIQUE STATE OF THE ART
La présente invention trouve une application, notamment dans le domaine de l’industrie fiduciaire et plus particulièrement dans la fabrication de documents de sécurité. The present invention finds an application, in particular in the field of the fiduciary industry and more particularly in the manufacture of security documents.
On entend par l’expression « document de sécurité », un document, par exemple en papier ou en plastique, qui inclut en son sein et/ou est revêtu de moyens permettant d’en sécuriser la fabrication, de manière à en rendre la reproduction frauduleuse impossible, ou à tout le moins particulièrement complexe, et d’en assurer l’authentification. The expression “security document” is understood to mean a document, for example made of paper or plastic, which includes within it and/or is coated with means making it possible to secure its manufacture, so as to make its reproduction fraudulent impossible, or at the very least particularly complex, and to ensure its authentication.
Des molécules douées de mécanochromisme sont connues de l’art antérieur. Molecules endowed with mechanochromism are known from the prior art.
Ainsi, l’article « Bromo induced reversible distinct color switching of a structurally simple donor-acceptor molecule by vapo, piezo and thermal stimuli” (Pachaiyappan Rajamalli et al., The Royal Society of Chemistry, 2015) décrit deux molécules de la famille des amines dont une possède la propriété de mécanochromisme avec un changement de couleur à la lumière du jour de l’orange-rouge vers le jaune et sous rayonnement ultraviolet (ci-après UV) du vert vers le rouge. Pour cela, il faut broyer le composé dans un mortier. Ce changement est réversible en chauffant le composé à 140°C pendant 10 minutes. Thus, the article “Bromo induced reversible distinct color switching of a structurally simple donor-acceptor molecule by vapo, piezo and thermal stimuli” (Pachaiyappan Rajamalli et al., The Royal Society of Chemistry, 2015) describes two molecules of the family of amines, one of which has the property of mechanochromism with a color change in daylight from orange-red to yellow and under ultraviolet radiation (hereinafter UV) from green to red. For this, the compound must be ground in a mortar. This change is reversible by heating the compound to 140°C for 10 minutes.
L’article « Thermo- and mechanical-grinding-triggered color and luminescence switches of the diimine-platinum(ii) complex with 4-bromo-2,2'- bipyridine » (Jun Ni et al., Dalton Trans., 2014, 43, 352-360) décrit un complexe de platine présentant un changement de couleur à la lumière du jour et sous UV lorsqu’il est broyé dans un mortier. Initialement, le complexe est jaune vert fluorescent et devient rouge fluorescent. Ce changement de couleur est réversible par exposition à un solvant. The article "Thermo- and mechanical-grinding-triggered color and luminescence switches of the diimine-platinum(ii) complex with 4-bromo-2,2'-bipyridine" (Jun Ni et al., Dalton Trans., 2014, 43, 352-360) describes a platinum complex showing a color change in daylight and under UV when ground in a mortar. Initially, the complex is yellow-green fluorescent and becomes fluorescent red. This color change is reversible by exposure to a solvent.
L’article « Solvatochromism, Reversible Chromism and Self- Assembly Effects of Heteroatom-Assisted Aggregation-Induced Enhanced Emission (AIEE) Compounds” (Caixia Niu et al, Chem.Eur.2015, 21 , 13983-13990) décrit deux molécules de la famille des anthracènes. Les deux composés montrent un changement de couleur de fluorescence sous UV après frottements, mais seul l’un des composés est mécanochrome. The article “Solvatochromism, Reversible Chromism and Self-Assembly Effects of Heteroatom-Assisted Aggregation-Induced Enhanced Emission (AIEE) Compounds” (Caixia Niu et al, Chem.Eur.2015, 21, 13983-13990) describes two molecules of the anthracene family. Both compounds show a fluorescence color change under UV after rubbing, but only one of the compounds is mechanochrome.
L’article « Effects of electron donor on luminescence and mechanochromism of D-n-A benzothiazole derivatives » (YanbingShen et Al., Dyes and PigmentsVolume 150, March 2018, Pages 354-362) décrit les propriétés de mécanofluorochromisme et mécanochromisme de deux dérivés de benzothiazole. L’un des deux montre un contraste très faible entre les couleurs avant et après frottement. The article "Effects of electron donor on luminescence and mechanochromism of D-n-A benzothiazole derivatives" (YanbingShen et Al., Dyes and PigmentsVolume 150, March 2018, Pages 354-362) describes the mechanofluorochromism and mechanochromism properties of two benzothiazole derivatives. One of the two shows a very low contrast between the colors before and after rubbing.
L’article “Mechanofluorochromism of a Series of Benzofuro[2,3- c]oxazolo[4,5-a]carbazole-Type Fluorescent Dyes (Yousuke Ooyama et Al., Eur.J.Org.Chem, 5321 -5326) décrit la propriété de mécanofluorochromisme pour la famille des benzofuro[2,3-c]oxazolo[4,5-a]carbazole, dont deux molécules changent de couleur dans le spectre visible après broyage. The article “Mechanofluorochromism of a Series of Benzofuro[2,3-c]oxazolo[4,5-a]carbazole-Type Fluorescent Dyes (Yousuke Ooyama et Al., Eur.J.Org.Chem, 5321 -5326) describes the mechanofluorochromism property for the benzofuro[2,3-c]oxazolo[4,5-a]carbazole family, two molecules of which change color in the visible spectrum after grinding.
Le document CN 108947933 décrit un composé diéthyl téréphthalate qui présente des propriétés de mécanochromisme. Document CN 108947933 describes a diethyl terephthalate compound which exhibits mechanochromism properties.
Le document CN 109053779 décrit un matériau mécanochromique difluoroboré et un procédé de préparation de celui-ci. Document CN 109053779 describes a mechanochromic difluoroboron material and a process for its preparation.
Les documents WO2013/158379, US9133362 et US8236914 décrivent l’utilisation de photochromes (spirooxazine, indenonaphthopyrane, spiropyrane) dans une matrice polymérique. Dans le premier document, le composé est lié de façon covalente à la matrice polymère alors que dans les deux autres brevets, le composé est utilisé sous sa forme cristalline. L’application d’une contrainte mécanique entraine un changement de couleur par modification chimique (ouverture de cycles). Documents WO2013/158379, US9133362 and US8236914 describe the use of photochromes (spirooxazine, indenonaphthopyran, spiropyran) in a polymer matrix. In the first document, the compound is covalently bonded to the polymer matrix, whereas in the other two patents, the compound is used in its crystalline form. The application of a mechanical stress leads to a change of color by chemical modification (opening of cycles).
On décrit dans WO2019/202280 un dispositif comprenant au moins deux couches disposées en regard l’une de l’autre. Ces couches comprennent un élément optiquement variable présentant un changement de couleur entre deux couleurs suffisamment contrastées par rapport à la deuxième couche. L'élément optiquement variable est constitué d'un composé de la famille des BODIPY (Bore-dipyrrométhène) et d'un composé de la famille des B- dicétonate de difluoroborane (BF2dbks). WO2019/202280 describes a device comprising at least two layers arranged facing each other. These layers include an optically variable element exhibiting a color change between two sufficiently contrasting colors with respect to the second layer. The optically variable element consists of a compound from the family of BODIPY (Boron-dipyrromethene) and a compound from the family of B-difluoroborane diketonate (BF2dbks).
Un composé décrit, identifié "composés", est jaune à la lumière visible. Il ne change pas de couleur dans le visible, même en cas de sollicitation. Il est vert fluorescent sous UV et devient jaune fluorescent sous UV lorsqu’on le gratte. A described compound, identified as "compounds", is yellow in visible light. It does not change color in the visible, even under stress. It is fluorescent green under UV and becomes fluorescent yellow under UV when scratched.
Imprimé sur un film plastique sur fond clair, il est jaune à la lumière du jour et devient vert sur fond noir. Printed on a plastic film on a light background, it is yellow in daylight and turns green on a black background.
Un art antérieur supplémentaire est constitué par le document W02020/044213. Additional prior art is WO2020/044213.
La plupart des molécules décrites dans ces documents montrent un changement de couleur réversible uniquement par chauffage ou exposition à des solvants, ce qui est problématique en termes de facilité d’utilisation, notamment lorsque ce composé est utilisé en lien avec des documents fiduciaires tels que des billets de banque. Most of the molecules described in these documents show a reversible color change only by heating or exposure to solvents, which is problematic in terms of ease of use, especially when this compound is used in connection with fiduciary documents such as Bank notes.
L’utilisation de photochromes comme composants mécanochromiques nécessite d’appliquer une contrainte mécanique très importante pour obtenir un changement de couleur, ce qui endommage le matériau polymérique hôte de façon irréversible. The use of photochromes as mechanochromic components requires the application of a very high mechanical stress to obtain a color change, which damages the host polymeric material in an irreversible way.
Le document W02011 /068537 se rapporte à des composés de la famille des beta-dicétones difluoroborées avec des propriétés de mécanochromisme de luminescence. Document WO2011/068537 relates to compounds of the difluoroborated beta-diketone family with luminescence mechanochromism properties.
Les documents FR2969034, FR2969152 et FR2999764 décrivent des molécules de la famille des béta-dicétones difluoroborées avec propriétés de mécanofluorochromisme pour l’authentification de billets de banque. The documents FR2969034, FR2969152 and FR2999764 describe molecules of the difluoroborated beta-diketone family with mechanofluorochromism properties for the authentication of banknotes.
Les composés décrits ci-dessus de la famille des béta-dicétones difluoroborées possèdent des propriétés de mécanofluorochromisme uniquement, ce qui sous-entend que le changement de couleur consécutif à un stress n’est visible que sous rayonnement ultraviolet. The compounds described above from the difluoroborated beta-diketone family have mechanofluorochromism properties only, which implies that the color change following stress is only visible under ultraviolet radiation.
Il découle de ce qui précède qu’il est nécessaire de disposer à minima d’une lampe à ultraviolet pour constater le changement de couleur. Il s’agit donc d’un élément de sécurité dit de deuxième niveau. It follows from the above that it is necessary to have at least an ultraviolet lamp to observe the change in color. It is therefore a so-called second level security element.
Or, dans le domaine fiduciaire, un changement de couleur observable sans aucun outil comme une preuve de l’authenticité du document fiduciaire est un moyen encore plus facile et désirable. Il s’agit d’un moyen de sécurité de premier niveau. However, in the fiduciary field, a change in color observable without any tool as proof of the authenticity of the document fiduciary is an even easier and desirable way. This is a first level security means.
La présente invention a pour but de répondre à ces difficultés et de proposer un élément de sécurité cumulant les fonctionnalités de premier et deuxième niveau dans la même molécule. The aim of the present invention is to respond to these difficulties and to propose a security element combining the first and second level functionalities in the same molecule.
PRESENTATION DE L'INVENTION PRESENTATION OF THE INVENTION
Ainsi, un premier objet de l’invention est relatif à un composé à la fois mécanochromique et mécanofluorochromique, qui répond à la formule (F) suivante : formule (F) dans laquelle : Thus, a first object of the invention relates to a compound that is both mechanochromic and mechanofluorochromic, which corresponds to the following formula (F): formula (F) in which:
R1 est choisi parmi : R 1 is chosen from:
- une chaîne alkyle en C1 à C4, linéaire ou ramifiée ; - a C1 to C4 alkyl chain, linear or branched;
- une chaîne alcoxy en C1 à C22 ; - a C1 to C22 alkoxy chain;
- un groupement dialkylamino en C1 à C4, et de préférence diméthylamino ;- a C1 to C4 dialkylamino group, and preferably dimethylamino;
- au moins un hétéroatome. - at least one heteroatom.
Avantageusement, R1 est - -CFhh. Advantageously, R 1 is - -CFhh.
Le présent demandeur a constaté que la molécule ci -dessus présente non seulement des propriétés de mécanochromisme mais également de mécanofluorochromisme. Exprimé autrement, le changement de couleur consécutif à une contrainte mécanique, notamment une friction, un grattage ou un frottement, est visible dans le spectre visible et également sous irradiation dans l’ultraviolet. The present applicant has found that the molecule above has not only mechanochromism properties but also mechanofluorochromism properties. Expressed otherwise, the change in color resulting from mechanical stress, in particular friction, scratching or rubbing, is visible in the visible spectrum and also under ultraviolet irradiation.
Cela a pour conséquence que lorsque cette molécule est apposée sur un support, il n’est pas nécessaire de disposer d’une lampe à UV pour constater le changement de couleur. On comprend que cela facilite grandement la vérification de l’authenticité de billets de banque par tout un chacun. This has the consequence that when this molecule is affixed to a support, it is not necessary to have a UV lamp to observe the color change. We understand that this greatly facilitates the verification of the authenticity of banknotes by everyone.
Ceci est d’autant plus étonnant que parmi les molécules de la famille des béta-dicétones difluoroborées, une infime partie d’entre elles possède des propriétés de mécanoluminescence et aucune n’est décrite comme mécanochrome. Ces molécules sont découvertes par hasard. Les études actuelles ne permettent pas de généraliser un tel mécanisme et donc d’anticiper si une molécule possède ou non la propriété en question. This is all the more surprising since among the molecules of the difluoroborated beta-diketone family, a tiny part of them has mechanoluminescent properties and none is described as mechanochrome. These molecules are discovered by chance. Current studies do not make it possible to generalize such a mechanism and therefore to anticipate whether or not a molecule possesses the property in question.
Selon d’autres caractéristiques avantageuses et non limitatives de cette composition, prises seules ou selon une combinaison techniquement compatible : According to other advantageous and non-limiting characteristics of this composition, taken alone or in a technically compatible combination:
- elle comprend une matrice liquide ou pâteuse qui contient un composé (F) tel que défini plus haut ; - it comprises a liquid or pasty matrix which contains a compound (F) as defined above;
- elle consiste en une encre ; - it consists of an ink;
- ladite encre est une encre liquide, notamment de viscosité comprise entre 0,01 et 1 Pa.s à 25 °C, ou une encre grasse, notamment de viscosité supérieure ou égale à 5 Pa.s à 25°C ; - said ink is a liquid ink, in particular with a viscosity of between 0.01 and 1 Pa.s at 25° C., or a greasy ink, in particular with a viscosity greater than or equal to 5 Pa.s at 25° C.;
- ladite encre est une encre pour impression selon l’une des techniques suivantes : offset, taille-douce, typographie, flexographie, héliogravure, jet d’encre et sérigraphie ; - the said ink is an ink for printing using one of the following techniques: offset, intaglio, typography, flexography, rotogravure, inkjet and screen printing;
- ladite encre est une encre à séchage par rayons ultraviolets ou à séchage oxydatif, c'est-à-dire par contact avec l’oxygène environnant ; - said ink is an ink drying by ultraviolet rays or oxidative drying, that is to say by contact with the surrounding oxygen;
- dans l’encre, ledit composé (F) est présent à hauteur de 1 à 30% en poids. - in the ink, said compound (F) is present at a level of 1 to 30% by weight.
La présente invention se rapporte également à un document de sécurité tel qu’un billet de banque ou un passeport, caractérisé par le fait qu’il comporte en son sein et/ou en surface un composé (F) décrit plus haut. The present invention also relates to a security document such as a banknote or a passport, characterized in that it comprises within it and/or on the surface a compound (F) described above.
Dans un mode de réalisation particulier de ce document, le composé est incorporé dans une encre. In a particular embodiment of this document, the compound is incorporated into an ink.
Dans une variante, ce composé est dispersé dans la masse du document. In a variant, this compound is dispersed in the mass of the document.
Avantageusement, quand le document incorpore au moins un fil de sécurité, ledit composé est apposé à la surface dudit fil. Advantageously, when the document incorporates at least one security thread, said compound is affixed to the surface of said thread.
Avantageusement, quand le document incorpore au moins un film, notamment un foil, une bande de lamination ou un patch, ledit composé est apposé à la surface dudit film, notamment dudit foil, de ladite bande de lamination ou dudit patch. Advantageously, when the document incorporates at least one film, in particular a foil, a lamination strip or a patch, said compound is affixed to the surface of said film, in particular of said foil, of said lamination strip or of said patch.
Un autre aspect de l’invention se rapporte à un procédé d’authentification d’un document tel que décrit plus haut, ledit document comportant au moins une première région revêtue dudit composé, ainsi qu’au moins une région additionnelle qui est revêtue d’une impression de la même couleur que ledit composé lorsqu’il est soumis à une excitation mécanique, mais qui est dépourvue dudit composé, qui comprend les étapes suivantes : Another aspect of the invention relates to a method for authenticating a document as described above, said document comprising at least a first region coated with said compound, as well as to the minus one additional region which is coated with an imprint of the same color as said compound when subjected to mechanical excitation, but which is free of said compound, which comprises the following steps:
- excitation mécanique de ladite première région de manière à provoquer le changement de couleur dudit composé ; - mechanical excitation of said first region so as to cause the color change of said compound;
- comparaison de cette couleur avec celle de ladite région additionnelle. - comparison of this color with that of said additional region.
DESCRIPTION DES FIGURES DESCRIPTION OF FIGURES
D'autres caractéristiques et avantages de l'invention apparaîtront de la description qui va maintenant en être faite, en référence aux dessins annexés, qui en représentent, à titre indicatif mais non limitatif, différents modes de réalisation possibles. Other characteristics and advantages of the invention will appear from the description which will now be made of it, with reference to the appended drawings, which represent, by way of indication but not limitation, various possible embodiments.
Sur ces dessins : In these drawings:
- la figure 1 est une vue partielle de dessus d’un billet de banque dont une zone a été recouverte d’un aplat d’encre incorporant le composé selon l’invention, dans un premier état dans lequel ladite zone n’est soumise à aucune contrainte mécanique ; - Figure 1 is a partial top view of a banknote, one area of which has been covered with a flat area of ink incorporating the compound according to the invention, in a first state in which said area is not subjected to no mechanical stress;
- la figure 2 est une vue analogue à la figure 1 , dans laquelle ladite zone a été soumise à une contrainte mécanique, par exemple par grattage partiel de sa surface, puis a été exposée à un rayonnement ultraviolet ; - Figure 2 is a view similar to Figure 1, in which said area has been subjected to mechanical stress, for example by partial scraping of its surface, and then has been exposed to ultraviolet radiation;
- la figure 3 est une vue de dessus d’une variante de réalisation du billet des figures précédentes, dans laquelle ladite zone incorpore un détrompeur. - Figure 3 is a top view of an alternative embodiment of the ticket of the previous figures, in which said zone incorporates a polarizer.
DESCRIPTION DETAILLEE DE L'INVENTION DETAILED DESCRIPTION OF THE INVENTION
Ainsi que cela a été indiqué plus haut, la présente invention se rapporte en premier lieu à un composé F tel que défini plus haut. As indicated above, the present invention relates primarily to a compound F as defined above.
Un exemple de synthèse possible d’une telle molécule est donné ci-après. An example of a possible synthesis of such a molecule is given below.
Cette synthèse s’opère en 3 étapes : This synthesis takes place in 3 steps:
Etape 1 : Une solution de chlorure d’acyle (3,92g, 0,05moles) dans 10ml de dichlorométhane est ajoutée goutte à goutte à une solution contenant 12,3g de triphénylamine (0,05moles) et 6,81g de ZnCl2 (0,05moles) dans 10ml de dichlorométhane. L’ensemble est chauffé à reflux pendant la nuit. Step 1 : A solution of acyl chloride (3.92g, 0.05moles) in 10ml of dichloromethane is added dropwise to a solution containing 12.3g of triphenylamine (0.05moles) and 6.81g of ZnCl2 (0.05moles) in 10ml of dichloromethane. The whole is heated under reflux overnight.
Après refroidissement, le milieu réactionnel est versé dans 150ml de solution de HCl 2M. Après séparation des phases, la phase organique est lavée à l’eau jusqu’à pH neutre. Après évaporation du solvant, le produit est purifié par recristallisation à chaud dans l’éthanol pour donner une poudre blanche (8,61g, 60%). After cooling, the reaction medium is poured into 150 ml of 2M HCl solution. After separation of the phases, the organic phase is washed with water until neutral pH. After evaporation of the solvent, the product is purified by hot recrystallization from ethanol to give a white powder (8.61 g, 60%).
Etape 2 : condensation de Claisen : Step 2: Claisen condensation:
Dans 100ml de toluène, sont introduits la 1 -(4-Diphenylamino- phenylj-ethanone (13,6g, 0,047moles), le 4-tert-butylbenzoate de méthyle (9,03g, 0,0517moles) et le tBuOK (8,44g, 0,0752moles). L’ensemble est chauffé à 70° C pendant la nuit. Into 100ml of toluene are introduced 1-(4-Diphenylamino-phenylj-ethanone (13.6g, 0.047mol), methyl 4-tert-butylbenzoate (9.03g, 0.0517mol) and tBuOK (8. 44g, 0.0752moles) The whole is heated to 70° C. overnight.
Après refroidissement, la réaction est arrêtée par ajout d’une solution aqueuse saturée de NaHCOs puis acidification avec une solution de HCl 2M. Après séparation des phases, la phase organique est lavée avec 3 x 150ml d’eau, puis séchée sur MgSÛ4. After cooling, the reaction is stopped by adding a saturated aqueous solution of NaHCOs then acidification with a 2M HCl solution. After separation of the phases, the organic phase is washed with 3 x 150ml of water, then dried over MgSÛ4.
Après évaporation du solvant, on obtient un solide jaune qui est engagé dans l’étape suivante sans purification supplémentaire. After evaporation of the solvent, a yellow solid is obtained which is used in the next step without additional purification.
Etape 3 : boration Step 3: Boration
Dans un tricol sous argon, la dicétone qui a été obtenue précédemment est mise en solution dans 100 ml de toluène, puis BFs.OEtz (6,38ml, 0,0517moles) est ajouté. L’ensemble est chauffé à 60° C sous agitation pendant la nuit. In a three-necked flask under argon, the diketone which was obtained previously is dissolved in 100 ml of toluene, then BFs.OEtz (6.38 ml, 0.0517 moles) is added. The whole is heated to 60° C. with stirring overnight.
Après refroidissement, la réaction est arrêtée par addition d’une solution saturée en NaHCOs. La phase organique est lavée à l’eau et séchée sur MgSÛ4. Après évaporation du solvant, le produit est purifié par recristallisation à chaud dans du toluène par ajout d’alcool isopropylique. After cooling, the reaction is stopped by adding a saturated solution of NaHCOs. The organic phase is washed with water and dried over MgSÛ4. After evaporation of the solvent, the product is purified by hot recrystallization from toluene by adding isopropyl alcohol.
On obtient ainsi une poudre cristalline rouge (13g, 56%). Celle-ci présente les caractéristiques suivantes : RMN1H (400MHz, CDC13) 5 (ppm) : 8,05 (d, J=8,7Hz, 2H), 7,99 (d, J=9,0Hz, 2H), 7,55 (d, J= 8,7Hz, 2H), 7,43-7,39 (m, 4H), 7,28-7,22 (m, 6H); 7,02 (s, 1H), 7,00 (d, J=9,0Hz, 2H), 1 ,38 (s, 1H). A red crystalline powder (13 g, 56%) is thus obtained. This has the following characteristics: 1H NMR (400MHz, CDC13) 5 (ppm): 8.05 (d, J=8.7Hz, 2H), 7.99 (d, J=9.0Hz, 2H), 7.55 (d, J = 8.7Hz, 2H), 7.43-7.39 (m, 4H), 7.28-7.22 (m, 6H); 7.02 (s, 1H), 7.00 (d, J=9.0Hz, 2H), 1.38 (s, 1H).
Avec cette poudre, on se propose de fabriquer une encre selon la méthodologie suivante. With this powder, it is proposed to manufacture an ink according to the following methodology.
On fabrique dans un premier temps une pâte concentrée à partir de 60% en poids d’une matrice offset portant la référence 9C0000S disponible auprès de la société SICPA et 40% en poids de pigment obtenu précédemment, broyé au broyeur à disques. A concentrated paste is first produced from 60% by weight of an offset matrix bearing the reference 9C0000S available from the company SICPA and 40% by weight of pigment obtained previously, ground in a disc mill.
L’encre finale est préparée par mélange de 50% en poids de la pâte concentrée précédemment obtenue et de 50% en poids de « blanc transparent 9C0000S » (société Sicpa), auxquels on ajoute 3 gouttes de siccatif. The final ink is prepared by mixing 50% by weight of the paste paste previously obtained and 50% by weight of "transparent white 9C0000S" (Sicpa company), to which 3 drops of siccative are added.
On procède ensuite à l’impression d’une bande de papier velin sur un appareil de type IGT modèle AIC2-5. A strip of vellum paper is then printed on an IGT model AIC2-5 type device.
Après séchage de l’encre qui a une couleur orange, lorsque l’on applique un frottement avec une spatule, on observe un changement de couleur de l’orange au rouge à la lumière du jour et de l’orange fluorescent au rouge fluorescent sous éclairage ultraviolet. After drying the ink which has an orange color, when applying a rub with a spatula, a change in color is observed from orange to red in daylight and from fluorescent orange to fluorescent red under ultraviolet lighting.
Ce changement est réversible à température ambiante en environ une heure ou en quelques secondes si on soumet l’encre à une source de chaleur telle qu’un sèche-cheveux. This change is reversible at room temperature in about an hour or in a few seconds if the ink is subjected to a heat source such as a hair dryer.
Cette encre peut être aussi bien une encre liquide qu’une encre grasse, c'est-à-dire une encre visqueuse qui ne coule pas. This ink can be either a liquid ink or a greasy ink, i.e. a viscous ink that does not flow.
Par ailleurs, il peut s’agir d’une encre pour impression selon l’une des techniques suivantes : offset, taille-douce, typographie, flexographie, héliogravure, jet d’encre et sérigraphie. In addition, it may be an ink for printing using one of the following techniques: offset, intaglio, letterpress, flexography, rotogravure, inkjet and screen printing.
Cette encre peut être une encre à séchage par rayons ultraviolets ou à séchage oxydatif, c'est-à-dire par contact avec l’oxygène environnant. This ink can be an ink drying by ultraviolet rays or oxidative drying, that is to say by contact with the surrounding oxygen.
Bien que l’encre ci-dessus convienne à une impression à la surface d’un document de sécurité tel qu’un billet de banque, elle convient également pour revêtir un élément de sécurité tel qu’un fil ou un film, notamment un foil, une bande de lamination ou un patch, notamment en matière plastique, que l’on se propose de positionner au moins partiellement à la surface d’un billet. Although the above ink is suitable for printing on the surface of a security document such as a banknote, it is also suitable for coating a security element such as a thread or a film, in particular a foil , a lamination strip or a patch, in particular made of plastic material, which it is proposed to position at least partially on the surface of a ticket.
Le composé précité se prête également à une introduction directe au sein d’un document de sécurité, par exemple dans la pâte à papier lorsqu’il s’agit d’un billet ou dans une matière plastique lorsqu’il s’agit d’une carte, par exemple d’identité. The aforementioned compound also lends itself to direct introduction into a security document, for example into paper pulp when it it is a ticket or in a plastic material when it is a card, for example identity.
Aux figures 1 et 2 est représenté schématiquement, vue de face, un document de sécurité qui consiste en un billet de banque 1. Il pourrait toutefois s'agir d'un autre type de document de sécurité tel qu'un visa ou un passeport. Il s'agit donc d'un simple exemple de réalisation. In Figures 1 and 2 is shown schematically, front view, a security document which consists of a banknote 1. It could however be another type of security document such as a visa or a passport. It is therefore a simple example of an embodiment.
Pour des raisons de facilité de lecture des figures, seule la valeur monétaire du billet, en l'occurrence la valeur "10" a été représentée sur cette face visible 2 qui est par exemple la face recto. Bien entendu, ce qui est dit pour la face recto peut être valable pour la face verso 3. For reasons of ease of reading the figures, only the monetary value of the banknote, in this case the value "10" has been represented on this visible face 2 which is for example the front face. Of course, what is said for the front side can be valid for the back side 3.
Toute ou partie des moyens de sécurité habituellement utilisés dans le domaine fiduciaire (hologramme, fil de sécurité, filigrane, impression, etc.) peuvent être intégrés dans ce billet, mais n'y sont volontairement pas représentés. All or part of the security means usually used in the fiduciary field (hologram, security thread, watermark, printing, etc.) can be integrated into this note, but are deliberately not represented there.
L’encre précitée est apposée sur le papier fiduciaire constitutif du billet de banque 1 selon l'une des méthodes connues de l'homme du métier. The aforementioned ink is affixed to the fiduciary paper constituting the banknote 1 according to one of the methods known to those skilled in the art.
Dans l'exemple représenté, il s'agit d'un aplat constituant une zone 4 de forme ovale. In the example represented, it is a solid area constituting an area 4 of oval shape.
Bien entendu, d'autres formes de zones peuvent être envisagées et leur nombre peut être variable. Of course, other shapes of zones can be envisaged and their number can be variable.
A l’état initial, c'est-à-dire en l’absence de tout stress mécanique ou d’apport d’énergie, l’intégralité de la zone 4 présente une même couleur orange Ci. Quand le billet 1 est soumis à un rayonnement ultraviolet R, la zone 4 prend une coloration orange fluorescente. C’est la situation de la figure 1 . In the initial state, that is to say in the absence of any mechanical stress or energy input, the entire zone 4 has the same orange color Ci. When the banknote 1 is subjected to ultraviolet R radiation, zone 4 takes on a fluorescent orange colour. This is the situation in Figure 1.
Lorsque l’on soumet au moins une partie de la zone 4 à un grattage ou à un frottement par exemple avec la tranche d’une pièce de monnaie, alors celle-ci passe de la couleur orange initiale Ci à la couleur rouge C2. When at least part of zone 4 is subjected to scratching or rubbing, for example with the edge of a coin, then this changes from the initial orange color Ci to the red color C2.
Cette méthode, simple à mettre en œuvre et à la portée de toute personne constitue une sécurité de premier niveau qui permet de garantir l’authenticité de la coupure. This method, simple to implement and accessible to anyone, provides first-level security that guarantees the authenticity of the cut.
De plus, quand le billet 1 est soumis à un rayonnement ultraviolet R, par exemple à l’initiative d’un commerçant possédant une lampe à UV, alors, la zone en question prend une coloration rouge fluorescente. Ceci constitue une sécurité de second niveau. L’élément de sécurité ainsi constitué permet donc une double authentification, et en particulier deux authentifications à différents niveaux de sécurité. In addition, when the ticket 1 is subjected to ultraviolet radiation R, for example on the initiative of a tradesman possessing a UV lamp, then the zone in question takes on a fluorescent red colour. This is second level security. The security element thus formed therefore allows double authentication, and in particular two authentications at different security levels.
Comme indiqué précédemment, la molécule de formule F, sous l’éclairage de la lumière du jour D65 est orange (L* = 84,22, a* = 24,93, b* = 57,29 selon CIE DE2000). As indicated previously, the molecule of formula F, under the illumination of daylight D65 is orange (L* = 84.22, a* = 24.93, b* = 57.29 according to CIE DE2000).
Lorsqu’elle est excitée, c'est-à-dire lorsqu’on lui apporte de l’énergie mécaniquement, elle passe au point de contact à la couleur rouge (L* = 77,86, a* = 32,54, b* = 61 ,51 selon CIE DE2000). Ces couleurs, bien que différentes, sont proches. When it is excited, i.e. when energy is brought to it mechanically, it changes at the point of contact to the color red (L* = 77.86, a* = 32.54, b * = 61.51 according to CIE DE2000). These colors, although different, are close.
Si un utilisateur exercé tel qu’un professionnel ne s’y trompe pas, la différence de couleur est plus difficile à appréhender pour l’homme de la rue. If an experienced user such as a professional is not mistaken, the difference in color is more difficult to grasp for the man in the street.
La solution illustrée à la figure 3 permet de pallier cette difficulté.The solution illustrated in FIG. 3 overcomes this difficulty.
Ainsi, comme dans le mode de réalisation précédent, le billet comporte une zone 4 réalisée sous la forme d’un aplat. Thus, as in the previous embodiment, the ticket includes an area 4 made in the form of a solid area.
Elle est toutefois réalisée en deux régions distinctes 40 et 41 . However, it is made in two distinct regions 40 and 41 .
La région 40 est revêtue, comme dans le cas précédent, d’une encre incorporant le composé F précité. Elle jouxte une seconde région 41 qui est revêtue d’une impression de couleur rouge, de teinte identique à celle identifiée C2, mais dépourvue de composé F. Region 40 is coated, as in the previous case, with an ink incorporating the aforementioned compound F. It adjoins a second region 41 which is coated with an impression of red color, of a shade identical to that identified C2, but devoid of compound F.
Dans ces conditions, dès que lorsqu’on excite mécaniquement une partie de la région 40, elle passe à la couleur rouge, selon une teinte que l’on peut comparer immédiatement à celle de la région 41 . Under these conditions, as soon as part of region 40 is mechanically excited, it changes to the color red, according to a hue that can be immediately compared to that of region 41 .
Ainsi, si les deux couleurs sont identiques, le billet peut être considéré comme authentique. En revanche, si les couleurs sont différentes (ou si la zone sollicitée ne change pas de couleur), alors il existe un doute sérieux sur l’authenticité, de sorte que le document doit être étudié de manière plus approfondie. Thus, if the two colors are identical, the banknote can be considered authentic. On the other hand, if the colors are different (or if the requested area does not change color), then there is a serious doubt about the authenticity, so the document must be investigated further.
Bien entendu, les régions 40 et 41 peuvent prendre une autre forme que celle représentée ici. Elles peuvent par exemple être graphiquement travaillées pour être intimement imbriquées. Of course, regions 40 and 41 can take a form other than that shown here. They can for example be graphically worked to be intimately nested.
Ci-après sont décrits des exemples de synthèse d'autres molécules de formule (F). Examples of the synthesis of other molecules of formula (F) are described below.
Exemple supplémentaire 1 : On se propose de synthétiser la molécule (F) suivante : Additional example 1: We propose to synthesize the following molecule (F):
Etape 1 : Step 1 :
Dans 45ml de diméthylformamide, du bromooctadodécane (33,34g 0,10mole), du méthyl parabène (15g, 0,10mole) et du carbonate de potassium (14,99g, 0,11 mole) sont chauffés à 85 °C pendant toute une nuit. In 45ml of dimethylformamide, bromooctadodecane (33.34g 0.10mole), methyl paraben (15g, 0.10mole) and potassium carbonate (14.99g, 0.11mole) are heated at 85°C for a whole night.
Après refroidissement, 100ml d’eau sont ajoutés. Le précipité est repris dans du dichlorométhane et la phase aqueuse est extraite avec du dichlorométhane. La phase organique est séchée sur MgSÛ4 puis le solvant est évaporé. On obtient un solide blanc (38g, 95% de rendement). After cooling, 100ml of water is added. The precipitate is taken up in dichloromethane and the aqueous phase is extracted with dichloromethane. The organic phase is dried over MgSÛ4 then the solvent is evaporated off. A white solid is obtained (38 g, 95% yield).
Etape 2 : 2nd step :
Dans 100ml de toluène, sont introduits de la 1 -(4-Diphenylamino-phenyl)- ethanone (5g, 0,02mole), l’intermédiaire obtenu à l'étape 1 ci-dessus (9,71g, 0,024mole) et du tBuOK (3,12g, 0,03mole). L’ensemble est chauffé à 70° C pendant la nuit. In 100ml of toluene, are introduced 1 - (4-Diphenylamino-phenyl) - ethanone (5g, 0.02mole), the intermediate obtained in step 1 above (9.71g, 0.024mole) and tBuOK (3.12g, 0.03mole). The whole is heated to 70°C overnight.
Après refroidissement, la réaction est arrêtée par ajout d’une solution aqueuse saturée de NaHCOs puis acidification avec une solution de HCl 2M. Après séparation des phases, la phase organique est lavée avec 3 X 150ml d’eau, puis séchée sur MgSÛ4. After cooling, the reaction is stopped by adding a saturated aqueous solution of NaHCOs then acidification with a 2M HCl solution. After separation of the phases, the organic phase is washed with 3 X 150ml of water, then dried over MgSÛ4.
Après évaporation du solvant, on obtient un solide jaune qui est engagé dans l’étape suivante sans purification supplémentaire. After evaporation of the solvent, a yellow solid is obtained which is used in the next step without additional purification.
Etape 3 : Dans un tricol sous argon, la dicétone qui a été obtenue à l'étape 2 est mise en solution dans 120 ml de toluène, puis BF3.OEt2 (2,71ml, 0,022mole) est ajouté. L’ensemble est chauffé à 60° C sous agitation pendant la nuit. Step 3: In a three-necked flask under argon, the diketone which was obtained in step 2 is dissolved in 120 ml of toluene, then BF3.OEt2 (2.71 ml, 0.022 mol) is added. The whole is heated to 60° C. with stirring overnight.
Après refroidissement, la réaction est arrêtée par addition d’une solution saturée en NaHCOs. La phase organique est lavée à l’eau et séchée sur MgSÛ4. Après évaporation du solvant, le produit est purifié par chromatographie sur gel de silice, éluant DCM/Heptane (80/20). On obtient une poudre jaune-orangée (1 ,5g, 10% de rendement). Celle-ci présente les caractéristiques suivantes : After cooling, the reaction is stopped by adding a saturated solution of NaHCOs. The organic phase is washed with water and dried over MgSÛ4. After evaporation of the solvent, the product is purified by chromatography on silica gel, eluent DCM/Heptane (80/20). A yellow-orange powder (1.5 g, 10% yield) is obtained. This has the following characteristics:
RMN 1H (400Hz, CDC13) ô (ppm) : 8,09 (d, J=8Hz, 2H), 7,97 (d, J=8Hz, 2H), 7,41 (m, 4H), 7,23 (m, 6H), 6,99 (m, 5H), 4,08 (m, 2H), 1 ,84 (m,2H), 1 ,39- 1 ,28 (m, 30H), 0,90 (t, J=8Hz, 3H). 1H NMR (400Hz, CDC13) δ (ppm): 8.09 (d, J=8Hz, 2H), 7.97 (d, J=8Hz, 2H), 7.41 (m, 4H), 7.23 (m, 6H), 6.99 (m, 5H), 4.08 (m, 2H), 1.84 (m,2H), 1.39-1.28 (m, 30H), 0.90 ( t, J=8Hz, 3H).
Exemple supplémentaire 2 : Additional example 2:
On se propose de synthétiser la molécule (F) suivante : We propose to synthesize the following molecule (F):
Cette synthèse est réalisée selon le même protocole que décrit de l'exemple précédent ( mais avec utilisation du bromodécane au lieu du bromooctadécane).This synthesis is carried out according to the same protocol as described in the preceding example (but with the use of bromodecane instead of bromooctadecane).
Après purification par chromatographie sur gel de silice, éluant heptane/ dichlorométhane (70/30) et une recristallisation TBME/heptane (50/50) à chaud, on obtient une poudre jaune-orangée (3,2g, 12% de rendement) avec les caractéristiques suivantes : After purification by chromatography on silica gel, eluent heptane/dichloromethane (70/30) and hot recrystallization TBME/heptane (50/50), a yellow-orange powder (3.2 g, 12% yield) is obtained with the following characteristics:
RMN 1H (400Hz, CDC13) ô (ppm) : 8,08 (d, J=8Hz, 2H), 7,96 (d, J=8Hz, 2H), 7,40 (m, 4H), 7,24 (m, 6H), 6,98 (m, 5H), 4,07 (t, J=8Hz, 2H), 1 ,83 (m, 2H), 1 ,49 (m, 2H), 1 ,42-1 ,30 (m, 12H), 0,91 (t, J=8Hz, 3H). 1H NMR (400Hz, CDC13) δ (ppm): 8.08 (d, J=8Hz, 2H), 7.96 (d, J=8Hz, 2H), 7.40 (m, 4H), 7.24 (m, 6H), 6.98 (m, 5H), 4.07 (t, J=8Hz, 2H), 1.83 (m, 2H), 1.49 (m, 2H), 1.42- 1.30 (m, 12H), 0.91 (t, J=8Hz, 3H).
Coordonnées colorimétriques des encres correspondantes selon CIE DE2000 (fabriquées selon le même procédé que l’invention) : Colorimetric coordinates of the corresponding inks according to CIE DE2000 (manufactured according to the same process as the invention):

Claims

REVENDICATIONS
1. Composé à la fois mécanochromique et mécanofluorochromique, qui répond à1. Both mechanochromic and mechanofluorochromic compound, which meets
(F) suivante : formule (F) dans laquelle : (F) next: formula (F) in which:
R1 est choisi parmi : R 1 is chosen from:
- une chaîne alkyle en C1 à C4, linéaire ou ramifiée ; - a C1 to C4 alkyl chain, linear or branched;
- une chaîne alcoxy en C1 à C22 ; - a C1 to C22 alkoxy chain;
- un groupement dialkylamino en C1 à C4, et de préférence diméthylamino ;- a C1 to C4 dialkylamino group, and preferably dimethylamino;
- au moins un hétéroatome. - at least one heteroatom.
2. Composé selon la revendication 1 , caractérisé par le fait que R1 est - -CFhh. 2. Compound according to claim 1, characterized in that R 1 is - -CFhh.
3. Composition à usage fiduciaire, caractérisée par le fait qu’elle comprend une matrice liquide ou pâteuse qui contient un composé (F) selon la revendication 1 ou 2. 3. Composition for fiduciary use, characterized in that it comprises a liquid or pasty matrix which contains a compound (F) according to claim 1 or 2.
4. Composition selon la revendication 3, caractérisée par le fait qu’elle consiste en une encre. 4. Composition according to claim 3, characterized in that it consists of an ink.
5. Composition selon la revendication 4, caractérisée par le fait que ladite encre est une encre liquide, notamment de viscosité comprise entre 0,01 et 1 Pa.s à 25 °C, ou une encre grasse, notamment de viscosité supérieure ou égale à 5 Pa.s à 25°C. 5. Composition according to Claim 4, characterized in that the said ink is a liquid ink, in particular with a viscosity of between 0.01 and 1 Pa.s at 25° C., or a greasy ink, in particular with a viscosity greater than or equal to 5 Pa.s at 25°C.
6. Composition selon la revendication 4 ou 5, caractérisée par le fait que ladite encre est une encre pour impression selon l’une des techniques suivantes : offset, taille-douce, typographie, flexographie, héliogravure, jet d’encre et sérigraphie. 6. Composition according to Claim 4 or 5, characterized in that the said ink is an ink for printing according to one of the following techniques: offset, intaglio, typography, flexography, heliogravure, inkjet and screen printing.
7. Composition selon l’une des revendications 3 à 6, caractérisée par le fait que ladite encre est une encre à séchage par rayons ultraviolets ou à séchage oxydatif, c'est-à-dire par contact avec l’oxygène environnant. 7. Composition according to one of Claims 3 to 6, characterized in that the said ink is an ink drying by ultraviolet rays or oxidative drying, that is to say by contact with the surrounding oxygen.
8. Composition selon l’une des revendications 3 à 7, caractérisée par le fait que ledit composé (F) est présent à hauteur de 1 à 30% en poids. 8. Composition according to one of Claims 3 to 7, characterized in that the said compound (F) is present in the amount of 1 to 30% by weight.
9. Document de sécurité (1 ) tel qu’un billet de banque ou un passeport, caractérisé par le fait qu’il comporte en son sein et/ou en surface un composé (F) selon la revendication 1 ou 2. 9. Security document (1) such as a banknote or a passport, characterized in that it comprises within it and / or on the surface a compound (F) according to claim 1 or 2.
10. Document (1) selon la revendication 9 dans lequel ledit composé est en surface, caractérisé par le fait que ledit composé (F) est incorporé dans une encre. 10. Document (1) according to claim 9 wherein said compound is on the surface, characterized in that said compound (F) is incorporated in an ink.
11. Document (1) selon la revendication 9, caractérisé par le fait que ledit composé (F) est dispersé dans sa masse. 11. Document (1) according to claim 9, characterized in that said compound (F) is dispersed in its mass.
12. Document (1 ) selon la revendication 9, qui incorpore au moins un fil de sécurité, caractérisé par le fait que ledit composé est apposé à la surface dudit fil. 12. Document (1) according to claim 9, which incorporates at least one security thread, characterized in that said compound is affixed to the surface of said thread.
13. Document (1) selon la revendication 9, qui incorpore au moins un film, tel qu’un foil, une bande de lamination ou un patch, caractérisé par le fait que ledit composé est apposé sur ledit film. 13. Document (1) according to claim 9, which incorporates at least one film, such as a foil, a lamination strip or a patch, characterized in that said compound is affixed to said film.
14. Procédé d’authentification d’un document (1 ) selon la revendication 9 ou 10, ledit document (1 ) comportant au moins une première région (40) revêtue dudit composé (F), ainsi qu’au moins une région additionnelle (41 ) qui est revêtue d’une impression de la même couleur que ledit composé (F) lorsqu’il est soumis à une excitation mécanique, mais qui est dépourvue dudit composé (F), qui comprend les étapes suivantes : 14. A method of authenticating a document (1) according to claim 9 or 10, said document (1) comprising at least a first region (40) coated with said compound (F), as well as at least one additional region ( 41) which is coated with a print of the same color as said compound (F) when subjected to mechanical excitation, but which is devoid of said compound (F), which comprises the following steps:
- excitation mécanique de ladite première région (40) de manière à provoquer le changement de couleur dudit composé (F) ; - mechanical excitation of said first region (40) so as to cause the color change of said compound (F);
- comparaison de cette couleur avec celle de ladite région additionnelle (41 ). - comparison of this color with that of said additional region (41).
EP21820271.1A 2020-12-22 2021-12-07 Mechanochromic and mechanofluorochromic compound, composition, and fiduciary document using same Pending EP4267588A1 (en)

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WO2009018111A1 (en) 2007-07-27 2009-02-05 The Board Of Trustees Of The University Of Illinois Self-assessing mechanochromic materials
US9074129B2 (en) 2009-12-01 2015-07-07 University Of Virginia Patent Foundation Mechanochromic luminescent difluoroboron beta-diketonates
FR2969034B1 (en) 2010-12-17 2014-02-21 Oberthur Technologies SAFETY DOCUMENT COMPRISING A REVERSIBLE MECANO LUMINESCENT COMPOUND
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US8815771B2 (en) 2012-04-16 2014-08-26 Ppg Industries Ohio, Inc. Mechanochromic coating composition
US9133362B2 (en) 2012-07-16 2015-09-15 Ppg Industries Ohio, Inc. Coating composition having mechanochromic crystals
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