AU2011343276B2

AU2011343276B2 - Security document comprising a reversible mecanoluminescent compound

Info

Publication number: AU2011343276B2
Application number: AU2011343276A
Authority: AU
Inventors: Xavier Borde; Ella Dermilly; Julien Gillot; Hubert Le Bozec; Regis Reau
Original assignee: Oberthur Fiduciaire SAS
Current assignee: Oberthur Fiduciaire SAS
Priority date: 2010-12-17
Filing date: 2011-12-16
Publication date: 2015-08-27
Anticipated expiration: 2031-12-16
Also published as: FR2969034A1; CN103415588A; BR112013015222B1; CN103415588B; WO2012080467A1; EP2652083A1; BR112013015222A2; AU2011343276A1; PL2652083T3; CA2820420A1; KR101961397B1; CA2820420C; EP2652083B1; RU2586816C2; FR2969034B1; RU2013132924A; ZA201304382B; KR20140092229A

Abstract

The present invention relates to a security document comprising within it or at the surface a reversible mecanoluminescent compound.

Description

SECURITY DOCUMENT COMPRISING REVERSIBLE MECANOLUMINESCENT COMPOUND 5 The present invention relates to a security document coated with or comprising a reversible mechanoluminescent compound. The present invention can be applied, especially in the field of the fiduciary industry and more particularly in the manufacture of security 10 documents. The expression "security document" means a document, for example made of paper, which includes inside it and/or is coated with means for securing its manufacture so as to make it impossible to 15 reproduce fraudulently, at the very least make it particularly complex, and ensure its authentication. In the technical field of security documents, protection against counterfeiting is done especially by a set of elements integrated into or 20 applied to the support. These security elements are classed according to several levels of security. These securities are usually distributed over three levels.

The security elements of luminescent type are known to the expert, Fluorescent and phosphorescent inks with one or more excitation wavelengths are widely used in the field of printing of security. Equipment 5 for controlling such inks is also well known and used publicly. The use and the widespread dissemination of these inks especially in sectors other than fiduciary printing (pharmacy, decorative paints, toys, etc,) has made them easy to supply via non-secure channels (for example, 10 Internet) making them easier to counterfeit, The aim of the present invention is to further reinforce the level of security of documents integrating fluorescent inks and preserve their ease of authentication. 15 In this way, the invention generally relates to a security document, especially a fiduciary document characterised in that it comprises inside it or at the surface a reversible mechanoluminescent compound. 20 In one aspect, the present invention provides a security document characterised in that it comprises inside it or at the surface a reversible mechanoluminescent compound, wherein said compound corresponds to the following formula: 25 in which n is a whole number between 1 and 4 The prior art in this respect especially comprises documents WO A 2002/062914, WO A 2002/062915, US A 6071632 and G. ZHANG, et al.: "Polymorphism and Reversible Mechanochromic Luminescence for Solid-State Difluoroboron Avobenzone" 5 The term "mechanoluminescent" means the capacity of material to become luminescent (or change luminescence colour) under the effect of any mechanical stress. This added characteristic makes the compound more difficult to produce, such that this complicates its use and reduces 10 fraudulent imitation, The term "reversible" means the fact that this compound loses the colour of the particular luminescence it has acquired during mechanical stressing. This phenomenon occurs in a few minutes, at ambient temperature or by heating. In other terms, this compound regains its initial 5 state shortly after the mechanical stress stops. In accordance with the advantageous and non-limiting characteristics of this document: - said compound is triboluminescent. 10 - said compound is organic. - said compound responds to the following formula: F F 0 B0 n n=1,2,3,4 15 in which n a whole number between 1 and 4. - when said compound is at the surface, it is integrated into ink or varnish.. - the document comprises a security element comprising at least one printed zone, for example in the form of an open-work patch or not, 20 this printing being carried out by a known process such as offset, typography, heliogravure, flexography, screen printing or copper-plate engraving especially, on this zone being printed, for example and without this being limiting, via offset, screen printing or copper-plate engraving, by means of a composition containing a compound such as defined 25 hereinabove, at least one pattern, - said zone and said pattern having a first colour identical in the visible light spectrum, - said zone and said pattern having a second colour, identical under ultra-violet light; - said pattern having a third colour, different to the first and second colours when it is subjected to mechanical stress. 5 - the document comprises a security element comprising at least one printed zone, for example in the form of an open-work patch or not, this printing being carried out by a known process such as offset, typography, heliogravure, flexography, screen printing or copper-plate engraving especially, on this zone being printed, for example and without 10 this being limiting, via offset, screen printing or copper-plate engraving, by means of a composition containing a compound such as defined hereinabove, at least one pattern, - said zone and said pattern having respectively a first and a second colour different in the visible light spectrum; 15 - said zone and said pattern having a third colour identical under ultra-violet light; - said pattern having a fourth colour, different to the preceding colours when it is subjected to mechanical stress. - the document comprises a security element comprising at least 20 one printed zone, for example in the form patch or not, this printing being carried out by a known process such as offset, typography, heliogravure, flexography, screen printing or copper-plate engraving especially, on this zone being printed, for example and without this being limiting, via offset, screen printing or copper-plate engraving, by means of a composition 25 containing a compound such as defined hereinabove, at least one pattern, and at least one abrasive textured region, such that said pattern becomes visible in a colour different to its initial colour by superposition of the abrasive textured region on said pattern and mechanical stress. - the document has a transparent part and said textured region is 30 integrated therein.

- said textured region is obtained by embossing, of copper-plate engraving dry seal type. - the document comprises a security element comprising at least one printed zone, for example in the form of an open-work patch or not, 5 this printing being carried out by a known process such as offset, typography, heliogravure, flexography, screen printing or copper-plate engraving especially, on this zone being printed, for example and without this being limiting, via offset, screen printing or copper-plate engraving, several patterns including one at least by means of a composition 10 containing a compound such as defined hereinabove, and has a transparent part comprising an abrasive textured region which has the same form as said pattern printed by means of said composition, such that by superposition and mechanical stress, said pattern becomes visible in a colour different to its initial colour. 15 - the document comprises a security element comprising at least one printed zone, for example in the form of a patch, this printing being carried out by a known process such as offset, typography, heliogravure, flexography, screen printing or copper-plate engraving especially, on this zone being printed, via offset, screen printing or copper-plate engraving, at 20 least one pattern comprising two adjacent regions, one of these regions being printed by means of a composition containing a compound such as defined hereinabove. - said printed zone is an open-work patch. - said mechanoluminescent compound is used for personalisation 25 of the document. Other characteristics and advantages of the present invention will emerge from the following description. 30 As is pointed out hereinabove, the present invention can make use of a compound such as defined hereinabove.

An example of possible synthesis of such a molecule is given schematically hereinbelow. 0 N0 TsCI O HO O OH _____ -o QnA. NaOH, THF/H 2 0 n K 2 COs, DMF n 1 2 NaH MeO F F THF I 0 n BF OEt 2 Qo~4 0 ~- CHCI 2 5 n 3 This synthesis is carried out in several steps. The first is a step tosylation known from the literature. 10 The second step is Williamson-type coupling between the derivative obtained earlier and 4-hydroxyacetophenone. The third step is a reaction of Claisen condensation type in the 15 presence of 4-fe/f- methyl butyl benzoate, resulting in the corresponding diketones. The fourth and final step is a boration reaction obtained previously by boron trifluoride-etherate, resulting in the compound I" with an overall 20 yield of 30 to 60%. Against all expectations, the present applicant noticed that this molecule has reversible luminescence properties, is relatively soluble in standard solvents, with pairs of characteristic colours, and can be used in low proportions without noticeable impact on the preferred visual effect. The following embodiments were produced. 5 A composition for fiduciary use was manufactured, by using a colourless "offset" matrix or practically colourless known as " transparent white " in industry terms, with reference 9C0000S and available form the company SICPA. This matrix mainly comprises siccative vegetable oils, 10 solvents, resins and additives (charges, siccatives etc). The compound I" which n is equal to 2 for one, and also to 3 was introduced to this matrix at the level of 10% by weight. 15 After fixing to the document and drying, the phenomenon of triboluminescence is observed in both cases and homogeneously over the entire zone subjected to friction. In addition, return to the initial state (colour) is almost 20 instantaneous. In its pure state, as for in the form of the above matrix, initial fluorescence of the colour blue for n = 2 and green for n = 3 is noted. In each case, the colour emitted under the effect of friction is a yellow colour. 25 A second matrix is tested. This is a colourless screen-printing matrix for printing via screen printing with ultra-violet light drying. This reference matrix 9ZOD000, also available from the company SICPA, mainly comprises monomers, oligomers and solvents. 30 A compound is introduced I" which n is equal to 2 at the level of 10% by weight, to which 5% of photoinitiator is added (designated 880337 from SICPA). When exposed to UV light, the photo-initiator initiates chemical reaction by generating reactive forms, free radicals. These 5 trigger a chain reaction binding the oligomers and monomers of the formulation. A reversible triboluminescence phenomenon (colour blue in the initial state and yellow under the effect of friction) is also evident here. 10 Finally, a matrix known as "transparent white" for copper-plate engraving printing is tested. This is the matrix designated 9SL0020S by the company SICPA. 15 The four compounds responding to the above formula are tested at different concentrations. In any case, triboluminescence is observed with good contrast between initial fluorescence (blue or green) and fluorescence after friction 20 (yellow). Return to the initial state occurs rapidly at ambient temperature. At the level of 5% by weight of compound 12 or 13, triboluminescence is clearly observed when a thickness of ink greater than 20 micrometers is used. Between 10 and 20 micrometers, the intensity of the fluorescence initial is low, but the triboluminescence phenomenon is still evident. 25 At a level of 3% by weight of compound 12 or 13, the triboluminescence phenomenon is clearly evident when the thickness of ink is greater than or equal to 25 micrometers. Between 15 and 25 micrometers, triboluminescence is evident, but with an intensity of low 30 initial fluorescence.

At a level of 1% by weight of compound 12 or 13, the triboluminescence phenomenon is clearly evident when the thickness of ink is greater than or equal to 40 micrometers. Between 20 and 40 micrometers, the triboluminescence is evident, but with an intensity of low 5 initial fluorescence. This shows that the compound can be employed in a small quantity in currently used inks and according to standard thicknesses. 10 The above compound is also suitable for introduction inside a security document, for example in paper pulp when this is a note or plastic material when this is a card, for example an ID card. Several embodiments will now be described, in reference to the 15 above diagrams. Figures 1A to 1C illustrate a first embodiment in which the document according to the invention consists of a bank note D. 20 As shown in figure 1A, this note comprises a security element 1 constituted here by a zone 2 of oval contour, printed in the form of a patch which, as a variant, can be open-work. Printed on this zone via screen printing or copper-plate engraving is a pattern 3 here reproducing the facial value of the bank note, in this case the figure "100". 25 In this embodiment, both the zone 2 and the pattern 3 exhibit an identical colour C1 in the visible light spectrum. This is the situation of figure 1A in which the pattern 3 is imperceptible, or is barely perceptible. Under fluorescent lighting, this zone 2 and the pattern 3 are illuminated by 30 the same colour of the same colour, or by a colour substantially identical in hue, for example in the colour blue (designated C2 in the figure). Still under lighting fluorescent, friction placed on the security element 1 will cause a change in fluorescence of the pattern 3, and reveal the value "100" under a different fluorescence colour C3, yellow for example. 5 In the embodiment of figure 2A, the security element 1 comprises a zone 2 printed in the form of a patch which, by way of variant, can be open-work. This zone has a colour C1 in the visible light spectrum. A pattern 3, which here also represents the value "100", is printed 10 on the zone 2 via screen printing or copper-plate engraving and its colour C2 is different to that of the zone 2. In these conditions, the pattern 3 is visible to the naked eye. When the security element is lit by fluorescent lighting, the zone 2 15 and the pattern 3 then put out the same colour C3, blue for example. This is the situation of figure 2B. Still under fluorescent lighting, the friction of the security element 1 by a pointed tool causes a change in fluorescence of the pattern 3, revealing the value "100" in a different colour C4, for example yellow (see Figure 2C). 20 In reference to figures 3A and 3B, these deal with a bank note of the same general type as that presented hereinabove. However, this note comprises an abrasive region 5 textured by 25 paper, ink or else a plastic element added to the paper which, as a variant, could be a transparent part. This abrasive textured region is for example obtained by embossing of dry seal copper-plate engraving type. In the visible light spectrum and as shown in figure 3A, the zone 2 30 and its pattern (not distinguishable here, consequently) show the same colour.

However, when the abrasive textured region 5 above the zone 2 is folded back and friction is applied, the pattern 3 of the note is revealed by modification of its fluorescence colour. 5 This pattern 3 can for example comprise a suite of figures which can be compared for example to the number of the note, which, designated 6, is printed on the same face as the pattern 3. 10 In reference to figures 4A and 4B, as in the preceding embodiment these relate to an abrasive textured region 5 borne by a transparent part 4 of the note. The textured region has the form of the digit "0". 15 Also, in the zone 2 are three patterns 3, 3' and 3" which jointly form the figure "100", the pattern 3' comprising the digit "0" being formed by triboluminescent ink, as opposed to patterns 3 and 3". 20 Therefore, and as shown in figure 4B, as soon as the part 4 is superposed and friction is applied to the pattern 3' by way of the textured zone 5, this reveals fluorescence which can be a colour identical to that of the patterns 3 and 3", as shown in figure 4C. 25 Finally, in reference to figures 5A to 5C, these relate to a pattern 3 which has two adjacent regions 30 and 31, the first being printed in fluorescent ink and the second in triboluminescent ink. Under visible lighting, the whole pattern is visible uniformly. 30 But, and as shown in figure 5B, under fluorescent lighting the regions 30 and 31 show different colours. When the region 31 is scraped with a pointed tool, its fluorescence colour is modified and becomes identical to that of the region 30. This is the situation of figure 5C. 5 In another embodiment, the two regions 30 and 31 could each be printed in triboluminescent ink, giving identical fluorescence colours but colours which are different after friction. 10 The different assays conducted by the applicant show that a wavelength value of ultraviolet light particularly appropriate for causing luminescence of the compounds used is 365 nm. A wavelength of 254 nm is also applicable, but with luminescence reaction of the disclosed compound which is less pronounced. 15 The triboluminescent compound can be incorporated into the paper pulp used for manufacturing the security document, such that the latter can of course be at least partly made of paper, or based on paper. 20 Another method which can be considered for attaching the triboluminescent compound to the document comprises first of hot depositing in onto a transfer film - by coating or standard printing for example - then secondly transferring and adhering this film to the document. 25 Also, it would be possible to provide a security document according to the present invention with a third level of authentication. For this purpose, it is possible to integrate a tracer-type element for a third level, for example having particular emission characteristics capable of being 30 detected by automatic screening machines into the composition (ink or varnish), at the same time as the triboluminescent compound.

Finally, the triboluminescent compound is likely to be incorporated into a composition compatible with digital printing means (ink jet, for example), for personalisation of the document, 5 It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. 10 In the claims which folow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or 15 addition of further features in various embodiments of the invention.

Claims

1. A security document characterised in that it comprises inside it or at the surface a reversible mechanoluminescent compound, wherein said 5 compound corresponds to the following formula: in which n is a whole number between 1 and 4 10

2. The document as claimed in Claim 1, characterised in that the document is a fiduciary document.

3 The document as claimed in Claim 1 or Claimn 2, in which said 15 compound is at the surface, characterised in that it is integrated into ink or varnish

4 The document as claimed in Claim 3, characterised in that it comprises a security element comprising at least one printed zone, on this 20 zone being printed, by means of a composition containing a compound as defined in any one of Claims I to 3, at least one pattern, - said zone and said pattern having a first colour identical in the visible light spectrum - said zone and said pattern having a second colour identical under 25 ultra-violet light; - said pattern having a third colour, different to the first and second colours when it is subjected to mechanical stress,

5. The document as claimed in Claim 3, characterised in that it comprises a security element comprising at least one printed zone, on this zone being printed, by means of a composition containing a compound as defined in any one of Claims I to 3, at least one pattern, 5 - said zone and said pattern having respectively a first and a second colour different in the visible light spectrum; ~ said zone and said pattern having a third colour identical under ultra-violet light; - said pattern having a fourth colour, different to the preceding 10 colours when it is subjected to mechanical stress.

6. The document as claimed in Claim 3, characterised in that it comprises a security element comprising at least one printed zone, on this zone being printed, by means of a composition containing a 15 compound as defined in any one of Claims I to 3, at least one pattern, and at least one abrasive textured region, such that said pattern becomes visible in a colour different to its initial colour by superposition of the abrasive textured region on said pattern and mechanical stress. 20

7, The document as claimed in Claim 6, characterised in that it has a transparent part and in that said textured region is integrated therein.

8. The document as claimed in Claim 7, characterised in that said textured region is obtained by embossing, of copper-plate dry seal type 25 engraving type.

9. The document as claimed in Claim 3, characterised in that it comprises a security element comprising at least one printed zone, on this zone being printed, several patterns including one at least by means of a 30 composition containing a compound as defined in any one of Claims I to 3, and that it has a transparent part comprising an abrasive textured region which has the same form as said pattern printed by means of said composition, such that said pattern becomes visible in a colour different to its initial colour by superposition and mechanical stress. 5 10. The document as claimed in Claim 3, characterised in that it comprises a security element comprising at least one printed zone on this zone being printed, at least one pattern comprising two adjacent regions, one of these regions being printed by means of a composition containing a compound such as defined in any one of Claims 1 to 3.

10

11. The document as claimed in any one of Claims 4 to 10, characterised in that the printed zone is in the form of a patch,

12. The document as claimed in any one of Claims 4 to 11, 15 characterised in that the at least one pattern or the several patterns is/are printed on the printed zone via offset, screen printing or copper-plate engraving.

13. The document as claimed in any one of Claims 4 to 12, 20 characterised in that printing of said printed zone is carried out by one of the following processes: - offset; - typography; - heliogravure; 25 flexography; - screen printing; - copper-plate engraving,

14. The document as claimed in any one of Claims 4 to 13, 30 characterised in that said printed zone is an open-work patch.

15. The document as claimed in any one of the preceding claims, characterised in that said mechanoluminescent compound is used for personalisation of the document. 5