AU2013357287A1

AU2013357287A1 - Composition for fiduciary use and security document using same

Info

Publication number: AU2013357287A1
Application number: AU2013357287A
Authority: AU
Inventors: Xavier Borde; Ella Dermilly; Mahdi EL-SAYED MOUSSA; Julien Gillot; Hubert Le Bozec; Regis Reau
Original assignee: Oberthur Fiduciaire SAS
Current assignee: Oberthur Fiduciaire SAS
Priority date: 2012-12-13
Filing date: 2013-12-13
Publication date: 2015-07-02
Anticipated expiration: 2033-12-13
Also published as: KR20150118099A; RU2656471C2; ZA201504286B; EP2931832A1; RU2015128046A; KR102214415B1; EP2931832B1; AU2013357287B2; CN105026517A; FR2999595B1; BR112015013911A2; PL2931832T3; CA2894433A1; FR2999595A1; WO2014090995A1; BR112015013911B1; CA2894433C; CN105026517B

Abstract

The invention concerns a composition for fiduciary use. It is remarkable in that it comprises a printing matrix that is liquid or pasty before drying, preferably colourless, and a reversible mecanoluminescent compound having the following chemical formula A: Formula (A), in which: - Ar represents a monosubstituted polycyclic aromatic hydrocarbon resulting from the single or multiple fusion of n benzene rings, n being between 4 and 10, - n1 is between 0 and 10, n2 is between 0 and 10, - n1 and n2 not being simultaneously equal to 0, - Y is an organic or heteroorganic group, chosen in particular from the cyano, trifluoromethyl, formyl, ester, nitro, halogen, sulfoxide, sulfonyl, tricyanoethenyl, ammonium and phosphonium groups.

Description

1 COMPOSITION FOR FIDUCIARY USE AND SECURITY DOCUMENT USING SAME The invention relates to the field of the fiduciary industry and more particularly to the manufacture of security documents. The present invention relates firstly to a 5 composition for fiduciary use containing a reversible mechanoluminescent compound and secondly to a security document coated with or containing this composition. The expression securityy document" denotes a document, for example made of paper, plastic or a 10 composite of the two materials, including therein and/or coated with means for protecting the manufacture thereof, so as to render the fraudulent reproduction thereof impossible or at the very least particularly complex, and to ensure the authentication thereof. 15 As such, use is already made, for example for the manufacture of bank notes, of prints produced using inks invisible to the naked eye, but detectable (luminescent) in ultraviolet radiation. Such luminescent (i.e. fluorescent or phosphorescent) inks 6589121_1 (GHMatters) P100181.AU DONNAL 2 in one or a plurality of excitation wavelengths are thus widely used in the security printing field. In such a case, a fraudulently produced photocopy will not reproduce this luminescence effect, forming 5 evidence of the lack of authenticity of the document. However, the use and mass distribution of these inks, particularly in sectors other than fiduciary printing (for example, pharmaceuticals, decorative paint, toys, etc.) has facilitated the procurement 10 thereof via non-secure channels (via the Internet for example) thus making counterfeit easier. The aim of the present invention is thus that of increasing the level of security of documents incorporating these inks further, by proposing various 15 reversible mechanoluminescent compositions, very different to the merely luminescent compositions existing on the market. The term "mechanoluminescence" denotes the capability of a compound of becoming luminescent or 20 changing luminescence colour, or of modifying, preferably increasing, the intensity of the luminescence thereof, under the effect of any mechanical stress, such as pressure, friction or bending. 25 Of the "mechanoluminescent" compounds, the term "triboluminescent" denotes more specifically those exhibiting the aforementioned properties under the effect of friction or scratching using a blunt instrument. 30 The term "reversible" denotes the fact that this compound loses the particular colour or intensity of 6589121_1 (GHMatters) P100181.AU DONNAL 3 the luminescence acquired during the mechanical stress, either in a few minutes at ambient temperature, or in a few seconds after heating. In other words, this compound is restored to the initial state thereof 5 shortly after discontinuing the mechanical stress. According to the article by M. Gorsane et al: "Helicenes: Synthese Photochimique Et Etude Rmn 19F, 13C et 1H De Fluoro-1-Hexahelicenes Et Fluoro-1 Heptahelicenes", Bulletin des Soci6t6 Chimiques Belges, 10 vol. 94, No. 3, 1 January 1985 (1985-01-01), pages 215 231, a compound is known comprising a polycyclic aromatic hydrocarbon resulting from the fusion of 4 benzene rings of which one is substituted by a fluorine group and of which another is substituted by a vinyl 15 benzene type derivative, and which is thus different from the compound according to formula A as proposed in the invention, wherein the polycyclic aromatic hydrocarbon is not substituted by a fluorine group. Furthermore, the compound described in this 20 article is not described as having a luminescence property, let alone mechanoluminescence. According to the article by YOSHIMITSU SAGARA ET AL: "Material Design for Piezochromic Luminescence: Hydrogen-Bond-Directed Assemblies of a Pyrene 25 Derivative", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 129, No. 6, 1 February 2007 (2007-02-01), pages 1520-1521, a mechanoluminescent compound C6TPPy represented in figure 1 is known, but wherein the chemical formula is different from formula A according 30 to the invention. 6589121_1 (GHMatters) P100181.AU DONNAL 4 According to the document US 2009/129053, a compound cited in example 12 is also known which is merely luminescent but not reversibly mechanoluminescent. 5 Finally, according to the document GB 2 232 119, a process for protecting a document using a phosphorus based inorganic triboluminescent compound is known. The aforementioned compound exhibits, however, the specificity of exhibiting persistent triboluminescence, 10 which does not pose problems when the product is present in a substrate for which the verification of the authenticity is merely sought, and which is not intended to be reused. This is particularly the case of entry tickets to a cultural or sports event, for 15 example. On the other hand, in the case of a fiduciary type security document, it is desirable for said document not to visually bear marks of the mechanical stress previously applied or in any case for said marks not to 20 appear in a particularly conspicuous manner. The aim of the present invention is thus that of resolving these difficulties and addressing the aforementioned shortcomings. To this end, the invention relates to a 25 composition for fiduciary use. According to the invention, this composition comprises a printing matrix that is liquid or pasty before drying, preferably colourless, and a reversible mechanoluminescent compound having the following 30 chemical formula A: 6589121_1 (GHMatters) P100181.AU DONNAL 5 wherein: - Ar represents a monosubstituted polycyclic 5 aromatic hydrocarbon resulting from the single or multiple fusion of n benzene rings, n being between 4 and 10, - nl is between 0 and 10, n2 is between 0 and 10, nl and n2 not being simultaneously equal to 0, 10 - Y is an organic or hetero-organic group, chosen in particular (preferably, chosen exclusively) from the cyano, trifluoromethyl, formyl, ester, nitro, halogen, sulphoxide, sulphonyl, tricyanoethenyl, ammonium and phosphonium groups. 15 According to further advantageous and non-limiting features of the invention, taken alone or in combination: - said compound having chemical formula A is present therein at a rate of 0.1% to 25% by weight, 20 preferably from 1% to 10% by weight, more preferably from 3% to 8% by weight, - Ar is a pyren-1-yl group, - Ar is a benzo[c]phenantren-2-yl group, - said reversible mechanoluminescent compound is 25 compound A wherein Ar is a pyren-1-yl group, nl is equal to 0 and n2 is equal to 1, 6589121_1 (GHMatters) P100181.AU DONNAL 6 - said reversible mechanoluminescent compound is compound A wherein Ar is a benzo[c]phenantren-2-yl group, nl is equal to 1 and n2 is equal to 1, - said reversible mechanoluminescent compound is 5 compound A wherein Ar is a pyren-1-yl group, nl is equal to 0 and n2 is equal to 2, - said reversible mechanoluminescent compound is compound A wherein Ar is a benzo[c]phenantren-2-yl group, nl is equal to 1 and n2 is equal to 0, 10 - Y is the CN group, - said printing matrix is an ink or a varnish, - said matrix is chosen from an offset, screen, intaglio, letterpress (typography), flexographic, ink jet, direct coating or photo-engraving printing matrix. 15 The invention also relates to a security document, such as a bank note, a chip card or a passport, coated with and/or containing a reversible mechanoluminescent compound having the following chemical formula A: Ar 20 wherein: - Ar represents a monosubstituted polycyclic aromatic hydrocarbon resulting from the single or 25 multiple fusion of n benzene rings, n being between 4 and 10, - nl is between 0 and 10, n2 is between 0 and 10, nl and n2 not being simultaneously equal to 0, 6589121_1 (GHMatters) P100181.AU DONNAL 7 - Y is an organic or hetero-organic group, chosen in particular, (preferably chosen exclusively), from the cyano, trifluoromethyl, formyl, ester, nitro, halogen, sulphoxide, sulphonyl, tricyanoethenyl, 5 ammonium and phosphonium groups. According to further advantageous and non-limiting features of the invention, taken alone or in combination: - said reversible mechanoluminescent compound 10 having formula A is on the surface, it takes the form of a print and it is initially contained before drying in a composition such as that cited above, - said print has a thickness between 1 pm and 200 pm, 15 - said print containing said reversible mechanoluminescent compound having formula A is coated with a varnish, intended to completely or partially coat the prints featuring on the security document, - said print containing said reversible 20 mechanoluminescent compound having formula A is coated with a continuous film made of polymer material, intended to completely or partially coat the prints featuring on the security document, - the document comprises a security element 25 consisting of at least one printed area, said printed area having: - a first colour which may be colourless, in the visible light spectrum, - a second colour different from the first in 30 ultraviolet light, and 6589121_1 (GHMatters) P100181.AU DONNAL 8 - a third colour different from said first and second colours or a modification of the intensity of the luminescence thereof, when said printed area is subjected to mechanical 5 stress also in ultraviolet light, the third colour or the modification of the intensity of the luminescence of the second colour of said printed area appearing at the location of said mechanical stress. 10 - the document comprises a security element consisting of at least one printed area, for example in the form of a uniform tint area, at least one pattern being printed on this area, by way of example and without being restrictive, by offset, screen or 15 intaglio printing, using the aforementioned composition, - said area and said pattern exhibiting in the visible light spectrum, a first identical or substantially identical colour, which may be colourless; 20 - said area and said pattern exhibiting in ultraviolet light, a second identical or substantially identical colour, different from said first colour; - said pattern exhibiting a third colour, 25 different from the first and second colours or a modification of the intensity of the luminescence thereof, when this pattern is subjected to mechanical stress also in ultraviolet light, the third colour or the 30 modification of the intensity of the luminescence of the second colour of said 6589121_1 (GHMatters) P100181.AU DONNAL 9 pattern appearing at the location of said mechanical stress. - the document comprises a security element consisting of at least one printed area, for example in 5 the form of a uniform tint area, at least one pattern being printed on this area, by way of example and without being restrictive, by offset, screen or intaglio printing, using a composition such as that cited above, 10 - said area and said pattern respectively exhibiting a first colour and a second colour which are different in the visible light spectrum; - said area and said pattern respectively 15 exhibiting a third colour different from the first colour and a fourth colour different from the second colour, in ultraviolet light; - said pattern exhibiting a fifth colour, different to the previous colours or a 20 modification of the intensity of the luminescence of the fourth colour, when subjected to mechanical stress, also in ultraviolet light. - the document comprises a security element 25 consisting of at least one printed area, for example in the form of a uniform tint area, at least one pattern being printed on this area, by way of example and without being restrictive, by offset, screen or intaglio printing, using a composition such as that 30 cited above, along with at least one abrasive textured region, such that by overlaying the abrasive textured 6589121_1 (GHMatters) P100181.AU DONNAL 10 region on said pattern and applying mechanical stress in ultraviolet light, said pattern becomes visible in a different colour to the initial colour thereof or exhibits a modification of the intensity of the 5 luminescence thereof, - the document has a transparent portion and said textured region is incorporated therein, - the document comprises a security element consisting of at least one printed area, for example in 10 the form of a uniform tint area, a plurality of patterns being printed on this area, by way of example and without being restrictive, by offset, screen or intaglio printing, of which at least one is printed using a composition such as that cited above, and it 15 has a transparent portion comprising an abrasive textured region which has the same shape as said pattern printed using said composition, such that by overlaying and applying mechanical stress in ultraviolet light, said pattern becomes visible in a 20 different colour to the initial colour thereof or exhibits a modification of the intensity of the luminescence thereof, - said textured region is obtained by dry stamp embossing or inked intaglio, 25 - the document comprises a security element consisting of at least one printed area, for example in the form of a uniform tint area, at least one pattern comprising two adjacent regions being printed on this area, by way of example and without being restrictive, 30 by offset, screen or intaglio printing, one of these 6589121_1 (GHMatters) P100181.AU DONNAL 11 regions being printed using a composition such as that cited above, - said print, said printed area or said pattern is embodied using one of the following processes: offset, 5 screen, intaglio, typography, flexography, ink-jet, direct coating or photo-engraving. Further features and advantages of the invention will emerge from the description which will now be given, with reference to the appended drawings, 10 representing, for indicative but non-limiting purposes, a possible embodiment. In these drawings: - figures 1A to 1C, 2A to 2C, 3A and 3B, 4A to 4C, 5A to 5C, and 6A to 6C are top views of six examples of 15 embodiments of a security document according to the invention, - and figure 7 is a curve representing the emission spectrum of one of the reversible mechanoluminescent compounds used in the invention 20 (expressed in nanometres), before and after friction. The invention relates to a composition for fiduciary use comprising a printing matrix that is liquid or pasty before drying, preferably colourless, and a reversible mechanoluminescent compound having the 25 chemical formula A mentioned above. The term "composition for fiduciary use" denotes a fiduciary document printing composition (i.e. a composition for printing fiduciary documents). The term "printing matrix" denotes a matrix for 30 carrying out printing in or on a document. 6589121_1 (GHMatters) P100181.AU DONNAL 12 Preferably, the compound having formula A is used in the dopant state in this matrix. In any case, it should be noted that Ar is a group monosubstituted by the group represented on the right 5 of formula A. Preferably, Ar is a pyren-1-yl group or a benzo[c]phenantren-2-yl group. The applicant observed that it possible to modulate the colour of the initial fluorescence of the 10 compound having formula A merely by changing the Ar groups or by modifying the length of the conjugated n system. This initial fluorescence colour may be blue, yellow or orange, for example. Furthermore, according to the substituents chosen, 15 it is possible to observe after friction, either a change in the luminescence colour, or an increase in the intensity of this initial luminescence colour. This luminescence may be a fluorescence or a phosphorescence. By way of non-limiting examples, the compound 20 having formula A may more particularly take the form of compounds (I), (II), (III) or (IV) hereinafter: 6I5 6589121_1 (GHMallers) P100181 .AU DONNAL 13 where Y has the same meaning as above. A number of examples of synthesis of various compounds having formula I, II, III and IV will be given hereinafter. 5 Synthesis and examples of compounds having formula I: - Br-kjY I Ck(~h~ C 1, MN E \f The compound 2-ethynylbenzo[ciphenanthrene (a) has previously been described in the literature (see: 10 Tetrahedron Letters 38, No. 12 (1997): 2145-2148). This true alkyne is engaged under conventional conditions in a Sonogashira coupling with 4-bromobenzene para substituted with the group Y sought (product b) in order to arrive at the compound having formula I. These 15 compounds were characterised by proton and carbon NMR spectroscopy and by elemental analyses. General method: Compound I-a: In a Schlenk tube, in argon, 2 20 ethynylbenzo[c]phenanthrene (a) (100 mg, 0.4 mmol), compound (b) (1.1 eq), Pd(PPh3)2Cl2 (5% mol), and CuI (5% mol) are vacuum-dried for one hour, and 10 ml of previously degassed triethylamine is added. The whole is stirred and heated to 70 0 C for 16 hours. After 25 evaporating the solvent, the residue is purified by silica gel chromatography with a 95:5 heptane/ethyl 6589121_1 (GHMatters) P100181.AU DONNAL 14 acetate eluent. Compound I-a is obtained in the form of a yellow powder with a 53% yield.

I

5 The NMR spectroscopy results are as follows: 1H NMR (400 MHz, CDCl3): 9.25 (s, 1H); 9.11 (d, J = 8.4 Hz, 1H); 8.06 (d, J = 7.6 Hz, 1H); 8.03 (d, J = 8.0 Hz, 1H); 7.95 (d, J = 8.4 Hz, 1H); 7.90 (m, 2H); 10 7.85 (d, J = 8.8 Hz, 1H); 7.79-7.74 (m, 2H); 7.72-7.67 (m, 5H). 13C NMR (100.6 MHz, CDCl3): 165.2; 133.6; 133.4; 132.2; 132.1; 131.9; 131.4; 130.1; 130.0; 128.8; 128.7; 128.3; 128.2; 128.1; 127.7; 127.1; 127.0; 126.7; 126.6; 15 126.2; 119.8; 118.6; 111.5; 94.8; 88.3. Compound I-b: Compound I-b was synthesised according to the method described above. 98:2 heptane/ethyl acetate eluent. Compound I-b is 20 obtained in the form of a yellow powder with a 65% yield. The NMR spectroscopy results are as follows: 1H NMR (400 MHz, CDCl3) : 10.04 (s, 1H); 9.34 (s, 25 1H); 9.13 (d, J = 8.4 Hz, 1H); 8.06 (d, J = 7.6 Hz, 1H); 8.01 (d, J = 8.0 Hz, 1H); 7.94 (d, J = 8.4 Hz, 1H); 6589121_1 (GHMatters) P100181.AU DONNAL 15 7.91-7.90 (m, 1H); 7.89-7.87 (m, 3H); 7.83 (d, J = 8.8 Hz, 1H); 7.78-7.76 (m, 2H); 7.76-7.75 (m, 1H); 7.70 7.66 (m, 1H). 13C NMR (100.6 MHz, CDC13) : 191.4; 135.4; 133.7; 5 133.3; 132.2; 131.8; 131.4; 130.1; 130.0; 129.7; 129.6; 128.8; 128.7; 128.4; 128.1; 128.0; 127.7; 127.1; 127.0; 126.7; 126.6; 126.2; 120.1; 94.5; 89.2. Compound I-c: Compound I-c was synthesised according to the same 10 method. 98:2 heptane/ethyl acetate eluent, followed by recrystallisation in a dichloromethane/pentane mixture. Compound I-c is obtained in the form of a pale yellow powder with a 60% yield. 15 The NMR spectroscopy results are as follows: 1H NMR (400 MHz, CDCl3) : 9.33 (s, 1H) ; 9.13 (d, J = 8.4 Hz, 1H); 8.39 (d, J = 7.2 Hz, 1H); 8.00-7.96 (m, 3H); 7.92 (d, J = 8.4 Hz, 1H); 7.88 (d, J = 8.8 Hz, 1H); 20 7.85 (d, J = 8.4 Hz, 1H) ; 7.82 (d, J = 8.8 Hz, 1H); 7.79-7.74 (m, 2H); 7.70-7.65 (m, 3H); 2.62 (s, 3H). 13C NMR (100.6 MHz, CDCl3) : 197.3; 136.2; 133.6; 133.3; 131.8; 131.7; 131.4; 130.1; 130.0; 128.7; 128.6; 128.5; 128.3; 128.1; 128.0; 127.8; 127.1; 127.0; 126.7; 25 126.6; 126.2; 120.3; 93.8; 89.2; 26.6. Compound I-d: Compound I-d was synthesised according to the same method. 6589121_1 (GHMatters) P100181.AU DONNAL 16 98:2 heptane/ethyl acetate eluent, followed by recrystallisation in a dichloromethane/pentane mixture. Compound I-d is obtained in the form of a pale yellow powder with a 55% yield. OCK 5 The NMR spectroscopy results are as follows: 1H NMR (400 MHz, CDCl3) : 9.33 (s, IH) ; 9.12 (d, J = 8.0 Hz, 1H); 8.07-8.04 (m, 3H); 8.00 (d, J = 8.0 Hz, 1H); 7.95 (d, J = 8.4 Hz, 1H); 7.94-7.88 (m, 2H); 7.83 10 (d, J = 8.0 Hz, 1H); 7.81-7.76 (m, 2H); 7.71-7.67 (m, 3H); 3.95 (s, 3H). 13C NMR (100.6 MHz, CDCl3) : 166.6; 133.6; 133.3; 131.7; 131.6; 131.4; 130.2; 130.1; 130.0; 129.6; 129.5; 128.7; 128.6; 128.5; 128.1; 128.0; 127.8; 127.1; 127.0; 15 126.7; 126.0; 126.15; 120.4; 93.4; 89.2; 52.2. These four compounds have the property of mechanoluminescence or more specifically of mechanofluorochromism (emission of fluorescent colour after mechanical excitation). When they are deposited 20 on a paper sheet, they are fluorescent blue. After mechanical disruption using a spatula, this fluorescence becomes more intense. This variation in intensity is perfectly visible to the naked eye. Return to the initial state takes place in a few seconds by 25 heating (100'C) or in a few minutes at ambient temperature. The results of tests performed with compound I-c are shown by way of example in figure 7. When compound I-c is deposited on fiduciary paper, a blue 6589121_1 (GHMatters) P100181.AU DONNAL 17 fluorescence is observed. The emission spectrum shows a very wide and low-intensity band with a peak at 448 nm (solid-line curve) . After friction, and in ultraviolet light, a slight shift in this wide band centred on 5 465 nm is observed, accompanied by a significant increase in the intensity of this fluorescence (dotted line curve). This spectrum clearly shows a great difference in emission between a weakly fluorescent state, in the initial state, and a strongly fluorescent 10 state after friction. Synthesis and example of a compound having formula II. Nal 17:1 The compounds of family II are obtained by means 15 of a Wadsworth-Emmons reaction on pyrene-1-carbaldehyde in the presence of diethylphosphonate substituted in position 4 by the group Y. Compound II-a: In a Schlenk tube, in argon, diethylphosphonate 20 having the group Y (5.90 mmol, 1 eq) is added to a suspension of NaH (720 mg) in 100 ml of freshly distilled Tetrahydrofuran (THF). The mixture is stirred for 2 hours at ambient temperature, and pyrene-1 carbaldehyde (1 eq) is added. After stirring at ambient 25 temperature overnight, the mixture is filtered on silica. Compound II-a is obtained after evaporating the solvent and recrystallisation in a 6589121_1 (GHMatters) P100181.AU DONNAL 18 dichloromethane/pentane mixture in the form of a solid with a 67% yield. /\f \CN 5 The NMR spectroscopy results are as follows: 1H NMR (500 MHz, CDCl 3 ): 5 = 7.23 (d, J = 16.0 Hz, 1 H), 7.62 (s (!), 4 H), 7.99 - 8.08 (m, 3 H), 8.11 8.15 (m, 2 H), 8.18 - 8.20 (m, 3 H), 8.25 (d, J = 8.0 10 Hz, 1 H), 8.40 (d, J = 9.6 Hz, 1 H). 13C NMR (126 MHz, CDCL 3 ): 5 = 110.5, 119.0, 122.5, 123.6, 124.8, 125.0, 125.1, 125.4, 125.7, 126.2, 126.9, 127.4, 127.8, 128.0, 128.7, 129.1, 129.4, 130.5, 130.7, 131.4, 131.5, 132.5, 142.0. 15 Our study shows that this compound has the property of reversible mechanofluorochromism. In the pure state, when spread onto paper, the initial fluorescence thereof is yellow. Following mechanical disruption such as friction with a spatula, this 20 fluorescence colour turns orange. Return to the initial yellow fluorescence colour takes place in a few minutes at ambient temperature or in a few seconds by heating (100-C). Synthesis and example of a compound having formula 25 111: 6589121_1 (GHMatters) P100181.AU DONNAL 19 \ ~ QHO The aldehyde I-b obtained above is engaged in a Wadsworth-Emmons reaction in the presence of diethylphosphonate substituted in position 4 by the 5 group Y, in order to arrive at compound III. Synthesis method of compound III-a: The aldehyde (I-b) obtained above is engaged in a Wadsworth-Emmons reaction in order to arrive at compound III-a. Z4D-HO C Nt 10 Nt-TH In a Schlenk tube, in argon, diethyl-4 cyanobenzylphosphonate (c) (134 mg, 0.563 mmol) is added to a suspension of NaH (70 mg, 2.92 mmol) in 70 ml of freshly distilled Tetrahydrofuran (THF) . The 15 mixture is stirred for 2 hours at ambient temperature, and 4-(benzo[c]phenanthren-2-ylethynyl)benzaldehyde (I b) is added. After stirring at ambient temperature overnight, the mixture is filtered on silica. Compound III-a is obtained after evaporating the 20 solvent and recrystallisation in a dichloromethane/pentane mixture in the form of a yellow solid (204 mg), with an 80% yield. The NMR spectroscopy results are as follows: 6589121_1 (GHMatters) P100181.AU DONNAL 20 1H NMR (400 MHz, CDCl3): 9.35 (s, 1H) ; 9.17 (d, J = 8.5 Hz, 1H); 8.07 (d, J = 7.5 Hz, 1H); 8.03 (d, J = 8.0 Hz, 1H); 7.96 (d, J = 8.5 Hz, 1H); 7.92 (d, J = 8.5 Hz, 1H); 7.88 (d, J = 8.5 Hz, 1H); 7.86 (d, J = 8.5 Hz, 5 1H); 7.81 -7.77 (m, 2H); 7.71-7.65 (m, 5H); 7.61 (d, J = 8.0 Hz, 2H); 7.57 (d, J = 8.0 Hz, 2H); 7.24 (d, J = 16 Hz, 1H); 7.15 (d, J = 16Hz, 1H). 13C NMR (100.6 MHz, CDCl3) : 90.0; 92.0; 110.8; 119.0; 120.1; 123.5; 126.1; 126.6; 126.8; 126.9 (5 10 peaks); 127.0; 127.1; 127.5; 127.8; 127.9; 128.5; 128.6; 128.7; 130.1; 130.2; 131.4; 131.5; 131.6; 132.2; 132.5 (2 signals); 132.5 (2 signals); 133.1; 133.6; 136.2; 141.5. In the pure solid state, this compound III-a has 15 the property of reversible mechanofluorochromism. When spread onto paper, the initial fluorescence thereof is blue (2 emission bands at 447 nm and 469 nm). Following mechanical disruption such as friction with a spatula, this fluorescence colour turns green (475 nm). Return 20 to the initial blue fluorescence colour takes place in a few minutes at ambient temperature or in a few seconds by heating (100 0 C). Synthesis and example of a compound having formula IV: 6589121_1 (GHMatters) P100181.AU DONNAL 21 In a first step, the cyano function of compound II-a is reduced by DiBAl-H and then hydrolysed. The compound (d) obtained is then engaged in a 5 Wadsworth-Emmons reaction in the presence of diethylphosphonate substituted in position 4 by the group Y, which makes possible to obtain compound IV-a. Compound IV-a: 10 In a first step, the cyano function of compound II-a is reduced by DiBAl-H and then hydrolysed. The compound (d) obtained is then engaged in a Wadsworth-Emmons reaction in the presence of 15 phosphonate (c), so as to obtain compound IV-a. 6589121_1 (GHMatters) P100181.AU DONNAL 22 Method: In a Schlenk tube, in argon, (E)-4-(2-(pyren-1 yl)vinyl)benzonitrile (300 mg, 0. 91 mmol) is solubilised in 25 ml of toluene. DibAl-H (0.23 ml, 5 1.37 mmol, 1.5 eq) is added and the whole is stirred and heated to 30 0 C overnight. The mixture is hydrolysed by adding an aqueous sulphuric acid solution. The aqueous phase is then extracted with toluene. The organic phase is dried on MgSO4, filtered and the 10 solvent is evaporated. The product is isolated by silica gel chromatography (95:5 heptane/ethyl acetate eluent), in the form of a yellow powder (150 mg), yield 49%. The product is then engaged in the Wadsworth Emmons reaction under the same conditions as those 15 described for compound III-a. The NMR spectroscopy results are as follows: 1H NMR (CD2Cl2, 400 MHz) : 8.56 (d, J = 9.2 Hz, 1H) ; 8.39 (d, J = 8.0 Hz, 1H); 8.29 (d, J = 16.4 Hz, 1H); 8.22 (d, J = 8.0 Hz, 2H); 8.19 (d, J = 9.2 Hz, 1H); 20 8.09 (s, 2H); 8.03 (m, 1H); 7.75 (d, J = 8.0 Hz, 2H), 7.69-7.63 (m, 7H); 7.42 (d, J = 16.0 Hz, 1H); 7.30 (d, J = 16.4 Hz, 1H); 7.20 (d, J = 16.0 Hz, 1H). 13C NMR (CD2Cl2, 100.6MHz) : 141.8; 138.1; 136.0; 132.6; 132.5; 131.8; 131.5; 131.0; 130.9; 128.4; 127.7; 25 127.4 (2 signals); 127.3; 127.2; 126.8; 126.7; 126.1; 125.9; 125.4; 125.4; 125.1 ; 123.5; 122.9; 110.6. In the pure solid state, this compound IV-a has the property of reversible mechanofluorochromism. When spread onto paper, the initial fluorescence thereof is 30 orange (A = 585 nm) . Following mechanical disruption such as friction with a spatula, this fluorescence 6589121_1 (GHMatters) P100181.AU DONNAL 23 colour turns yellow-orange. Return to the initial fluorescence colour takes place in a few seconds by heating (100 C). The printing matrix used in the composition for 5 fiduciary use is a matrix that is liquid or pasty before drying, preferably colourless so as not to interfere with the changes in colour or intensity of the compound having formula A cited above. This matrix is for example an ink or a varnish. It 10 may also be chosen from a printing matrix of the following types: - offset, for example a matrix referred to under the terms of the art as "transparent white" bearing the reference 9C00005 available from SICPA, such a matrix 15 essentially consists of siccative plant oils, solvents, resins and additives (fillers, siccative agents, etc.), - screen printing, for example a colourless matrix for ultraviolet drying screen printing, such as that referenced 9ZOD000 from SICPA and essentially 20 consisting of monomers, oligomers and solvents, - intaglio, for example a transparent white matrix, such as that referenced 9SL00205 from SICPA, - letterpress (typography), - flexographic, 25 - ink-jet, - the printing process known to those skilled in the art as "direct coating", - for photo-engraving, - or a carrier suitable for impregnating the paper 30 directly during the manufacture thereof, for example during the sizing step which is a process for 6589121_1 (GHMatters) P100181.AU DONNAL 24 impregnating fibres with a coating solution or slip generally mostly based on PVA (polyvinyl alcohols) and intended to seal the pores of the paper, protect the paper against external damage and facilitate the 5 printing thereof. Advantageously, in the composition for fiduciary use, the compound having formula A is present at a rate of 0.1% to 25% by weight, preferably between 1% and 10% by weight, more preferably between 3% and 8% by weight. 10 The thinner the printing thickness, the higher the percentage of compound A required in the composition for the mechanoluminescence phenomenon to be observable. With thicker printing thicknesses, a lower percentage of the compound having formula A may be used. 15 The prints produced with the fiduciary composition according to the invention are preferably between 1 pm and 200 pm. Three examples of fiduciary compositions are given hereinafter. 20 Example of fiduciary composition No. 1: Compound II-a is introduced at a rate of 5% by weight into a "transparent white" ink or varnish type matrix for intaglio printing. The ink or varnish is then applied onto the fiduciary paper according to 25 methods known to those skilled in the art. In this matrix, the compound is fluorescent yellow. After mechanical disruption using a spatula, an increase in the intensity of the yellow fluorescence is observed. The contrast between the disrupted and non 30 disrupted areas is excellent and easily identifiable. This variation in intensity is reversible at ambient 6589121_1 (GHMatters) P100181.AU DONNAL 25 temperature in a few minutes or in a few seconds by heating. Compound II-a may thus be used as a dopant in a matrix while retaining the property thereof. Example of fiduciary composition No. 2: 5 A second fiduciary composition is obtained by mixing compound III-a at a rate of 5% by weight in a "transparent white" ink or varnish type matrix for intaglio printing. In this matrix, as in the pure state, the compound 10 is fluorescent blue. After mechanical disruption using a spatula, an increase in the intensity of the initial fluorescence is observed. The contrast between the disrupted and non-disrupted areas is very good. Reversibility of the property is obtained in a few 15 seconds by heating (100 C). Example of fiduciary composition No. 3: Compound IV-a is introduced at a rate of 5% by weight into a "transparent white" ink or varnish type matrix for intaglio printing. In this matrix, the 20 compound retains the orange fluorescence thereof. An increase in the intensity of fluorescence after mechanical disruption is also observed in this case. Return to the initial status takes place by heating in a few seconds (100 C). 25 The composition according to the invention including the mechanoluminescent compound having formula A cited above is also suitable for introduction into a security document, for example into the paper pulp in the case of a note or into a plastic material 30 in the case of a card, for example an identity card. 6589121_1 (GHMatters) P100181.AU DONNAL 26 Some examples of embodiments are described hereinafter, with reference to the drawings cited above. As such, figures 6A to 6C represent a first embodiment wherein the document according to the 5 invention consists of a bank note D. As can be seen in figure 6A, the document D comprises a security element 1 consisting of a printed area 2 with an oval contour. This area has a first colour Cl, which may optionally be colourless, in the 10 visible light spectrum. In fluorescent (ultraviolet) light represented in figure 6B, this area 2 is illuminated with a second colour C2, different from the first. Finally, as represented in figure 6C, again in 15 ultraviolet light and at the point subject to mechanical stress (in this case with a blunt instrument T), the printed area 2 takes on a third colour C3, different from said first and second colours Cl, C2 or exhibits a modification of the 20 intensity of the luminescence thereof. A further embodiment will now be described in conjunction with figures 1A to 1C. As shown in figure 1A, this note comprises a security element 1 consisting herein of an area 2 with 25 an oval contour, printed in the form of a block (i.e. uniform tint area) which, alternatively, may be perforated. In this area, a pattern 3 reproducing herein the face value of the bank note, in this instance the 30 figure "100", is printed by means of screen or intaglio printing. 6589121_1 (GHMatters) P100181.AU DONNAL 27 In this embodiment, both the area 2 and the pattern 3 exhibit an identical or substantially identical colour Cl, which may be colourless, in the visible light spectrum. This is thus the situation of 5 figure 1A wherein the pattern 3 is not perceptible, or perceptible with difficulty. This area 2 and the pattern 3, in fluorescent (ultraviolet) light are illuminated by the same colour, or a substantially identical colour in terms of shade, 10 for example in the colour yellow (reference C2 in the figure), (different from the first Cl). Again in fluorescent (ultraviolet) light, friction applied to the security element 1 will induce a change of luminescence (fluorescence) of the pattern 3, and 15 revealing the value "100" in a different fluorescent colour C3, for example orange or will induce a modification of the intensity of the luminescence thereof also revealing the value "100". In the embodiment in figure 2A, the security 20 element 1 consists of an area 2 printed in the form of a block (i.e. uniform tint area) which, alternatively, may be perforated. This area exhibits a colour Cl in the visible light spectrum. A pattern 3, which herein also represents the 25 value "100", is printed on the area 2 by means of screen or intaglio printing and the colour C2 thereof is different from that of the area 2. Under these conditions, the pattern 3 is visible to the naked eye. When the security element is lit by fluorescent 30 lighting, the area 2 and the pattern 3 respectively emit a third colour C3, different from the first 6589121_1 (GHMatters) P100181.AU DONNAL 28 colour Cl and a fourth colour C4, different from the second colour C2. This is the situation in figure 2B. Again in fluorescent light, friction of the security element 1 with a sharp instrument induces a change of 5 fluorescence of the pattern 3, revealing the value "100" in a different fifth colour C5 (see Figure 2C) or in a change of the intensity of the luminescence thereof. With reference to figures 3A and 3B, a note of the 10 same general type as that described above is involved. However, this note comprises an abrasive textured region 5 of paper, ink or a plastic element added to the paper which, in one alternative embodiment, could be a transparent part of the note. This abrasive 15 textured region is for example obtained by dry stamp embossing or inkless intaglio but may also be obtained in an inked version. In the visible light spectrum and as shown in figure 3A, the area 2 and the pattern thereof (hence 20 not distinguishable herein) exhibit the same colour. However, by folding the abrasive textured region 5 over the area 2 and applying friction in ultraviolet light, the pattern 3 of the note is then revealed, by the modification or the colour thereof or of the 25 intensity of fluorescence thereof. This pattern 3 may for example consist of a sequence of figures which may for example by compared with the number of the note, which, referenced 6, is printed on the same side as the pattern 3. 30 With reference to figures 4A to 4C, as in the previous embodiment, an abrasive textured region 5 6589121_1 (GHMatters) P100181.AU DONNAL 29 borne by a transparent portion 4 of the note is involved. The textured region exhibits the shape of the figure "0". 5 Moreover, the area 2 contains three patterns 3, 3' and 3'' which together form the figure "100", the pattern 3' forming the figure "0" being embodied with the mechanoluminescent composition according to the invention, unlike the patterns 3 and 3''. 10 As such, and as shown in figure 4B, once the portion 4 is overlaid and friction of the pattern 3' is applied using the textured area 5 and in ultraviolet light, fluorescence is revealed which may be of an identical colour to that of the patterns 3 and 3'', as 15 represented in figure 4C or a modification of the intensity of the luminescence thereof. Finally, with reference to figures 5A to 5C, a pattern 3 exhibiting two adjacent regions 30 and 31 is involved, the first being printed with a fluorescent 20 ink and the second with the composition for fiduciary use according to the invention. In visible light, the entire pattern is uniformly visible. However, as shown in figure 5B, in fluorescent 25 light, the regions 30 and 31 show different colours. When the region 31 is scratched using a sharp instrument, the colour or the intensity of fluorescence thereof is modified and becomes identical to that of the region 30. This is the situation in figure 5C. 30 In a further embodiment, the two regions 30 and 31 could each be printed with a composition according to 6589121_1 (GHMatters) P100181.AU DONNAL 30 the invention, giving identical fluorescence colours but different colours or intensities after friction. From all the examples described in the present invention, but also the embodiment not described herein, 5 it is easy to understand that an ordinary person, faced with a document, for example a bank note or other document, whereon such a person is in doubt of the authenticity thereof will be able to clear any such doubt immediately by scratching or rubbing the 10 pattern 3 gently in ultraviolet light if said pattern changes intensity or colour of luminescence at the point subject to mechanical stress. The present invention helps, simply and directly, to demonstrate the authenticity of said document and 15 thus obviously increases the level of security of fluorescent and phosphorescent prints. The various tests conducted by the applicant demonstrate that a particularly suitable ultraviolet light wavelength value for inducing the luminescence of 20 the compounds used is 365 nm. A wavelength of 254 nm is also applicable, but with a luminescence reaction of the exposed compound which is less pronounced. The mechanoluminescent compound A may be incorporated into the paper pulp used for the 25 manufacture of the security document, provided obviously that said document is at least partially made of paper, or based on paper. A further method which may be envisaged to affix the mechanoluminescent compound A on the document 30 consists, in a first phase, of depositing same on a hot-transfer film - by means of coating or standard 6589121_1 (GHMatters) P100181.AU DONNAL 31 printing for example - and, in a second phase, of transferring and adhering this film onto the document. It is also possible to carry out cold transfer. Moreover, it would be possible to provide a 5 security document according to the present invention with a third level of authentication. For this purpose, it is possible to incorporate into the composition (ink or varnish), at the same time as the mechanoluminescent compound A, a tracer type element for a third level, 10 for example particular emission features suitable for being detected by an automatic sorting machines (e.g. photodiodes) or off-line equipment (e.g. spectrophotometer, SEM, etc.). Finally, the mechanoluminescent compound A is 15 suitable for being incorporated into a composition compatible with digital printing means (ink-jet for example), for the purposes of document customisation. 6589121_1 (GHMatters) P100181.AU DONNAL

Claims

1. Composition for fiduciary use, characterised in that it comprises a printing matrix that is liquid or pasty before drying, preferably colourless, and a reversible mechanoluminescent compound having the 5 following chemical formula A: A wherein: 10 - Ar represents a monosubstituted polycyclic aromatic hydrocarbon resulting from the single or multiple fusion of n benzene rings, n being between 4 and 10, - nl is between 0 and 10, n2 is between 0 and 10, 15 nl and n2 not being simultaneously equal to 0, - Y is an organic or hetero-organic group, chosen in particular from the cyano, trifluoromethyl, formyl, ester, nitro, halogen, sulphoxide, 6589121_1 (GHMatters) P100181.AU DONNAL 33 sulphonyl, tricyanoethenyl, ammonium and phosphonium groups.

2. Composition according to claim 1, characterised in that the group Y is chosen exclusively from the 5 cyano, trifluoromethyl, formyl, ester, nitro, halogen, sulphoxide, sulphonyl, tricyanoethenyl, ammonium and phosphonium groups.

3. Composition according to claim 1 or 2, characterised in that said compound having chemical 10 formula A is present therein at a rate of 0.1% to 25% by weight, preferably from 1% to 10% by weight, more preferably from 3% to 8% by weight.

4. Composition according to any of claims 1 to 3, characterised in that Ar is a pyren-1-yl group. 15

5. Composition according to any of claims 1 to 3, characterised in that Ar is a benzo[c]phenantren-2 yl group.

6. Composition according to claim 4, characterised in that said reversible mechanoluminescent compound is 20 compound A wherein Ar is a pyren-1-yl group, nl is equal to 0 and n2 is equal to 1.

7. Composition according to claim 4, characterised in that said reversible mechanoluminescent compound is compound A wherein Ar is a pyren-1-yl group, nl is 25 equal to 0 and n2 is equal to 2.

8. Composition according to claim 5, said reversible mechanoluminescent compound is compound A wherein Ar is a benzo[c]phenantren-2-yl group, nl is equal to 1 and n2 is equal to 1. 30

9. Composition according to claim 5, characterised in that said reversible mechanoluminescent compound is 6589121_1 (GHMatters) P100181.AU DONNAL 34 compound A wherein Ar is a benzo[c]phenantren-2-yl group, nl is equal to 1 and n2 is equal to 0.

10. Composition according to any of claims 6 to 9, characterised in that Y is the CN group. 5

11. Composition according to any of the above claims, characterised in that said printing matrix is an ink or a varnish.

12. Composition according to any of claims 1 to 10, characterised in that said matrix is chosen from an 10 offset, screen, intaglio, typography, flexographic, ink-jet, direct coating or photo-engraving printing matrix.

13. Security document, such as a bank note, a chip card or a passport, characterised in that it is coated 15 with and in that it contains a reversible mechanoluminescent compound having the following chemical formula A: A 20 wherein: - Ar represents a monosubstituted polycyclic aromatic hydrocarbon resulting from the single or multiple fusion of n benzene rings, n being 25 between 4 and 10, - nl is between 0 and 10, n2 is between 0 and 10, nl and n2 not being simultaneously equal to 0, 6589121_1 (GHMatters) P100181.AU DONNAL 35 - Y is an organic or hetero-organic group, chosen in particular from the cyano, trifluoromethyl, formyl, ester, nitro, halogen, sulphoxide, sulphonyl, tricyanoethenyl, ammonium and 5 phosphonium groups.

14. Security document according to claim 13, characterised in that the group Y is chosen exclusively from the cyano, trifluoromethyl, formyl, ester, nitro, halogen, sulphoxide, sulphonyl, 10 tricyanoethenyl, ammonium and phosphonium groups.

15. Document according to claim 13 or 14, characterised in that said reversible mechanoluminescent compound having formula A is on the surface, in that it takes the form of a print and in that it is 15 initially contained before drying, in a composition according to any of claims 1 to 12.

16. Document according to claim 15, characterised in that said print has a thickness between 1 pm and 200 pm. 20

17. Document according to claim 15 or 16, characterised in that said print containing said reversible mechanoluminescent compound having formula A is coated with a varnish, intended to completely or partially coat the prints featuring on the security 25 document.

18. Document according to claim 15 or 16, characterised in that said print containing said reversible mechanoluminescent compound having formula A is coated with a continuous film made of polymer 30 material, intended to completely or partially coat the prints featuring on the security document. 6589121_1 (GHMatters) P100181.AU DONNAL 36

19. Document according to any of claims 13 to 18, characterised in that it comprises a security element (1) consisting of at least one printed area (2), said printed area (2) having: 5 - a first colour (Cl) which may be colourless, in the visible light spectrum, - a second colour (C2) different from the first in ultraviolet light, and - a third colour (C3) different from said first 10 and second colours (Cl, C2) or a modification of the intensity of the luminescence thereof, when said printed area (2) is subjected to mechanical stress also in ultraviolet light, the third colour (C3) or the modification of 15 the intensity of the luminescence of the second colour (C2) of said printed area (2) appearing at the location of said mechanical stress.

20. Document according to any of claims 13 to 18, characterised in that it comprises a security 20 element (1) consisting of at least one printed area (2), for example in the form of a uniform tint area, at least one pattern (3) being printed on this area, by way of example and without being restrictive, by offset, screen or intaglio printing, 25 using a composition according to any of claims 1 to 12, - said area (2) and said pattern (3) exhibiting in the visible light spectrum, a first identical or substantially identical 30 colour (Cl), which may be colourless; 6589121_1 (GHMatters) P100181.AU DONNAL 37 - said area (2) and said pattern (3) exhibiting in ultraviolet light, a second identical or substantially identical colour (C2), different from said first colour; 5 - said pattern (3) exhibiting a third colour (C3), different from the first and second colours or a modification of the intensity of the luminescence thereof, when this pattern (3) is subjected to mechanical stress also in 10 ultraviolet light, the third colour (C3) or the modification of the intensity of the luminescence of the second colour (C2) of said pattern (3) appearing at the location of said mechanical stress. 15

21. Document according to any of claims 13 to 18, characterised in that it comprises a security element (1) consisting of at least one printed area (2), for example in the form of a uniform tint area, at least one pattern (3) being printed on 20 this area (2), by way of example and without being restrictive, by offset, screen or intaglio printing, using a composition according to any of claims 1 to 12, - said area (2) and said pattern (3) respectively 25 exhibiting a first colour (Cl) and a second colour (C2) which are different in the visible light spectrum; - said area (2) and said pattern (3) respectively exhibiting a third colour (C3) different from 30 the first colour (Cl) and a fourth colour (C4) 6589121_1 (GHMatters) P100181.AU DONNAL 38 different from the second colour (C2), in ultraviolet light; - said pattern (3) exhibiting a fifth colour (C5), different from the previous colours or a 5 modification of the intensity of the luminescence of the fourth colour, when subjected to mechanical stress, also in ultraviolet light.

22. Document according to any of claims 13 to 18, 10 characterised in that it comprises a security element (1) consisting of at least one printed area (2), for example in the form of a uniform tint area, at least one pattern (3) being printed on this area (2), by way of example and without being 15 restrictive, by offset, screen or intaglio printing, using a composition according to any of claims 1 to 12, along with at least one abrasive textured region (5), such that by overlaying the abrasive textured region (5) on said pattern (3) and 20 applying mechanical stress in ultraviolet light, said pattern becomes visible in a different colour to the initial colour thereof or exhibits a modification of the intensity of the luminescence thereof. 25

23. Document according to claim 22, characterised in that it has a transparent portion (4) and said textured region (5) is incorporated therein.

24. Document according to any of claims 13 to 18, characterised in that it comprises a security 30 element (1) consisting of at least one printed area (2), for example in the form of a uniform tint 6589121_1 (GHMatters) P100181.AU DONNAL 39 area, a plurality of patterns (3, 3', 3'') being printed on this area, by way of example and without being restrictive, by offset, screen or intaglio printing, of which at least one (3') is printed 5 using a composition according to any of claims 1 to 12, and in that it has a transparent portion (4) comprising an abrasive textured region (5) which has the same shape as said pattern (3') printed using said composition, such that by overlaying and 10 applying mechanical stress in ultraviolet light, said pattern (3') becomes visible in a different colour to the initial colour thereof or exhibits a modification of the intensity of the luminescence thereof. 15

25. Document according to any of claims 22 to 24, characterised in that said textured region (5) is obtained by dry stamp embossing or inked intaglio.

26. Document according to any of claims 13 to 18, characterised in that it comprises a security 20 element (1) consisting of at least one printed area (2), for example in the form of a uniform tint area, at least one pattern (3) comprising two adjacent regions (30, 31) being printed on this area, by way of example and without being 25 restrictive, by offset, screen or intaglio printing, one of these regions being printed using a composition according to any of claims 1 to 12.

27. Document according to any of claims 15 to 26, characterised in that said print, said printed 30 area (2) or said pattern (3) is embodied using one of the following processes: offset, screen, 6589121_1 (GHMatters) P100181.AU DONNAL 40 intaglio, typography, flexography, ink-jet, direct coating or photo-engraving. 6589121_1 (GHMatters) P100181.AU DONNAL