OPTICAL MARKING DEVICE

专利摘要:
The invention relates to an optical marking device comprising at least a first layer and a second layer arranged at least partially facing each other, at least one of said first and second layers comprising an optically variable element ( 4, 5) having a color change between a first color and a second color, said first and second colors being contrasted with respect to a color of the other layer so that, when the optically variable element (4, 5) said first color, the first layer is visible and when the optically variable element (4, 5) has said second color, the second layer is visible or when the optically variable element (4, 5) has said first color, the second layer is visible and when the optically variable element (4, 5) has said second color, the first layer is visible.
公开号:FR3080325A1
申请号:FR1853464
申请日:2018-04-19
公开日:2019-10-25
发明作者:Cosimo Prete；Jeremy Malinge；Gautier Alloyez
申请人:Crime Science Tech；
IPC主号:

专利说明:

The present invention relates to the field of securing and authenticating products, in particular documents.
It relates more particularly to the securing and authentication of identity, fiduciary or administrative documents or even brand labels.
Nowadays, counterfeiting and the production of counterfeits are increasing significantly in many sectors with high added value such as luxury goods, automotive and aeronautical parts or packaging, especially medicines such as blisters.
With the development of identity theft and the introduction, in particular, of driver's licenses in some countries, identity and administrative documents are increasingly the target of falsification. The security and authenticity of this type of product and document are therefore essential and have both national and international security challenges.
It is therefore necessary to continually provide new means making it possible to fight effectively against forgery, in particular the alteration of an original document, or counterfeiting (production of forgeries).
For the remainder of the description, the term document refers to an assembly formed by a support and information. The support can be of different natures, take different forms and can comprise a polymer or a mixture of polymers. This support can for example consist entirely or in part of a polymer material.
Examples of documents include identity documents such as passports, identity cards, driving licenses or health cards, but also fiduciary documents such as banknotes and checks or administrative documents such as registration certificates.
The documents can therefore be in the form of paper, booklet or even in the form of a card and the information can be printed and / or engraved on the surface in the case of paper or card as well as in the sheets when it is a booklet.
Due to the high value associated with the information contained, documents need to be secure.
At present, documents are secured by security elements that can be classified according to three levels of security depending on the means used for detection. Thus, level 1 security elements are elements that can be detected by at least one of the five senses or by means of a contrasting background. In this level we will find in particular guilloches, optical variability devices such as iridescent prints, holograms, optically variable ink (Optical Variable Ink), markers, variable laser images (Changeable Laser Image) or laser images multiple (Multiple Laser Image).
Level 2 security elements are elements detectable using simple equipment such as an Ultra-Violet lamp, a convex lens or a flash light from a mobile phone. This level contains detectable elements such as micro-prints, fluorescent inks, as well as fluorescent fibers or platelets.
Finally, level 3 security elements are elements detectable using sophisticated equipment such as a spectrofluorometer or an electron microscope. In this category are found in particular nano-etched pigments, biometric chips as well as fluorescent markers not detectable with the naked eye (English: taggants).
Generally, a document incorporates several security elements of different levels.
Although existing security solutions prove to be interesting, they are sometimes difficult to implement and / or control. There is therefore a real need for new security means that are simple to implement, stable and then allows rapid control of the authenticity of the products or documents, while ensuring a high level of security. These means should not be mutually exclusive.
To this end, the subject of the invention is an optical marking device comprising at least a first layer and a second layer arranged at least partially opposite one another, at least one of said first and second layers includes an optically variable element having a color change between a first color and a second color, said first and second colors being contrasted with a color of the other layer so that when the optically variable element exhibits said first color , the first layer is visible and when the optically variable element has said second color, the second layer is visible or when the optically variable element has said first color, the second layer is visible and when the optically variable element has said second color, the first layer is visible.
Thus, the device according to the present invention makes it possible to control the authenticity of products, such as documents, in particular identity, fiduciary or administrative documents, but also such as the packaging of medication (in particular blisters) or even luxury products (identification of Mark).
According to another characteristic of the invention, the device comprises a pattern provided with said optically variable element.
According to another characteristic of the invention, the device comprises a substrate on which rests at least one of said first and second layers.
According to another characteristic of the invention, the two layers are in contact with each other.
According to another characteristic of the invention, at least one of the two layers is at least partially reflective in the visible light spectrum and / or has shades of gray.
According to another characteristic of the invention, at least one of the two layers (2, 3) is at least partially diffusing in the visible light spectrum.
According to another characteristic of the invention, the optically variable element comprises one or more fluorescent compound (s).
According to another characteristic of the invention, the optically variable element comprises one or more compound (s) from the family of 4,4difluoro-4-bora-3a, 4a-diaza-s-indacenes.
According to another characteristic of the invention, in which the compound (s) of the family of 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacènes are chosen from those of formula I:
in which,
R ¹ is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted by one or more groups chosen from C1 to C2 alkyl, hydroxy, R ⁵ COO 'and halogen;
R ² and R ² are independently selected from hydrogen and C1 to C2 alkyl;
R ³ and R ³ are independently selected from hydrogen and C1 to C3 alkyl;
R ⁴ and R ⁴ 'are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups chosen from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group ;
R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl.
According to another characteristic of the invention, the optically variable element comprises one or more compound (s) from the family of difluoroborane β-diketonate (BF2bdks).
According to another characteristic of the invention, the compound (s) of the family of difluoroborane β-diketonate (BF2bdks) are chosen from those of formula II:
R ³ (D in which,
L ¹ is an unsaturated or nonexistent aliphatic chain,
L ² is an unsaturated or nonexistent aliphatic chain,
R ¹ is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group,
R ² is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group, and
R ³ is chosen from hydrogen, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.
According to another characteristic of the invention, the device comprises a polymer for incorporating the optically variable element.
According to another characteristic of the invention, the polymer is chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride), polyamides, polyaramides, vinylethylene acetate (EVA), polyurethane, thermoplastic polyurethane (TPU), cyanoacrilate, rosin resins, pine resins, photopolymerizable resins or mixtures thereof.
According to another characteristic of the invention, one of said first and second colors of the layer comprising the optically variable element is the color complementary to the color of the other layer.
According to another characteristic of the invention, the two layers comprise an optically variable element having a color change, the two optically variable elements being at least partially superimposed and configured so that only the first layer is visible when a first stimulation is applied to the device and only the second layer is visible when a second stimulation is applied to the device.
According to another characteristic of the invention, the device comprises an element configured to polarize light passing through said optical marking device.
The invention also relates to an identity, fiduciary, administrative document or a label comprising at least one optical marking device as described above.
Other characteristics and advantages of the invention will appear on reading the description which follows. This is purely illustrative and should be read in conjunction with the accompanying drawings in which:
- Figure 1 illustrates a schematic sectional view of an optical marking device according to the present invention;
- Figures 2 to 4 illustrate top views respectively of a first layer, a second layer and a device according to a first embodiment of the invention;
- Figures 5 to 7 illustrate top views respectively of a first layer, a second layer and a device according to a second alternative embodiment of the invention; and
- Figures 8 to 11 illustrate top views respectively of a first layer, a second layer and a device according to a third alternative embodiment of the invention.
Optical marking device
The subject of the invention is an optical marking device for a product, such as a document. The optical marking device is referenced 1 in the figures.
For the remainder of the description, the term document refers to an assembly formed by a support and information. The support can be of different natures, take different forms and can comprise a polymer or a mixture of polymers. This support can for example consist entirely or in part of a polymer material.
Examples of documents include identity documents such as passports, identity cards, driving licenses or health cards, but also fiduciary documents such as banknotes and checks or administrative documents such as registration certificates.
The documents can therefore be in the form of paper, booklet or even in the form of a card and the information can be printed and / or engraved on the surface in the case of paper or card as well as in the sheets when it is a booklet
The device 1 comprises at least a first layer and a second layer, called optical marking layers.
In the figures, the device 1 comprises two layers of optical marking, referenced 2 and 3.
Of course, the invention is not limited to this configuration and one can provide a multilayer having more than two layers.
In the illustrated embodiments, the layers 2 and 3 are exactly superposed on each other, in direct contact with each other, which is particularly advantageous.
Nevertheless, provision can be made for the layers 2 and 3 to only partially overlap and / or for them not to be in direct contact but, on the contrary, spaced apart from each other, for example by other layers of the device 1.
At least one of the two layers 2, 3 comprises an optically variable element.
In the first alternative embodiment illustrated in FIGS. 2 to 4, each of the two layers 2, 3 comprises an optically variable element referenced respectively 4, 5.
In the second variant embodiment illustrated in FIGS. 5 to 7, only the layer 2 comprises an optically variable element referenced 4.
In the third variant embodiment illustrated in FIGS. 8 to 11, each of the two layers 2, 3 comprises an optically variable element, referenced respectively 4, 5.
Each optically variable element has a color change between a first color and a second color, as will be described later.
The optical marking device 1 is configured so that, when the optically variable element has the first color, the first layer is visible and when the optically variable element has said second color, the second layer is visible or when the element optically variable has the first color, the second layer is visible and when the optically variable element has said second color, the first layer is visible, as will be detailed in relation to each variant embodiment of the invention.
Advantageously, at least one of the two layers comprises a pattern at least partially superimposed with the optically variable element.
The motif may preferably be a symbol, a drawing, a photograph, or a fixed or variable mention which participates in identifying the product equipped with the device 1.
The pattern can for example be printed with ink or varnish or even laser engraved.
In FIG. 1, the device 1 comprises a substrate 11 for supporting the optical marking layers 2, 3.
The substrate 11 is for example a layer of transparent polymer.
Advantageously, the substrate 11 is a layer of polypropylene, polycarbonate, or polyethylene of controlled thickness (for example between 10 μm to 800 μm, preferably a thickness ranging from 50 μm to 600 μm for polycarbonate, 10 μm up to 600 µm, and preferably 30 µm to 150 µm for polypropylene and 5 µm to 500 µm, preferably 10 µm for PET) transparent.
Optically variable element
By optically variable element is meant any physicochemical element which exhibits a color shift between a first color and a second color as a function of a physicochemical stimulus.
The physico-chemical stimulus, also called stimulation, can be a light irradiation, a change in temperature or pressure or even a modification of an observation condition (such as the angle of incidence of the observation of the element)
In the embodiments which will be detailed, the optically variable element comprises a given concentration of an active substance comprising one or more fluorescent compound (s), particularly from the family of 4,4-difluoro-4-bora-3a , 4a-diaza-sindacènes or of the family of difluoroborane β-diketonate (BF2bdks), detailed later.
However, the invention is not limited to this type of optically variable element.
As an example, it can also be a thermochromium, a liquid crystal ink or an optically variable ink of the type known under the name "OVI" (trademark registered by the company "SICPA> >).
Preferably, the layer 2 or 3 comprising the optically variable element also comprises a polymer in which the compound (s) are (are) incorporated in a polymer, and in particular a polymer matrix constituting the document or the product in question.
For the rest of the description, the terms “compound (s) 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene (s) >>,“ «difluoroborane β-diketonate (BF2bdks) >> will be used interchangeably. , and "fluorescent dye (s)".
It is noted that the active substance can be mixed with one or more types of inks.
The compounds 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacènes are fluorescent dyes, the first synthesis of which was published in 1968 (A. Treibs et al, Justus Liebigs Ann. Chem. 1968, 718 , 208). Since then, several other syntheses have been published (for example: Chem. Eur. J., 2009, 15, 5823; J. Phys. Chem. C, 2009, 113,11844; Chem. Eur. J., 2011, 17, 3069; J. Phys. Chem. C, 2013, 117, 5373) and many 4,4-difluoro4-bora-3a, 4a-diaza-s-indacènes compounds are commercially available, for example from ThermoFisher Scientific (Waltham, MA USA).
They have remarkable absorption and emission properties and in particular have relatively narrow excitation and fluorescent emission bands with high iques quantum yields between 0.5 and 1, which makes them very fluorescent.
In addition, these compounds exhibit good photostability as well as significant thermal stability. In fact, the fluorescent dyes according to the invention are generally stable up to 300 ° C.
Thanks to this significant thermal stability, these fluorescent dyes can easily be incorporated into polymer matrices in the molten state and against all expectations, the performance in terms of absorption and remission of fluorescence is not impaired by the incorporation into a polymer matrix.
This good stability allows the compound (s) to be incorporated into a relevant ink, which ensures high stability with regard to photobleaching, unlike the technologies of the prior art.
The compounds 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacènes all have an absorption band in the visible and the color perceived with the naked eye corresponds to the color complementary to the absorbed color. For example, an absorbent compound around 480-490 nm, which corresponds to a green / blue color, will appear to the naked eye in orange / red tones.
This property thus makes it possible to obtain level 1 security elements.
Concerning the fluorescence properties, the compounds of the family of 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacènes according to the invention all have excitation bands in Ultra-Violet (UV ) and visible emission bands. They can therefore be excited in particular by means of a UV lamp emitting between 100 nm and 400 nm and the fluorescence can be detected with the naked eye, which makes it possible to obtain level 2 security elements.
Finally, the emission wavelength can be determined using a low-resolution spectrofluorometer or fluorimeter with a single network (detection by photodiode or photomultiplier tube), which gives the security elements according to the present invention a level 3 of security.
The compound (s) 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene (s) used in the present invention can be chosen from those of formula I below:
in which,
R ¹ is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted by one or more groups chosen from C1 to C2 alkyl, hydroxy, R ⁵ COO 'and halogen;
R ² and R ² 'are independently selected from hydrogen and C1 to C2 alkyl;
R ³ and R ³ 'are independently selected from hydrogen and C1 to C3 alkyl;
R ⁴ and R ⁴ 'are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups chosen from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group ;
R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl.
Preferred compounds of formula I are those in which one or more of R ¹ , R ² , R ² , R ³ , R ³ , R ⁴ , R ⁴ and R ⁵ are defined as follows: R ¹ is a phenyl substituted by a or more groups chosen from methyl, fluoro, hydroxy, acetyl and methacrylate, preferably from methyl, fluoro, hydroxy and acetyl and more preferably from methyl or fluoro;
R ² and R ² are independently selected from hydrogen and methyl;
R ³ and R ³ are independently chosen from hydrogen, methyl, ethyl, n-propyl and preferably ethyl;
R ⁴ and R ⁴ are independently chosen from methyl, vinyl, aryl, heteroaryl, adamanthyl, said vinyl and aryl being optionally substituted by one or more groups chosen from phenyl, C1 to C2 alkyl, said phenyl being optionally substituted by one or more groups chosen from C1 to C2 alkyl, hydroxy, bromo, nitro, dimethylamine, preferably R ⁴ and R ⁴ are independently chosen from methyl, vinyl, phenyl, phenanthrenacenyl, naphthalenyl, pyrenyl, thiphenyl, benzofuranyl, said vinyl, aryl and naphthalenyl being optionally substituted by one or more methyl, hydrocy, bromo, nitro and dimethylamino;
R ⁵ is methyl or ethenyl.
Particularly preferred compounds of formula I are those of the table below:
No. Fluorescent dye 1 JUk> ^ν 'β' ^ν Ύ γΤί ^F2 γΑί
2 'F2' 3 OH 0 Xn. / B / f ₂ 4 Λ 0 VN. , N - </ / B / f ₂ 5 X ^ N. .NOT-#o o 6 F Ύ T ^ ίγ ' ^f / vJ ^ rVyv> ^ν ' β ^ ^ν Ύ / F2 ' 7 JUk ^R ^ TkO ^ ^R K / B Z Λ ^ Χ ^{1 = 2} ζ ^ Λ y) w R = Me, Et, n-Pr
13 JUL _R —ΛκΤ Γ ^ν 'β' ^ν V ^F2 X ^R R = n-Pr14 XX R— ¥ ^N · ^ Lv ^F2 A ^r oR = And15 jO r — ΛτΤ> ^ν 'β' ^ν v ^F2 X ^R R = Me16 F Fx / LT ^F 'i ^x Έ./ X '-X ^F2 N ~ - /Q HO17 FHe Ί -F ^fZx i 'F,V ^ N. .N Γ F * VS/
18 JULÇ% ' ^N 9Â ^F2 Z ^ O O 019 FThere 1 -F ^F ^ T 'F. .NOTΓ B O / Z Λ 20 FT T -F ^ρΖχ ι 'F. ^ Îk .N / B / τ == ^F2 = ¾. O / Z 1HOOH 21 FTl Ί -F ^ Ι 'F, ^ N. .N / B / ==== ^{F2 Η (} λ / == Λ J3HIY ₂ N - #v y ~~ NO ₂ no ₂ o ₂ n22 ri ^r ÇCO ^r çd'-d ^Z R = Me, Et, n4 »r 23 JCt ^R ^ ÇÔ- -y-R R = H, Me, Et, n-Pr
24 at€ ΤΏΜ3 25 λ y 26 Λf8r , Ν ^A '®ο ο 27 jQl Çî / nO f Β Λ “X ^{F î} Χλ Ο ÎJ * 0 Ο /> - -q 28 JQL Çn. , N ~ jz Γ B Λ 0 4 ^Fl fi O 8 fi 29 r ^ r ΊΝ. "Λν/ B X4 Fz V fo m
30 F F ^ J ^ F ί JL ^f ra /, N <f ~ 'JK c 0 NN—. / 31 F F ^ J ^ F jX r ^H -rT 0 ^Fe v 32 J ^ L. 'XCX ⁷ / if ₂ 33 p ™ X /, v / rrv. /YSN. "N- /> U 'OH in position o, m or p 34 0- [φ JXt4 / JB / f ₂ 35 Χχ XX ^ Xx RR F _s W 36 V 37 HnLJ / N. , Ν ^ ΧΧ (Λ B Λ) f ₂ W
38 x Lm / VsN, f B Λ / F _a 39
For the description of the compounds used in the present invention, the terms and expressions used must, unless otherwise indicated, be interpreted according to the definitions below.
The term "halogen" denotes fluoro, chloro, bromo or iodo. Preferred halogen groups are fluoro and bromo, fluoro being particularly preferred.
The term “alkyl” designates a hydrocarbon radical of formula CnH2n + 1, linear or branched, in which n is an integer greater than or equal to 1. The preferred alkyl groups are the C1 to C6 alkyl groups, linear or branched.
The term "alkenyl" denotes an unsaturated, linear or branched alkyl group comprising one or more carbon-carbon double bonds. Suitable alkenyl groups comprise from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms and more preferably still 2 or 3 carbon atoms. Nonlimiting examples of alkenyl groups are ethenyl (vinyl), 2-propenyl (allyl), 2-butenyl and 3-butenyl, ethenyl and 2-propenyl being preferred.
The term "cycloalkyl (e)", alone or as part of another group, denotes a saturated mono-, di- or tri-cyclic hydrocarbon radical having 3 to 12 carbon atoms, in particular 5 to 10 carbon atoms , more particularly 6 to 10 carbon atoms. Suitable cycloalkyl radicals include, but are not limited to, cyclopentyl, cyclohexyl, norbornyl, adamantyl, especially cyclohexyl and adamantyl. Preferred cycloalkyl groups include cyclohexyl, adamant-1-yl and adamant-2-yl.
The term "aryl" denotes a polyunsaturated, aromatic, monocyclic (for example phenyl) or polycyclic (for example naphthyl, anthracenyl, phenantracenyl, pyrenyl) hydrocarbon radical. Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenantracenyl, pyrenyl.
The term "heteroaryl" denotes an aromatic ring having 5 to 12 carbon atoms in which at least one carbon atom is replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen atoms and sulfur can optionally be oxidized and which nitrogen atom can optionally be quaternized, or a ring system containing 2 to 3 fused rings each containing typically 5 or 6 atoms and of which at least one ring is aromatic, at least one carbon atom of the at least one aromatic ring being replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen and sulfur atoms may optionally be oxidized and which nitrogen atom may optionally be quaternized . Examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyridinyl and benzofuranyl.
The compounds used in the present invention can be synthesized according to methods known to those skilled in the art. He may in particular refer to the publication of A. Loudet et al. (Chem. Rev. 2007, 107, 4891-4932).
According to another embodiment, the optically variable element comprises a fluorescent composition comprising a polymer matrix incorporating a compound of the family of difluoroborane β-diketonate (BF ₂ bdk) chosen from the formulell compounds below:
in which,
L ¹ is an unsaturated or nonexistent aliphatic chain,
L ² is an unsaturated or nonexistent aliphatic chain,
R ¹ is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group,
R ² is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group, and
R ³ is chosen from hydrogen, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.
Compounds of the family of the preferred difluoroborane β-diketonate of formula I are those in which one or more of L ¹ , L ² , R ¹ , R ² , and R ³ are defined as follows:
L ¹ is an unsaturated aliphatic chain, preferably at C2 to C8 or nonexistent,
L ² is an unsaturated aliphatic chain, preferably at C2 to C8 or nonexistent,
Ri is an unsubstituted or substituted aryl group, preferably an aryl group unsubstituted or substituted by at least one electron donor or electron withdrawing group,
R ₂ is an unsubstituted or substituted aryl group, preferably an aryl group which is unsubstituted or substituted by at least one electron donor or electron withdrawing group, and
R3 is chosen from hydrogen and a substituted or unsubstituted aryl group.
Compounds of the family of the preferred difluoroborane β-diketonate of formula I are those in which one or more of L ¹ , L ² , R ¹ , R ² , and R ³ are defined as follows:
L ¹ is an aliphatic chain unsaturated in C2 to C4 or nonexistent,
L ² is an aliphatic chain unsaturated in C2 to C4 or nonexistent,
Ri is an aryl group which is unsubstituted or substituted by at least one group chosen from hydroxy, alkoxy, alkyl, aryl, dialkylamino, thioalkoxy, halogen,
R ₂ is an aryl group which is unsubstituted or substituted by at least one group chosen from hydroxy, alkoxy, alkyl, aryl, dialkylamino, thioalkoxy, halogen, and
R3 is chosen from hydrogen and an unsubstituted aryl group.
Compounds of the family of the preferred difluoroborane β-diketonate of formula I are those in which one or more of L ¹ , L ² , R ¹ , R ² , and R ³ are defined as follows:
L ¹ is an aliphatic chain unsaturated in C2 to C4 or nonexistent,
L ² is an aliphatic chain unsaturated in C2 to C4 or nonexistent,
Ri is an aryl group unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, C1 to C8 alkyl, aryl, C1 to C4 dialkylamino, C1 to C4 thioalkoxy, halogen, preferably fluorine,
R ₂ is an aryl group unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, C1 to C8 alkyl, aryl, C1 to C4 dialkylamino, C1 to C4 thioalkoxy, halogen, preferably fluorine , and
R ₃ is a hydrogen atom.
Compounds of the family of the preferred difluoroborane β-diketonate of formula I are those in which one or more of L ¹ , L ² , R ¹ , R ² , and R ³ are defined as follows:
L ¹ is an aliphatic chain unsaturated in C2 or nonexistent,
L ² is an aliphatic chain unsaturated in C2 or nonexistent,
Ri is an aryl group, preferably phenyl, biphenyl or naphthyl, unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, preferably methoxy, C1 to C8 alkyl, preferably te / t / o -butyl, aryl, C1 to C4 alkylamino, preferably dimethylamino,
R2 is an aryl group, preferably phenyl, biphenyl or naphthyl, unsubstituted or substituted by at least one group chosen from hydroxy, C1 to C4 alkoxy, preferably methoxy, C1 to C8 alkyl, preferably te / t / o -butyl, aryl, C1 to C4 alkylamino, preferably dimethylamino, and
R3 is a hydrogen atom.
Preferred compounds of the difluoroborane β-diketonate family are those of formula I ₂ below:
In which R ¹ , R ² and R ³ are as defined in formula I.
Preferred compounds of the difluoroborane β-diketonate family are those of formula l ₃ below:
In which L ¹ , R ¹ , R ² and R ³ are as defined in formula I.
Preferred compounds of the family of difluoroborane β-diketonate are those of formula l ₄ below:
In which L ² , R ¹ , R ² and R ³ are as defined in formula I.
Particularly preferred compounds of the family of difluoroborane β-diketonate of formula I are the following:
Compound 7
Compound 9
Compound 10
Compound 12
The term “alkyl” designates a hydrocarbon radical of formula CnH2n + 1, linear or branched, in which n is an integer greater than or equal to 1. The preferred alkyl groups are linear or branched C1 to C6 alkyl groups.
The term "alkenyl" denotes an unsaturated, linear or branched alkyl group comprising one or more carbon-carbon double bonds. Suitable alkenyl groups comprise from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms and more preferably still 2 or 3 carbon atoms. Nonlimiting examples of alkenyl groups are ethenyl (vinyl), 2-propenyl (allyl), 2-butenyl and 3-butenyl, ethenyl and 2-propenyl being preferred.
The term "cycloalkyl (e)", alone or as part of another group, denotes a saturated mono-, di- or tri-cyclic hydrocarbon radical having 3 to 12 carbon atoms, in particular 5 to 10 carbon atoms , more particularly 6 to 10 carbon atoms. Suitable cycloalkyl radicals include, but are not limited to, cyclopentyl, cyclohexyl, norbornyl, adamantyl, especially cyclohexyl and adamantyl. Preferred cycloalkyl groups include cyclohexyl, adamant-1 -yle and adamant-2yle.
The term "aryl" denotes a polyunsaturated, aromatic, monocyclic (for example phenyl) or polycyclic (for example naphthyl, anthracenyl, phenantracenyl, c) hydrocarbon radical. Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenantracenyl, pyrenyl.
The term "heteroaryl" denotes an aromatic ring having 5 to 12 carbon atoms in which at least one carbon atom is replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen atoms and sulfur can optionally be oxidized and which nitrogen atom can optionally be quaternized, or a ring system containing 2 to 3 fused rings each containing typically 5 or 6 atoms and of which at least one ring is aromatic, at least one carbon atom of the at least one aromatic ring being replaced by an oxygen, nitrogen or sulfur atom or by -NH, which nitrogen and sulfur atoms may optionally be oxidized and which nitrogen atom may optionally be quaternized . Examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyridinyl and benzofuranyl.
The term "halogen" denotes fluoro, chloro, bromo or iodo. Preferred halogen groups are fluoro and bromo, fluoro being particularly preferred.
Thus, when the layer 2, 3 comprising the optically variable element is deposited on a light background, the intrinsic color is observed (that is to say the color complementary to the color absorbed by the fluorescent compound (s) ).
On the other hand, on a dark background, the fluorescence color due to the fluorescent compound (s) is observed.
The physico-chemical stimulus consists in placing the device 1 on a light then dark background, or on the contrary on a dark then light background.
The incorporation can be done in all types of polymer such as for example polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride), polyamides, polyaramides, vinylethylene acetate (EVA), polyurethane, thermoplastic polyurethane (TPU), cyanoacrilate, rosin resins, pine resins, photopolymerizable resins or mixtures thereof. Preferably, the incorporation can be done in a polymer chosen from polycarbonate, thermoplastic polyurethane and photopolymerizable resins, preferably from polycarbonate and thermoplastic polyurethane, more preferably the polymer is polycarbonate.
The quantity of fluorescent dye to be incorporated is that necessary for the detection of the absorbance and fluorescence properties. The fluorescent dyes according to the invention have the advantage of allowing properties to be detected even when they are incorporated into the polymer in very small quantities.
In fact, quantities of fluorescent dyes ranging from 0.0001% to 5% by weight relative to the total weight of the polymer are sufficient for detection, preferably quantities ranging from 0.001% to 2% by weight relative to the total weight of the polymer and even more preferably, amounts ranging from 0.01% to 1%, by weight relative to the total weight of the polymer.
The quantities of fluorescent dye (s) will be adapted by the skilled person according to the shaping of the polymer and the desired visual effect.
Each layer comprising an optically variable element is advantageously prepared by techniques known to a person skilled in the art, such as for example rolling, extrusion, calendering, or calendering extrusion. These techniques will be chosen according to the polymer used. For example, if the polymer is a polycarbonate or a thermoplastic polyurethane, the principle of calendering extrusion will be preferred. A set of layers within the meaning of the present invention can for example be obtained by laminating two or more layers of polymer incorporating one or more fluorescent dyes.
Advantageously, the layer 2, 3 has in particular a thickness ranging from 10 μm to 800 μm, preferably a thickness ranging from 50 μm to 600 μm, for polycarbonate, 10 μm to 600 μm, and, preferably, 30 μm to 150 μm for polypropylene and from 5 μm to 500 μm, preferably from 10 μm for PET, to which an ink thickness of 0.1 μm up to 200 μm is added, preferably from 1 μm to 100 μm.
When the layer has a thickness of less than 0.100 mm, it is also called film and will find a very particular application in the case of flat products, in particular documents and more particularly identity, fiduciary or administrative documents and may be applied to at least one part of one side of the product.
First variant
As shown in FIGS. 2 to 4, the optical marking device 1 comprises a first layer of optical marking and a second layer of optical marking 3.
In FIG. 4, layer 3 is superimposed on layer 2.
Each of the layers 2, 3 comprises an optically variable element 4, 5.
The first layer 2 comprises a pattern 9 in the shape of a disc.
The disc 9 incorporates the optically variable element 4 of the layer 2.
This is for example an ink or a varnish incorporating the active substance.
The second layer 3 includes a pattern 10 in the shape of a triangle. The triangle 10 integrates the optically variable element 5 of the layer 2.
This is for example an ink or a varnish incorporating the active substance.
Pattern 10 covers pattern 9.
The patterns 9, 10 are at the center of their respective layers 2, 3.
Of course, the invention is not limited to this configuration and the patterns can on the contrary be offset.
Each of the optically variable elements 4, 5 comprises one or more fluorescent compound (s) as described above, preferably incorporated into a polymer.
In FIG. 2, a first half 2-1 of the first layer 2 comprising a first half 9-1 of the disc 9 is illustrated on a light background.
A second half 2-2 of the first layer 2 comprising a second half 9-2 of the disc 9 is illustrated on a dark background.
In FIG. 3, a first half 3-1 of the second layer 3 comprising a first half 10-1 of the triangle 10 is illustrated on a light background.
A second half 3-2 of the second layer 3 comprising a second half 10-2 of the triangle 10 is illustrated on a dark background.
The intrinsic colors of the layers 2, 3 and advantageously their light intensity are chosen so that, on a light background, it is the pattern 10 of the second layer 3 which is visible while, on a dark background, it is the pattern 9 of the first layer 2 which is visible.
For example, the first half 9-1 is pink (shown in dotted lines), which, as already indicated, corresponds to the intrinsic color of layer 2.
The second half 9-2 is green (represented by hatching), which, as already indicated, corresponds to the fluorescence color of layer 2.
The first half 10-1 is blue (shown in parallel dotted lines), which, as already indicated, corresponds to the intrinsic color of layer 3.
And, the second half 10-2 is red in color (shown in parallel dotted lines, in a direction different from that of the half ΙΟΙ), which, as already indicated, corresponds to the fluorescence color of layer 3.
In Figure 4, a first half 1-1 of the device 1 is placed on the light background while a second half 1-2 of the device 1 is placed on the dark background.
On the light background, it is the second layer 3 which is visible and we observe the blue triangle 10-2.
On the dark background, it is the first layer 2 which is visible and we observe the green circle 9-1.
It is noted that the optical effect obtained is enabled by the concentration in the second layer 3 of active substance of the ink or varnish used to produce the pattern and chosen to minimize its visibility on a light background, as well as by the choice of the active substance in the pattern of the first layer 2, the fluorescence color of which is contrasted with that of layer 3, advantageously being of color complementary (in subtractive synthesis) to that of the second layer 3.
Thus, if an operator scrolls a product equipped with the marking device 1 on a light then black background, he observes the blue triangle then the green circle.
The passage of the white background or dark background is in this case the physical stimulus allowing the change of color of the marking device 1.
It is advantageously added that the intrinsic colors of the first layer 2 and of the second layer 3 respectively are chosen so that on a white background only layer 2 is visible.
The fluorescence colors are chosen so that only layer 3 is visible (dark background). For example, the fluorescence color of the first layer is complementary to that of the second layer, as already noted. In fact, layer 3 filters all the wavelengths of radiation below its color.
We note that the transition from a white background to a black background is a special case but we can of course use other background colors.
The table below summarizes the different colors of the device 1
Layer 2 Layer 3 (Lower)(Upper) couple of Couple of colors A / Bcolors C / DColorATVSintrinsicColor of ATperceived device sure light backgroundColor of BDfluorescenceColor of Dperceived device sure dark background
Second variant
As shown in FIGS. 5 to 7, the optical marking device 1 comprises a first layer of optical marking 2 and a second layer of optical marking 3.
In FIG. 7, layer 3 is superimposed on layer 2.
Only the first layer 2 comprises an optically variable element
4.
As shown in FIG. 5, the first layer 2 is identical to the first layer 2 detailed in relation to the first variant embodiment.
The second layer 3 has no optically variable element.
The second layer 3 has a color, obtained by all the techniques known to a person skilled in the art (mass dyeing, varnishing for example).
The color is for example red.
On a light background, the color appears light red and on a black background, the color appears dark red.
As shown in FIG. 7, a first half 1-1 of device 1 is placed on the light background while a second half 1-2 of device 1 is placed on the dark background.
On the light background, it is the second layer 3, red, which is visible only.
On the dark background, the first layer 2 is visible and we observe the green semicircle 9-2 on a dark red background.
The passage of the white background or dark background is in this case the physical stimulus allowing the change of color of the marking device 1.
It is noted that the optical effect obtained is allowed by the concentration of active substance of the ink or varnish used to produce the pattern 9 of the first layer 2 chosen to minimize its visibility on a light background as well as by the choice of color. of the second layer 3, the color of which is contrasted with the fluorescence color, and preferably of a color corresponding to the color complementary to the fluorescence used in the first layer 2.
Third variant
According to this third variant, the marking device 1 comprises a first layer 2 and a second layer 3.
The second layer 3 is identical to the second layer 3 detailed in relation to the first alternative embodiment.
The first layer 2 comprises, similarly to the first alternative embodiment, a pattern 9 comprising an optically variable element.
The first layer 2 or the second layer 3 is at least partially reflective in the visible light spectrum.
To do this, layer 2 can be a layer of metallized polymer (polycarbonate, polypropylene, PET) or a metallic layer directly. Layer 2 can also include micro-mirrors.
According to other variants not illustrated, the device 1 also comprises the substrate 11 which is metallized, or else the layer 2 is coated with a layer of ink having metallic reflections.
According to this third variant, the stimulus is the tilting of the angle of observation of the device 1, as a function of the light environment (that is to say light or dark environment).
Depending on the angle of observation, there is minimization or, on the contrary, maximization of the light capture, which allows the color switching of the device 1.
As can be seen in FIG. 8, when the observation direction D extends in a first direction, for example a direction N normal to a plane P of the device 1, the second layer 3 has the intrinsic color.
As can be seen in FIG. 9, when the direction of observation D makes a non-zero angle with the plane P, the second layer 3 has the color of fluorescence.
As can be seen in FIG. 10, when the observation direction D extends in the direction N, the blue triangle 10 of the second layer 3 is visible.
As can be seen in FIG. 11, when the direction D makes a non-zero angle with the direction N, the green disc 9 of the first layer 2 is visible.
According to a variant not illustrated, the first layer 2 comprises shades of gray.
It is noted that the optical effect obtained is enabled by the concentration of active substance to produce the pattern of the second layer 3 in order to minimize its visibility under normal observation, by the choice of the color of the first layer 2 which is contrasted with the complementary color of the fluorescence of the active substance of the second layer 3, and preferably the complementary color, as well as the tilt angle according to a gray level of the reflecting surface (the more the surface will be reflective (low level of gray), the smaller the tilt angle and vice versa).
According to another variant not shown, the optical color switching effect can be obtained when at least one of the layers 2, 3 has optical scattering properties.
Preferably, the layer 2, 3 having diffusing properties is for example matt.
In this case, depending on the angle of observation, the diffusion prevents fluorescence, and only the intrinsic color appears.
Other variant
Advantageously, the optical marking device 1 comprises a polarizing film, not shown.
The polarizing film can be constituted by layer 2 or the substrate 11 for example.
In this case, the substrate 11 is not necessarily transparent, unlike the variants described above.
The polarization of the light allows the viewing of one of the layers 2 then of the other layer 3.
applications
The subject of the invention is also an identity, fiduciary, administrative document or a label, comprising at least one optical marking device 1.
For example, the document can be an identity card, passport, permit, certificate, diploma, checkbook, register, stamp, seal, visa, bank card, banknote.
The motif can be a national symbol, or a symbol of a company or national, a logo associated with a brand, or a fixed or variable mention, or a nominal value.
The marking device 1 occupies all or part of the document.
Benefits
As appears from the above description, the marking device according to the present invention has the advantage of effective securing of a document using in particular physico-chemical stimuli, such as passing over a light background and then dark background, or change of viewing angle.
Any agent will be able to carry out a simple and rapid verification of the document, since it is not necessary that it be provided with an expensive accessory and that a single gesture is sufficient for verification.
The family of fluorescent compounds of 4,4-difluoro-4-bora-3a, 4adiaza-s-indacènes and / or the family of difluoroborane β-diketonate (BF2bdks), ensures (s) a simple process for manufacturing the device for marking 1 since they are easily incorporated into a polymer, and have good thermal stability, which also makes possible all the steps necessary for manufacturing the document in which one or more marking device (s) 1 are integrated.
It is added that the embodiments described are combinable insofar as they are not incompatible.

权利要求:
Claims (17)
[1" id="c-fr-0001]
1. Optical marking device comprising at least a first layer (2) and a second layer (3) arranged at least partially opposite one another, at least one of said first and second layers comprising an element optically variable (4, 5) having a color change between a first color and a second color, said first and second colors being contrasted with a color of the other layer so that when the optically variable element (4 , 5) has said first color, the first layer (2) is visible and when the optically variable element (4, 5) has said second color, the second layer (3) is visible or when the optically variable element (4 , 5) has said first color, the second layer (3) is visible and when the optically variable element (4, 5) has said second color, the first layer (2) is visible.
[2" id="c-fr-0002]
2. Device according to claim 1, wherein at least one of the two layers (2, 3) comprises a pattern (9, 10) provided with said optically variable element (4, 5).
[3" id="c-fr-0003]
3. Device according to one of the preceding claims, comprising a substrate (11) on which rests at least one of said first and second layers.
[4" id="c-fr-0004]
4. Device according to one of the preceding claims, in which the two layers (2, 3) are in contact with one another.
[5" id="c-fr-0005]
5. Device according to one of the preceding claims, in which at least one of the two layers (2, 3) is at least partially reflective in the visible light spectrum and / or has shades of gray.
[6" id="c-fr-0006]
6. Device according to one of the preceding claims, in which at least one of the two layers (2, 3) is at least partially diffusing in the visible light spectrum.
[7" id="c-fr-0007]
7. Device according to one of the preceding claims, in which the optically variable element (4, 5) comprises one or more fluorescent compound (s).
[8" id="c-fr-0008]
8. Device according to the preceding claim, wherein the optically variable element (4, 5) comprises one or more compound (s) of the family of 4,4-difluoro-4-bora-3a, 4a-diaza-s- indacenes.
[9" id="c-fr-0009]
9. Device according to the preceding claim, in which the compound (s) of the family of 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacènes are chosen from those of formula I:

in which,
R ¹ is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, said phenyl group being optionally substituted by one or more groups chosen from C1 to C2 alkyl, hydroxy, R ⁵ COO 'and halogen;
R ² and R ² are independently selected from hydrogen and C1 to C2 alkyl;
R ³ and R ³ are independently selected from hydrogen and C1 to C3 alkyl;
R ⁴ and R ⁴ 'are independently chosen from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted by one or more groups chosen from C1 to C3 alkyl, aryl , hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to C2 alkyl, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted by a C1 to C2 alkyl group ;
R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl.
[10" id="c-fr-0010]
10. Device according to one of the preceding claims, in which the optically variable element (4, 5) comprises one or more compound (s) from the family of difluoroborane β-diketonate (BF2bdks).
[11" id="c-fr-0011]
11. Device according to the preceding claim, in which the compound (s) of the family of difluoroborane β-diketonate (BF2bdks) are chosen from those of formula II:
B
R ¹ ----- L ¹ (I) in which,
L ¹ is an unsaturated or nonexistent aliphatic chain,
L ² is an unsaturated or nonexistent aliphatic chain,
R ¹ is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group,
R ² is an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group, and
R ³ is chosen from hydrogen, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.
[12" id="c-fr-0012]
12. Device according to one of the preceding claims, comprising a polymer for incorporating the optically variable element (4, 5).
[13" id="c-fr-0013]
13. Device according to the preceding claim, wherein the polymer is chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride), polyamides, polyaramides , vinylethylene acetate (EVA), polyurethane, thermoplastic polyurethane (TPU), cyanoacrilate, rosin resins, pine resins, photopolymerizable resins or mixtures thereof.
[14" id="c-fr-0014]
14. Device according to one of the preceding claims, in which one of said first and second colors of the layer comprising the optically variable element is the color complementary to the color of the other layer.
[15" id="c-fr-0015]
15. Device according to one of the preceding claims, in which the two layers (2, 3) comprise an optically variable element (4, 5) having a color change, the two optically variable elements (4, 5) being at least partially overlapped and configured so that only the first layer (2) is visible when a first stimulation is applied to the device (1) and that only the second layer is visible (3) when a second stimulation is applied to the device (1).
[16" id="c-fr-0016]
16. Device according to one of the preceding claims, comprising an element configured to polarize light passing through said optical marking device (1).
[17" id="c-fr-0017]
17. Identity, fiduciary, administrative document or a label comprising at least one optical marking device (1) according to one of the preceding claims.

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同族专利:

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公开号 | 公开日

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CN112154072A|2020-12-29|

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KR20210005892A|2021-01-15|

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JP2021522082A|2021-08-30|

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FR3080325B1|2020-10-02|

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US20210039421A1|2021-02-11|

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EP3781409A1|2021-02-24|

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BR112020021340A2|2021-01-19|

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AU2019254794A1|2020-12-03|

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WO2019202280A1|2019-10-24|

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CA3099006A1|2019-10-24|

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法律状态:
2019-02-20| PLFP| Fee payment|Year of fee payment: 2 |

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2019-10-25| PLSC| Publication of the preliminary search report|Effective date: 20191025 |

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2020-03-30| PLFP| Fee payment|Year of fee payment: 3 |

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2021-02-22| PLFP| Fee payment|Year of fee payment: 4 |

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2022-02-23| PLFP| Fee payment|Year of fee payment: 5 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1853464|2018-04-19|

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FR1853464A|FR3080325B1|2018-04-19|2018-04-19|OPTICAL MARKING DEVICE|FR1853464A| FR3080325B1|2018-04-19|2018-04-19|OPTICAL MARKING DEVICE|

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CA3099006A| CA3099006A1|2018-04-19|2019-04-19|Optical marking device|

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JP2020557244A| JP2021522082A|2018-04-19|2019-04-19|Optical marking device|

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BR112020021340-3A| BR112020021340A2|2018-04-19|2019-04-19|OPTICAL MARKING DEVICE|

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AU2019254794A| AU2019254794A1|2018-04-19|2019-04-19|Optical marking device|

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CN201980033675.7A| CN112154072A|2018-04-19|2019-04-19|Optical marking device|

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KR1020207033172A| KR20210005892A|2018-04-19|2019-04-19|Optical marking device|

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PCT/FR2019/050946| WO2019202280A1|2018-04-19|2019-04-19|Optical marking device|

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US17/048,268| US20210039421A1|2018-04-19|2019-04-19|Optical marking device|

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EP19728479.7A| EP3781409A1|2018-04-19|2019-04-19|Optical marking device|