EP4164891A1

EP4164891A1 - Fluorescent composition comprising at least one benzazole compound for the securement of products

Info

Publication number: EP4164891A1
Application number: EP21736639.2A
Authority: EP
Inventors: Cosimo PRETE; Jérémy MALINGE; Alexis DEPAUW
Original assignee: Crime Science Technology SAS
Current assignee: Crime Science Technology SAS
Priority date: 2020-06-10
Filing date: 2021-06-10
Publication date: 2023-04-19
Also published as: MX2022015817A; WO2021250358A1; CN115768631A; AU2021286927A1; FR3111354A1; KR20230031208A; BR112022025158A2; US20230235190A1; JP2023531167A; CA3185150A1

Abstract

The invention relates to the use of a fluorescent composition for the securement of a product, said composition comprising a polymer matrix incorporating a compound having formula I: (Formula I)

Description

Title: Fluorescent composition comprising at least one benzazole-type compound for securing products

Technical area

The present invention relates to the field of securing and authenticating products. More particularly, the invention relates to a fluorescent composition for securing and authenticating products such as identity, fiduciary and administrative documents.

Prior art

[0002] Counterfeiting and the production of fakes are developing significantly in a good number of sectors such as that of packaging, in particular the blister packaging of drugs, but also in sectors with high added value such as luxury goods, automotive or aeronautics. With the development of identity theft and the introduction, in particular, of points-based driving licenses in certain countries, identity and administrative documents are also the target of falsification. Securing and authenticating products is therefore essential and involves both national and international security issues.

Regarding product security such as an identity, fiduciary or administrative document, various companies provide visual authentication solutions, for example using holograms or laser engravings, which can allow the insertion of information about a plastic card body such as an identity card, health card or driver's license.

[0004] Document EP0708935 A1 describes for example a set of holographic protection layers. This assembly consists of a support film having at least one layer formed by a protective varnish, a reflective or transparent layer bearing a diffracting microstructure, and finally, an adhesive layer. Once the set of layers has been transferred to a document, the latter is secured. As described in document WO2010 / 086522, this system was then improved by means of perforations making it more difficult the separation of the different layers. However, the set of layers, even perforated, consists of a multitude of parts that it is necessary to assemble which represents additional constraints in terms of time and cost.

[0005] Document FR 16 50164, of which the Applicant is the holder, describes the use of a compound of the family of 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacenes for the preparation of an element for securing a product, in particular a document, said securing element comprising a polymer and the compound being incorporated into said polymer. Although interesting, the use of the compounds described only allows fluorescence emissions to be obtained within the range from 500 nm to infrared, and thus does not cover the entire range of the visible spectrum.

[0006] Application US 2008/0081913 A1 describes compounds of benzoxazole and benzothiazole type exhibiting fluorescent properties and having utility in particular as authentication compounds in data storage media and data storage substrates.

[0007] The products, and in particular the documents, can be secured by security elements that can be classified according to three security levels depending on the means implemented for their detection. Thus, level 1 security elements are elements that can be detected by at least one of the five senses or through a contrasting background. In this level we will find in particular guilloches, optical variability devices such as iridescent prints, holograms, optically variable inks ("Optical Variable Ink"), markers, variable laser images ("Changeable Laser Image") or again the multiple laser images ("Multiple Laser Image").

[0008] The level 2 security elements are elements that can be detected by means of simple equipment such as an Ultra-Violet lamp, a convex lens or even a flash light from a mobile phone. Detectable elements such as micro-prints, fluorescent inks, as well as fluorescent fibers or plates are found in this level. Finally, the level 3 security elements are elements detectable by means of sophisticated equipment such as for example a spectrofluorimeter or an electron microscope. In this category are found in particular nano-engraved pigments, biometric chips as well as fluorescent markers not detectable with the naked eye (in English: taggants).

In general, a secure product incorporates several security elements of different levels.

[0011] Although the existing security solutions are of interest, some can be difficult to implement and / or to control and the need to develop alternatives, especially in the visible spectrum, is still present.

[0012] There is therefore a real need to develop new means of securing that are simple to use, stable, having fluorescence emissions and allowing rapid control of the authenticity of the products. These new means must ensure a high level of security and must not be mutually exclusive and existing means.

[0013] It is therefore to the credit of the inventors to have achieved all or part of these objectives by identifying and developing compounds which make it possible to obtain a particularly advantageous fluorescent composition for use in the field of product security.

Summary

The present relates to a fluorescent composition comprising a polymer matrix incorporating a compound of formula I:

[Chem. 1] in which,

X is selected from NH, O and S;

Z is selected from OH, NHR ⁵ and N (R ⁵ ) 2; R is selected from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH ₂ , -NHR ⁴ , -N (R ⁴ ) ₂ , -N ⁺ (R ⁴ ) ₃ , -NHCOR ⁴ , -CHO, - C (0) 0H, -C (0) 0R ⁴ , -CFs, C1-C6-alkoxy, aryloxy, -SH, -SOsH, -SR ⁴ ;

R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR ⁴ , -N (R ⁴ ) 2, -N ⁺ (R ⁴ ) 3, -NHCOR ⁴ , -CHO, -C (0) 0H, -C (0) 0R ⁴ , -CFs, C1 -C6-alkoxy, aryloxy, -SH, -SOsH, - SR ⁴ ;

R ⁴ is selected from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;

R ⁵ is chosen from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1 -C6-alkyloxycarbonyl, C1 -C6-alkylaminocarbonyl, C1 -C6-alkylaminothionyl, di-C1-C6-alkylaminothionyl , arylaminocarbonyl, arylaminothionyl, arylsulfonyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted with C1-C6-alkyl, C1- C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; with the proviso that Z is not OH when R ² is -NHCOR ⁴ ; and in which the symbol means that R can be substituted one more than once at any free position of the benzene ring. According to another aspect, there is proposed the use of a fluorescent composition according to the invention for securing a product.

According to another aspect, there is provided a method for securing a product comprising a step of preparing a fluorescent composition as defined above and a step of securing by applying said fluorescent composition to at least one part of the product to be secured.

According to another aspect, there is proposed a compound of formula (II):

[0018] [Chem. 2.] in which,

R ¹ , and R ² and R ³ are independently selected from hydrogen, C1 -C6-alkyl, C3- C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR ⁴ , -N (R ⁴ ) 2, - N ⁺ (R ⁴ ) ₃ , -NHCOR ⁴ , -CHO, -C (0) 0H, -C (0) 0R ⁴ , -CFS, C1 -C6-alkoxy, aryloxy, -SH, -SOsH , -SR ⁴ ; R ⁴ is selected from C1 -C6-alkyl, C1 -C6-cycloalkyl and aryl;

R ⁵ is chosen from C1-C6-alkyl, hydroxy-C1 -C6-alkyl, C1 -C6-alkyloxycarbonyl, di-C1 -C6-alkylaminothionyl, C1 -C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5 , 6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1 -C6-alkyl, C1 -C6-alkoxy, trifluoro-C1 -C6-alkyl, C1 -C6-alkylamino or hydroxy-C1 -C6- alkylamino; and with the condition that:

R ¹ , R ² and R ³ are not all three hydrogen when R ⁵ is cinnamoyl, or benzoyl optionally substituted with methyl, methoxy, chloro or trifluoromethyl; R ¹ is not methyl when R ⁵ is benzoyl;

R ² is not methyl when R ⁵ is benzoyl; and

R ³ is not methyl, methoxy or chloro when R ⁵ is benzoyl.

Detailed description of the invention [0019] A first object of the invention relates to a fluorescent composition comprising a polymer matrix incorporating a compound of formula I:

[0020] [Chem. 1] wherein, X is selected from NH, O and S; preferably X is S;

Z is selected from OH, NHR ⁵ and N (R ⁵ ) 2; preferably Z is NHR ⁵ or N (R ⁵ ) 2; more preferably Z is NHR ⁵ ;

R is chosen from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, C (0) 0H, -C (0) 0R ⁴ , -CF3, aryloxy, -SH, -SO3H, -SR ⁴ ; preferably R is chosen from hydrogen, C1-C4-alkyl, halogen, -NO2, -NH2, -NHR ⁴ , -N (R ⁴ ) 2, C1-C4-alkoxy; more preferably R is chosen from hydrogen, C1-C2-alkyl, halogen, C1-C4-alkoxy; more preferably, R is hydrogen;

R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR ⁴ , -N (R ⁴ ) 2, -N ⁺ (R ⁴ ) 3, -NHCOR ⁴ , -CHO, -C (0) 0H, -C (0) 0R ⁴ , -CFs, C1-C6-alkoxy, aryloxy, -SH, -SOsH, - SR ⁴ ; preferably R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; more preferably R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably R ¹ , R ² and R ³ are independently chosen from hydrogen, C1 -C2-alkyl, C1 -C2-alkoxy, halogen and -NO2; even more preferably R ¹ , R ² and R ³ are independently chosen from hydrogen, methyl, methoxy, bromo, chloro and -NO2;

R ⁴ is selected from alkyl, cycloalkyl and aryl; preferably R ⁴ is chosen from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;

R ⁵ is chosen from C1 -C6-alkyl, hydroxy-C1 -C6-alkyl, halogen, aryl, acyl, C1 -C6-alkyloxycarbonyl, C1 -C6-alkylaminocarbonyl, C1 -C6-alkylaminothionyl, di-C1 -C6-alkylaminothionyl , arylaminocarbonyl, arylaminothionyl, arylsulfonyl, C1 -C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1 -C6-alkyl, C1 - C6-alkoxy, trifluoro-C1 -C6-alkyl, C1 -C6-alkylamino or hydroxy-C1 -C6-alkylamino; preferably R ⁵ is chosen from cinnamoyl, benzoyl, 2, 3, 4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1 -C6-alkyl, C1 -C6-alkoxy, trifluoro- C1 -C6-alkyl, C1 -C6-alkylamino or hydroxy-C1 -C6-alkylamino; more preferably R ⁵ is chosen from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2, 3,5,6-tetrafluorobenzoyl, optionally substituted by C1 -C4-alkyl, C1 -C4-alkoxy, trifluoro -C1 -C4-alkyl, C1 -C4-alkylamino or hydroxy-C1 -C4-alkylamino; more preferably R ⁵ is chosen from cinnamoyl, benzoyl, 2, 3, 4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted by methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino; for example R ⁵ is chosen from benzoyl, 4- (trifluomethyl) benzoyl, 3,5- bis (trifluomethyl) benzoyl, 2,3,4,5,6-pentafluorobenzoyl, 4- (butylamino) -2, 3,5, 6- tetrafluorobenzoyl, cinnamoyl and 4 - ((2-hydroxyethyl) amino) benzoyl; in particular R ⁵ is chosen from benzoyl, 3,5-bis (trifluomethyl) benzoyl, 4- (butylamino) -2,3,5,6-tetrafluorobenzoyl and cinnamoyl with the condition that Z is not OH when R ¹ is -NHCOR ⁴ .

It is understood in the present application that when several preference levels are given for different substituents of a Markush formula, different preference levels can be combined with one another. In other words, it is understood that all the combinations of the different levels of preference are explicitly envisaged. The polymer matrix of the fluorescent composition according to the invention can be obtained from an amorphous or semi-crystalline polymer chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride), polyamides, polyaramides, vinyl ethylene acetate, polyurethane, thermoplastic polyurethane, cyanoacrylate, rosin resins, pine resins, light-curing resins, acrylic and theirs mixtures. Preferably, the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polyethylene, thermoplastic polyurethane, acrylic and photopolymerizable resins and their mixtures, and more preferably polymer matrix is a polycarbonate or polypropylene matrix. For example, the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (vinyl chloride) , polyamides, polyaramides, polyurethane, thermoplastic polyurethane (TPU), cyanoacrylate, rosin resins, pine resins, light-curing resins, acrylic and their mixtures. In particular, the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, thermoplastic polyurethane, photopolymerizable resins, acrylic, and mixtures thereof. More particularly, the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polyethylene, polypropylene, polyethylene terephthalate and their mixtures. More particularly still, the polymer matrix of the fluorescent composition can be obtained from a polymer chosen from polycarbonate, polypropylene, polyethylene terephthalate and mixtures thereof. Still more particularly, the polymer matrix of the fluorescent composition can be obtained from polycarbonate or polyethylene terephthalate.

According to a particular embodiment, the polymer matrix is a semi-crystalline polymer matrix. Advantageously, the polymer matrix does not contain an anti-UV additive in order thus to allow optimum maintenance of the fluorescence properties. Likewise, it is also advantageous to use a polymer matrix which retains its transparency properties even after a shaping step.

By the expression "polymer matrix incorporating a compound of formula I" is meant within the meaning of the present invention that the compound of formula I is intimately integrated into the polymer matrix so as to form a mixture. Preferably, the compound of formula I is intimately integrated into the polymer matrix so as to form a homogeneous mixture exhibiting no dispersion. The integration of the compound into the polymer matrix can for example be carried out hot. In this scenario, the polymer matrix is heated to its melting point, then the compound of formula I is added to the melt before the whole is mixed. Thus, the integration of the compound into the polymer matrix can be carried out by melt, extrusion, calendering extrusion, extrusion spinning, plastic injection or dyeing.

[0026] In a particularly advantageous manner, the inventors have found that the compounds of formula I according to the invention can be incorporated into polymer matrices without altering either the performance of the matrix, or especially that of the incorporated compounds.

In one embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are the compounds of formula I in which X is S.

Thus, according to this embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are those of formula la:

[0029] [Chem. 3.] wherein R, R ¹ , R ² , R ³ and Z are as defined in formula I.

Preferred compounds of formula la are those in which R, R ¹ , R ² , R ³ and / or Z are defined as follows: Z is NHR ⁵ or N (R ⁵ ) ₂ ;

R is selected from hydrogen, C1-C4-alkyl, halogen, -NO2 and C1-C4-alkoxy; preferably R is hydrogen;

R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; preferably R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, Cl, F and -NO2; even more preferably R ¹ , R ² and R ³ are independently chosen from hydrogen, methyl, methoxy, Cl, F and - NO2; R ⁵ is chosen from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1 -C6-alkyloxycarbonyl, di-C1 -C6-alkylaminothionyl, arylaminocarbonyl, arylsulfonyl, C1-C6-alkylsulfonyl, cinnamoyl , benzoyl and 2, 3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; preferably R ⁵ is chosen from cinnamoyl, benzoyl and 2, 3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; more preferably R ⁵ is chosen from cinnamoyl, benzoyl and 2, 3,5,6-tetrafluorobenzoyl, optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, trifluoro-C1-C4-alkyl, C1-C4-alkylamino or hydroxy-C1-C4-alkylamino; more preferably R ⁵ is chosen from cinnamoyl, benzoyl and 2, 3,5,6- It is tetrafluorobenzoyl, optionally substituted by methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino; for example R ⁵ is chosen from benzoyl, 4- (trifluomethyl) benzoyl, 3,5-bis (trifluomethyl) benzoyl,

2,3,4,5,6-pentafluorobenzoyl, 4- (butylamino) -2,3,5,6-tetrafluorobenzoyl, cinnamoyl and 4 - ((2-hydroxyethyl) amino) benzoyl; in particular R ⁵ is chosen from benzoyl, 3,5-bis (trifluomethyl) benzoyl, 4- (butylamino) -2, 3,5,6-tetrafluorobenzoyl and cinnamoyl.

According to a variant of this embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are those of formula Ib: [0032] [Chem. 4] wherein R, R ¹ , R ² , R ³ and R ⁵ are as defined in formula I.

Preferred compounds of formula Ib are those in which R, R ¹ , R ² , R ³ and R ⁵ are defined as follows: R is chosen from hydrogen, C1-C4-alkyl, halogen, -NO2 and C1-C4-alkoxy; preferably R is hydrogen;

R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; preferably R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably R ¹ , R ² and R ³ are independently selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, Cl, F and -NO2; even more preferably R ¹ , R ² and R ³ are independently chosen from hydrogen, methyl, methoxy, Cl, F and - NO2;

R ⁵ is selected from cinnamoyl, benzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted with C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; preferably R ⁵ is chosen from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, trifluoro-C1-C4-alkyl, C1-C4-alkylamino or hydroxy-C1-C4-alkylamino; more preferably R ⁵ is chosen from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted by methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino; for example R ⁵ is chosen from benzoyl, 4- (trifluomethyl) benzoyl, 3,5-bis (trifluomethyl) benzoyl, 2, 3, 4,5,6-pentafluorobenzoyl, 4- (butylamino) -2,3,5, 6-tetrafluorobenzoyl, cinnamoyl and 4- ((2-hydroxyethyl) amino) benzoyl; in particular R ⁵ is chosen from benzoyl, 3,5- bis (trifluomethyl) benzoyl, 4- (butylamino) -2,3,5,6-tetrafluorobenzoyl and cinnamoyl.

According to another variant of this embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are those of formula le:

[0035] [Chem. 5] in which R, R ¹ , R ² , R ³ and R ⁵ are as defined in formula I. [0036] In one embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are the compounds of formula I wherein Z is NHR ⁵ or N (R ⁵ ) 2, preferably Z is NHR ⁵ . In one embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are the compounds of formula I in which R is hydrogen.

Particularly preferred compounds of formula I incorporated into the polymer matrix of the fluorescent composition of the invention are those listed in Table 1 below:

[0039] [Table 1]

Compounds of formula I incorporated into the polymer matrix of the fluorescent composition more particularly preferred of the invention are the compounds 3, 4, 5, 8, 9, 10, 11, 12, 13, 14, 16, 27, 29 and 35 listed in Table 1 above.

[0041] Even more particularly preferred compounds of formula I incorporated into the polymer matrix of the fluorescent composition are compounds 3, 13, 14 and 27 listed in Table 1 above.

[0042] Even more particularly preferred compounds of formula I incorporated into the polymer matrix of the fluorescent composition are compounds 13, 14 and 27 listed in Table 1 above.

[0043] Within the fluorescent composition according to the invention, the polymer matrix incorporates an amount of compound of formula I necessary for the detection of the properties of absorbances and fluorescences. The compounds of formula I according to the invention have the advantage of allowing detection of said properties, even when they are incorporated in small amounts within the polymer matrix. Thus, the amounts of compounds of formula I ranging from 0.005% to 20% by weight relative to the total weight of the polymer matrix are sufficient for detection, preferably amounts ranging from 0.01% to 15% by weight relative to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix. In particular, the amount of compound of formula I incorporated into the polymer matrix of the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10%, between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.

According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above.

According to another particular embodiment, the fluorescent composition consists essentially of a polymer matrix integrating a compound of formula I as defined above. The expression “essentially constituted” is understood to mean, within the meaning of the present invention, that the composition fluorescent consists of more than 96%, 97%, 98%, or even more than 99% of a polymer matrix integrating a compound of formula I.

According to a first variant of the invention, the fluorescent composition further comprises a second compound of formula I as defined above, or one of its sub-formulas la, Ib and le.

According to this variant, the amounts of second compound of formula I are from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably amounts ranging from 0.01% to 15% by weight relative to to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix. In particular, the amount of the second compound of formula I incorporated into the polymer matrix of the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10% , between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.

According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above and a second compound of formula I as defined above.

According to a particular embodiment, the fluorescent composition also comprises a difracting network or a reasoning network.

The fluorescent composition according to the invention comprising a polymer matrix in which are integrated two different compounds of formula I, or one of its sub-formulas la, Ib and le, as defined above allows to obtain fluorescent compositions with particularly advantageous properties.

In fact, when two different compounds of formula I are mixed together, or one of its sub-formulas la, Ib and le, and that said compounds emit at different wavelengths, it is then possible to modify the fluorescence color emitted under UV irradiation The composition is then colored only under UV (level 2) and this color is the mixture of the emissions of the two compounds of formula I.

According to a second variant of the invention, the fluorescent composition also comprises a compounds of the family of 4-bora-3a, 4a-diaza-s-indacene, also called "BODIPY", said BODIPY being incorporated into the matrix polymer. Very particularly, according to this embodiment, the BODIPYs can be compounds of formula III below:

[0053] [Chem. 6] 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; preferably R ¹ is phenyl optionally substituted with one or more groups chosen from C1 to C2 alkyl; more preferably R ¹ is phenyl substituted with one or more groups chosen from C1 to C2 alkyl; more preferably R ¹ is phenyl substituted with several groups chosen from C1 to C2 alkyl; more preferably R ¹ is phenyl substituted with several methyl groups; more preferably R ¹ is 2,4,6-trimethylphenyl;

R ² and R ^{2 '} are independently selected from hydrogen and C1 to C2 alkyl; preferably R ² and R ^{2 '} are hydrogen;

R ³ and R ^{3 '} are independently selected from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups chosen from C1 to C4 alkyl, aryl, hydroxy and ferrocene, said aryl group being optionally substituted by one or more groups chosen from aryl, C1 to alkyl C2, halogen, hydroxy, dimethylamino, nitro, said aryl being optionally substituted with a C1 to C2 alkyl group; preferably R ³ and R ^{3 '} are hydrogen;

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 ; preferably R ⁴ and R ^{4 '} are aryl optionally substituted with one or more groups chosen from C1 to C3 alkyl; more preferably R ⁴ and R ^{4 '} are phenyl optionally substituted with one or more groups chosen from C1 to C2 alkyl; more preferably R ⁴ and R ^{4 '} are phenyl substituted with one or more groups chosen from C1 to C2 alkyl; more preferably R ⁴ and R ^{4 '} are phenyl substituted by several groups chosen from C1 to C2 alkyl; more preferably R ⁴ and R ^{4 '} are phenyl substituted with several methyl groups; more preferably R ⁴ and R ^{4 '} are 2,4,6-trimethylphenyl;

R ⁵ is C1 to C4 alkyl or C2 to C4 alkenyl.

R ⁶ and R ^{6 '} are independently selected from halogens, C1 to C4 alkoxy, C2 to C4 alkenyloxy, C1 to C4 alkyl, C2 to C4 alkenyl, CN or aryl, said aryl being optionally substituted with one or more groups selected from C1 to C2 alkyl, hydroxy, R ⁵ COO- and halogen; preferably R ⁶ and R ^{6 '} are independently chosen from halogens; more preferably R ⁶ and R ^{6 '} are fluorine atoms.

According to this variant, the amounts of compound of formula III are from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably amounts ranging from 0.01% to 15% by weight relative to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix. In particular, the amount of compound of formula III incorporated into the polymer matrix of the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10%, between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.

According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above and a second compound of formula III as defined above.

The fluorescent composition according to this second variant comprising a polymer matrix in which are integrated a compound of formula I as defined above and a compound of formula III as defined above makes it possible to obtain fluorescent compositions with particularly advantageous properties. .

In fact, when a compound of each family is mixed together and said compounds emit at different wavelengths, it is then possible to modify the fluorescence color emitted under UV. However, and advantageously, the detection properties of the fluorescent composition according to level 1 and level 2 by flash light of a mobile phone remain unchanged and are not altered.

The fluorescent composition thus obtained exhibits a color on a white background and a color visible, for example on a black background and under flash light from a mobile telephone obtained from the compound of formula III. Under UV irradiation (level 2), the composition exhibits a third color resulting from the mixture of the emissions of the compounds of formula I and of formula III. According to a third variant of the invention, the fluorescent composition further comprises a fluorescent compound whose response under UV radiation is controlled, which absorbs ultraviolet electromagnetic radiation, in particular between 300 and 400 nm, of wavelength and then re-emits this energy by fluorescence in the visible range, and in particular between 400 and 500 nm.

According to this variant, the amounts of fluorescent compound whose response under UV radiation is controlled are from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably amounts ranging from 0.01% to 15 % by weight relative to the total weight of the polymer matrix and even more preferably, amounts ranging from 0.05% to 10% by weight relative to the total weight of the polymer matrix. In particular, the amount of fluorescent compound whose response under UV radiation is controlled in the fluorescent composition is between 0.005% and 10% by weight relative to the total weight of the polymer matrix, more particularly between 0.01% and 10% , between 0.01% and 5%, between 0.01% and 1%, between 0.05% and 5%, between 0.05% and 1%, by weight relative to the total weight of the polymer matrix.

According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound of formula I as defined above and a fluorescent compound whose response under UV radiation is controlled.

The fluorescent composition according to this second variant comprising a polymer matrix in which are integrated a compound of formula I as defined above and a fluorescent compound whose response under UV radiation is controlled makes it possible to obtain fluorescent compositions with particularly advantageous properties. .

Thus, a second object of the invention relates to the use of a fluorescent composition according to the invention for securing a product. A product within the meaning of the present invention can be any type of product suitable for receiving said fluorescent composition. The product can thus be a solid or a liquid. It may for example be plastic objects such as parts or packaging, luxury products such as leather goods, cosmetics, paintings or even documents. Preferably, the products are documents.

The term document refers in particular to an assembly formed by a support and an item of information. The support can be of different natures, take different forms, and can optionally comprise a polymer or a mixture of polymers. This support can for example be made entirely or in part of a polymer material. By way of example of a document, we can cite in particular identity documents such as passports, identity cards, driving licenses or health cards, but also fiduciary documents such as banknotes and checks, or even administrative documents such as registration certificates. The documents can therefore be in the form of paper, a booklet or even a map, and the information can also be printed and / or engraved on it.

By the expression "securing a product" is meant within the meaning of the present invention that the fluorescent composition is integrated into the product or into the product to be secured at any time during its design. Thus, the fluorescent composition can equally well be used for securing the product during its manufacture, as well as being applied or integrated subsequently into the latter. For example, in the context of securing a document-type product, the fluorescent composition can be applied a posteriori to all or part of the document. This point is developed further in the description.

In all cases, the products are secured by the use of a fluorescent composition comprising a polymer matrix incorporating a compound of formula I described above, a mixture of two compounds of formula I, or a mixture of a compound of formula I and of a compound of formula III, and can be authenticated by virtue of the properties and effects conferred by the fluorescent composition. In fact, the secure products in accordance with the invention can be authenticated by virtue of the unique combination of the absorbed wavelength and of the specific fluorescence of the fluorescent composition. Thus, only a genuine product will exhibit both the good absorption and fluorescence emission properties. Authentication within the meaning of the present invention is understood to mean the verification of the authenticity of a product by the detection of the fluorescent composition or of the security means incorporated therein. In the case of the use of a composition comprising a compound of formula I and a compound of formula III, this detection of the presence or absence of coloration or fluorescence thus makes it possible to authenticate or not the product in question. . A product is therefore authentic when detection reveals the presence of the fluorescent composition, as opposed to a non-authentic product for which the detection will not allow the fluorescent composition to be demonstrated. The products secured according to the invention by means of a fluorescent composition can be authenticated on the three security levels described below thanks to the sole presence of said fluorescent composition comprising a compound of formula I and a compound of formula III .

In fact, in the case of the use of a composition comprising a compound of formula I and a compound of formula III, the compounds of formula III contained in the fluorescent composition may exhibit an absorption band in the visible range. and the color perceived with the naked eye will correspond to the color complementary to the color absorbed. For example, a compound absorbing around 500-520 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.

Regarding the fluorescence properties, the compounds of formula I according to the invention all have excitation bands in Ultra-Violet (UV). They can therefore be excited by means in particular of a UV or LED lamp emitting between 100 nm and 400 nm, which makes it possible to obtain level 2 security. This property makes it possible to obtain an activation / deactivation effect (on / off) which therefore corresponds to the visualization of a color change following a stimulation of the fluorescence of the fluorescent composition, in particular by a light source of the LED or UV type.

Finally, the emission wavelength can be determined using a low resolution spectrofluorimeter or fluorimeter with a single grating (detection by photodiode or photomultiplier tube), which gives security elements according to the present invention a level 3 security.

Thus, the products and in particular the secure documents according to the present invention will be, thanks to the association of absorption and fluorescence properties, detectable on levels 2 and 3 in the case of the use of a composition. comprising a compound of formula I or a mixture of two compounds of formula I, and on the 3 levels of security in the case of the use of a composition comprising a compound of formula I and a compound of formula III.

The fluorescent composition according to the present invention can be in several forms which are adapted by a person skilled in the art depending on the product to be secured. For example, if the product is a document, the fluorescent composition may be in the form of a layer, a set of layers, or a film.

According to a particular embodiment, the fluorescent composition is used in the form of a layer or of a set of layers prepared by techniques known to those skilled in the art such as, for example, lamination, extrusion, calendering, or extrusion calendering. These techniques will be chosen according to the polymer matrix used. By way of example, if the matrix is made of polycarbonate or thermoplastic polyurethane, shaping by calendering extrusion is preferred. Again by way of example, if the matrix is made of polypropylene, the principle of inflation extrusion is preferred, in particular the principle of inflation extrusion with bi-stretching. A set of layers within the meaning of the present invention can for example be obtained by laminating two or more layers of polymer matrix each incorporating one or more fluorescent compositions. Such a layer or set of layers finds a particularly advantageous application in the securing of documents, and more particularly identity, fiduciary or administrative documents. According to this particular embodiment, the layer or the set of layers is in the form of a card. Examples of cards are in particular professional cards, bank cards, or any other type of polymer matrix card. In this case, the fluorescent composition according to the invention constitutes the support of the document as such. The cards could for example be obtained by laminating several layers of polymer, at least one of which is the fluorescent composition according to the present invention.

In a particularly advantageous manner, in the case of the use of a composition comprising a compound of formula I, the layer or the set of layers is transparent which makes it possible to obtain, in addition to the above effects described, the following effects:

- waveguide effect: the presence of grooves in the layer or the whole layer generates a different diffraction index which stimulates the fluorescence of the secure layer. Thus, the color observed at the groove is different from that observed on the rest of the layer or the entire layer. Under UV irradiation, this constitutes level 2 safety.

- side-effect: this effect corresponds to the observation of a color complementary to the absorbed color which is different on the edges of the layer or of the set of layers, from that observed on the faces. Under UV irradiation, this constitutes level 2 safety.

In a particularly advantageous manner, in the case of the use of a composition comprising a mixture of a compound of formula I and of a compound of formula III, the layer or the set of layers is transparent. which makes it possible to obtain, in addition to the effects described above, the following effects:

- waveguide effect: the presence of grooves in the layer or the whole layer generates a different diffraction index which stimulates the fluorescence of the secure layer. Thus, the color observed at the groove is different from that observed on the rest of the layer or the entire layer. This constitutes level 1 security.

- change of color effect (switch-color): this effect corresponds to a change of color during the superposition of the layer or the whole of layers on a contrasting background (dark background type, in particular black, or light background, in particular white. We can thus observe the color complementary to the color absorbed on a light background and the fluorescence color on a dark background. This constitutes a level 1 security.

- side-effect: this effect corresponds to the observation of a color complementary to the absorbed color which is different on the edges of the layer or of the set of layers, from that observed on the faces. This constitutes level 1 security.

- shadow effect: this effect, linked to the presence of the compound of formula III, corresponds, when the fluorescence is stimulated by an LED or UV light and observed on a light background, in particular white, to the visualization both of the fluorescence color at the level of the layer and of the projection of the color complementary to the color absorbed on the light background. This constitutes level 2 security.

Advantageously, a layer has in particular a thickness ranging from 0.050 mm to 0.800 mm, preferably a thickness ranging from 0.200 mm to 0.600 mm, such as for example a thickness of approximately 0.400 mm. When the layer has a thickness of less than 0.100 mm, it is also called a film.

[0080] According to a particular embodiment, the fluorescent composition used for securing a product comprises only a polymer matrix integrating a compound of formula I as defined above.

According to another particular embodiment, the fluorescent composition used for securing a product essentially consists of a polymer matrix integrating a compound of formula I as defined above. For the purposes of the present invention, the expression “essentially constituted” is understood to mean that the fluorescent composition consists of more than 96%, 97%, 98%, or even more than 99% of a polymer matrix incorporating a polymer matrix. compound of formula I. According to another particular embodiment, the fluorescent composition used for securing a product consists of approximately 50% of a polymer matrix integrating a compound of formula I as defined above.

[0083] According to a particular embodiment, the fluorescent composition used for securing a product comprises only a polymer matrix integrating a mixture of two different compounds of formula I as defined above.

The fluorescent composition thus obtained exhibits a color resulting from the mixture of the colors of each of the two compounds of formula I and which is visible only under UV irradiation (level 2).

According to another particular embodiment, the fluorescent composition used for securing a product comprises only a polymer matrix integrating a compound of formula I and a compound of formula III as defined above.

In fact, when a compound of formula I and a compound of formula III are mixed together and said compounds emit at different wavelengths, it is then possible to modify the fluorescence color emitted under UV irradiation. However, and advantageously, the detection properties of the fluorescent composition according to level 1 and level 2 by flash light of a portable telephone remain unchanged and are not altered.

The fluorescent composition thus obtained has three colors, a first which is visible on a white background (level 1), a second which is visible for example on a black background or under flash light from a mobile phone (level 1) , and a third under UV irradiation (level 2).

Thus, the use of a composition comprising a mixture of compound of formula I and of a compound of formula III makes it possible to complexify level 2.

According to a particular embodiment, the fluorescent composition is used in the form of a fluorescent ink. According to this embodiment, the fluorescent ink is an ink suitable for printing, in particular for screen printing, offset printing, flexography, heliography, jet printing. ink, digital printing, intaglio printing and 3D printing, preferably for offset printing, and inkjet printing. Completely surprisingly, the inventors have advantageously observed that the fluorescent inks according to the invention could be used in printing without causing clogging of the print heads.

[0090] According to a particular embodiment, the fluorescent composition is used in the form of an aqueous ink.

[0091] According to another particular embodiment, the fluorescent composition is used in the form of a fluorescent varnish.

According to a particular embodiment, the fluorescent composition is used in the form of a film, that is to say a layer having a thickness less than 0.100 mm, in particular ranging from 0.050 mm to 0.100 mm, which is used to laminate both sides of a document, including an identity, fiduciary or administrative document. In a variant of this embodiment, such a film is applied only to one of the two sides of a document, in particular of an identity document. In yet another variant of the embodiment, such a film is applied only to a part of one of the two sides of a document, in particular of an identity document. In yet another variant of the embodiment, such a film is applied only to a part of each of the two sides of a document, in particular of an identity document.

[0093] According to another particular embodiment, the fluorescent composition is put in the form of a fiber. This shaping can be done by the techniques conventionally used to obtain fibers, said fibers can equally well be woven fibers or non-woven fibers.

According to this embodiment, the fibers are preferably obtained by the melt spinning technique, via an extrusion-spinning process. The manufacture of fibers by the melt spinning method involves first melting the mixture of polymer and fluorescent compound in an extruder. The molten material is then sent under pressure through a die made up of a multitude of heads. On leaving the die, the filaments are cooled by air, stretched then wound on a support. Generally, a size product can be applied to the lower part of the spinning stack.

According to one embodiment, the compound of formula I, the mixture of two compounds of formula I or the mixture of a compound of formula I and of a compound of formula III can be integrated into a polymer matrix without having recourse to extrusion, in particular by wire impregnation.

The shape of the fluorescent fiber obtained according to the extrusion-spinning processes can in particular be determined by the shape of the heads of the die. Thus, the fiber can in particular have a cylindrical, three-lobed, octalobed, hollow or multiple hollow shape. Changing the shape of the fibers can be beneficial in that it allows visual effects to be changed on a macroscopic scale. Indeed, the discontinuity of a section or the refractive index of light within the fiber can modify the transmission of light and therefore, the effects observed at the macroscopic scale.

According to another particular embodiment, several fluorescent compositions are used to secure the same product, the fluorescent compositions being different from each other at least by the nature of the compound of formula I, of the mixture of two compounds of formula I or the mixture of a compound of formula I and a compound of formula III, integrated into the polymer matrix. This embodiment advantageously makes it possible to better secure the product in question.

According to another particular embodiment, the polymer matrix is a photopolymerizable resin and the fluorescent composition also comprises a polar solvent to facilitate integration between the resin and the compound of formula I, the mixture of two compounds of formula I or the mixture of a compound of formula I and a compound of formula III. The fluorescent composition obtained thus finds a very particular application in certain 3D printing techniques, for example for the manufacture of holograms, said holograms then exhibiting a greater level of security.

A third object of the invention relates to a method for securing a product comprising the following steps of: - preparation of a fluorescent composition as defined above,

- securing by applying said fluorescent composition prepared in the previous step, to at least one of the parts of said product.

The first step therefore consists in obtaining a fluorescent composition as defined above.

[0101] According to a particular embodiment, the first step of the securing process consists in preparing a fluorescent composition comprising only a polymer matrix integrating a compound of formula I as defined above.

[0102] According to another particular embodiment, the first step of the securing process consists in preparing a fluorescent composition essentially consisting of a polymer matrix incorporating a compound of formula I as defined above. For the purposes of the present invention, the expression “essentially constituted” is understood to mean that the fluorescent composition consists of more than 96%, 97%, 98%, or even more than 99% of a polymer matrix incorporating a polymer matrix. compound of formula I.

According to a particular embodiment, the first step of the securing process consists in preparing a fluorescent composition comprising only a polymer matrix integrating two different compounds of formula I as defined above.

According to a particular embodiment, the first step of the securing process consists in preparing a fluorescent composition comprising only a polymer matrix integrating a compound of formula I as defined above and a compound of formula III as defined above. above.

[0105] According to a particular embodiment, the fluorescent composition is a fluorescent ink. According to this embodiment, the fluorescent ink is obtained from an ink known to those skilled in the art, said inks comprising a polymer matrix, in which is incorporated a compound of formula I, a mixture of two different compounds of formula I, or a mixture of a compound of formula I and a compound of formula III, so as to obtain the ink fluorescent. According to this embodiment, the securing step is advantageously carried out by printing fluorescent ink on the product to be secured, such as for example a document.

[0106] According to a particular embodiment, the fluorescent composition is a fluorescent varnish. According to this embodiment, the securing step can for example be carried out by coating or varnishing said fluorescent varnish on the product to be secured.

[0107] The step of securing all or part of the product to be secured is adapted by those skilled in the art depending on the product to be secured but also on the form of said composition.

[0108] The securing step consists of integrating the fluorescent composition into the product to be secured. Thus, the securing step can equally well be carried out during the manufacture of the product, as well as be carried out afterwards to the latter. For example, in the context of securing a document-type product, the securing step can be performed on the finished product. In addition, this step can be repeated several times on the same product in order to increase the level of security of the product.

[0109] The securing step can be carried out according to techniques known to those skilled in the art, for example by lamination, by printing, by weaving, by varnishing, by lacquering, by gluing, by coating or even by impregnation.

[0110] According to a particular embodiment, the fluorescent composition according to the invention comprising a compound of formula I and a compound of formula III is applied by coating on a reflecting surface or a metallized surface. The product is then secured by applying the assembly consisting of the reflective or metallized layer coated with the fluorescent composition. The metallized surfaces are layers known to those skilled in the art, it may be, for example, an aluminum metal layer.

Advantageously, according to this embodiment, the fluorescence properties of the fluorescent composition interact with the appearance. reflective layer of the reflective layer and this achieves specific visual effects for securing a product. At equivalent concentration, a reflecting surface enhances the light intensity compared to a non-reflecting surface.

[0112] The securing method according to the invention can also include a step of shaping the fluorescent composition before the securing step. The shaping step can be carried out according to techniques known to those skilled in the art which make it possible, for example, to obtain a layer, a set of layers, a film or fibers. This formatting step can thus facilitate the subsequent securing step by application.

According to a particular embodiment, the first step of the process consists in preparing several fluorescent compositions which differ by the nature of the compound of formula I integrated into the polymer matrix. According to this embodiment, the securing step consists in applying simultaneously or in a delayed manner the compositions prepared and thus increasing the level of security conferred on the product.

[0114] The method according to the invention can be used to secure any type of product suitable for receiving said fluorescent composition. For example, it can be plastic objects such as coins or packaging, luxury products such as leather goods, or even documents. Preferably, the products secured according to the method described are documents.

[0115] According to a particular embodiment, the product to be secured is a document such as an identity, fiduciary or administrative document. According to this embodiment, the application of the fluorescent security composition can be carried out on at least part of one face of the product. According to a variant of this embodiment, the fluorescent security composition is put in the form of a film before being hot or cold laminated on all the faces of the document. In another variant, the film is applied only to one of the sides of a document. In yet another variant, the film is only applied to a part of one of the two sides of a document and in yet another variant, the film is only applied to a part of each of the sides. of a document. According to another particular embodiment, the polymer matrix of the fluorescent composition also incorporates a compound of formula II defined above.

Another subject of the invention relates to a compound of formula II: [0118] [Chem. 2] in which,

R ¹ , and R ² and R ³ are independently selected from hydrogen, C1-C6-alkyl, C3- C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR ⁴ , -N (R ⁴ ) 2, - N ⁺ (R ⁴ ) s, -NHCOR ⁴ , -CHO, -C (0) 0H, -C (0) 0R ⁴ , -CFs, C1 -C6-alkoxy, aryloxy, -SH,

-SO3H, -SR ⁴ ; preferably R ¹ , and R ² and R ³ are independently selected from hydrogen, C1-C6-alkyl, C1-C6-alkoxy, halogen and -NO2; preferably R ¹ , and R ² and R ³ are independently selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen and -NO2; more preferably R ¹ , and R ² and R ³ are independently chosen from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, chloro, fluoro and -NO2; more preferably R ¹ , and R ² and R ³ are independently chosen from hydrogen, methyl, methoxy, chloro, fluoro and -NO2; even more preferably R ¹ , and R ² and R ³ are independently chosen from hydrogen, methyl, methoxy, chloro and fluoro; R ⁴ is selected from C1 -C6-alkyl, C1 -C6-cycloalkyl and aryl;

R ⁵ is chosen from C1-C6-alkyl, hydroxy-C1-C6-alkyl, C1-C6-alkyloxycarbonyl, di-C1-C6-alkylaminothionyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5 , 6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; preferably R ⁵ is chosen from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2, 3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro- C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; more preferably R ⁵ is chosen from cinnamoyl, benzoyl, 2, 3, 4,5,6- pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, trifluoro -C1-C4-alkyl, C1-C4-alkylamino or hydroxy-C1-C4-alkylamino; more preferably R ⁵ is chosen from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by C1-C2-alkyl, C1-C2-alkoxy, trifluoro- C1-C2-alkyl, C1-C4-alkylamino or hydroxy-C1-C2-alkylamino; more preferably still R ⁵ is chosen from cinnamoyl, benzoyl, 2, 3, 4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino; still more preferably R ⁵ is chosen from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by trifluoromethyl, butylamino or hydroxyethylamino; for example R ⁵ is chosen from benzoyl, 4- (trifluomethyl) benzoyl, 3,5-bis (trifluomethyl) benzoyl, 2, 3, 4,5,6-pentafluorobenzoyl, 4- (butylamino) -2,3,5, 6-tetrafluorobenzoyl, cinnamoyl and 4- ((2-hydroxyethyl) amino) benzoyl; and with the condition that:

R ¹ , R ² and R ³ are not all three hydrogen when R ⁵ is cinnamoyl, or benzoyl optionally substituted with methyl, methoxy, chloro or trifluoromethyl;

R ¹ is not methyl when R ⁵ is benzoyl;

R ² is not methyl when R ⁵ is benzoyl; and

R ³ is not methyl, methoxy or chloro when R ⁵ is benzoyl.

In one embodiment, the compounds of formula II are those of formula IIa:

[0120] [Chem. 7] wherein R ¹ and R ⁵ are as defined in formula II.

Preferred compounds of formula IIa are those in which R ¹ is methoxy or chloro. In one embodiment, the compounds of formula II are those of formula IIb:

[0123] [Chem. 8] wherein R ² and R ⁵ are as defined in formula II. Preferred compounds of formula IIa are those in which R ² is chosen from methyl, methoxy, fluoro and NO2.

In one embodiment, the compounds of formula II are those of formula Ile:

[Chem. 9] wherein R ³ and R ⁵ are as defined in formula II.

Preferred compounds of formula III are those in which R ³ is chloro.

Particularly preferred compounds of formula II of the invention are those listed in Table 2 below:

[0128] [Table 2]

Definitions

[0129] The definitions and explanations below relate to the terms and expressions as used in the present application, comprising the description as well as the claims. For the description of the compounds of the invention, the terms and expressions used should, unless otherwise indicated, be interpreted according to the definitions below.

The term "alkyl", alone or as part of another group, denotes a hydrocarbon radical of formula CnPLn _{+ i} in which n is an integer greater than or equal to 1. 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. Appropriate 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. Non-limiting examples of alkenyl groups are ethenyl (vinyl), 2-propenyl (allyl), 2-butenyl and 3-butenyl, with 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, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, especially adamant-1-yl and adamant-2-yl, 1-decalinyl. Preferred cycloalkyl groups include cyclopropyl, cyclohexyl, and cycloheptyl. A particularly preferred cycloalkyl group is cyclohexyl.

The term "aryl (e)", alone or as part of another group, denotes a polyunsaturated aromatic hydrocarbon radical having a single ring (phenyl) or several aromatic rings condensed together (for example naphthyl) typically containing 5 to 12 atoms, preferably 6 to 10, in which at least one of the rings is aromatic. Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenantracenyl, pyrenyl. A particularly preferred aryl group is phenyl. The term "heteroaryl (e)", alone or as part of another group, designates, without being limited thereto, aromatic rings or ring systems containing one to two rings condensed between them, typically containing 5 to 12 atoms, in which at least one of the rings is aromatic, and in which one or more carbon atoms in one or more of these rings are replaced by oxygen, nitrogen and / or sulfur atoms, the heteroatoms of nitrogen and sulfur can optionally be oxidized and the nitrogen heteroatoms can optionally be quaternized. Preferred but non-limiting heteroaryl groups are pyridinyl, pyrrolyl, furanyl, thiophenyl. Particularly preferred heteroaryl groups are thiophenyl and pyridinyl.

[0136] The term "halo", alone or as part of another group, denotes fluoro, chloro, bromo, or iodo. Preferred halo groups are chloro and fluoro, fluoro being particularly preferred.

The term "haloalkyl (e)", alone or as part of another group, denotes an alkyl radical as defined above in which one or more hydrogen atoms are replaced by a halo group such as as defined above. The haloalkyl radicals according to the present invention can be linear or branched, and comprise, without being limited thereto _{, radicals of formula C n} _{F2n + i} in which n is an integer greater than or equal to 1, preferably an integer between 1 and 10. Preferred haloalkyl radicals include trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, nonafluoro-n-butyl, 1,1,1 -trifluor-n-butyl, 1, 1, 1-trifluoro-n-pentyl and 1, 1, 1-trifluoro-n-hexyl, trifluoromethyl being particularly preferred.

The present invention will be better understood by reference to the following examples. These examples are representative of certain embodiments of the invention and in no way limit the scope of the invention. The figures serve to illustrate the experimental results.

Examples

CHEMICAL SYNTHESIS All the temperatures are expressed in ° C. and all the reactions were carried out at room temperature (RT), unless otherwise indicated.

The reactions were monitored by thin layer chromatography (TLC) carried out on ready-to-use aluminum sheets and covered with silica gel and a UV254 fluorescence indicator (Kieselgel® 60 0.2mm thick Merck F254) or equivalent.

The NMR analyzes were carried out on a Bruker 300 MHz, 400 MHz or 600 MHz spectrometer. The spectra are recorded in solution in deuterated chloroform (CDCl3). Chemical shifts are given in ppm, followed for proton spectra of multiplicity, where s, si, d, t, q, dd, td and m denote singlets, broad singlets, doublets, triplets, quadruplets, doublets of doublets, triplets of doublets and multiplets (or unresolved massive). The multiplicities are followed, where appropriate, by the value of the coupling constants noted and expressed in Hertz (Hz).

[0142] The HRMS analyzes were carried out in positive electrospray ionization mode (ESI +).

[0143] Solvents, reagents and starting materials have been purchased from well known chemical suppliers such as Sigma Aldrich, Acros Organics, Fluorochem, Eurisotop, VWR International, Sopachem and Polymer. Solvents, unless otherwise specified, were purified by distillation before use. Reagents and starting materials, unless otherwise indicated, were used without additional purifications.

[0144] The following abbreviations have been used:

HRMS: high resolution mass spectrometry,

NMR: nuclear magnetic resonance,

TA: ambient temperature,

THF: tetrahydrofuran.

[0145] Compound 3: N- (2- (benzo [d] thiazol-2-yl) phenyl) -3,5- bis (trifluoromethyl) benzamide [0146] [Scheme 1] In a 50 mL round-bottomed flask equipped with a stirrer and a temperature indicator, 2- (1, 3-benzothiazol-2-yl) aniline (0.5 g) and pyridine ( 0.9 mL) were added to tetrahydrofuran (7 mL). 3,5-Bis (trifluoromethyl) benzoyl chloride (0.44 g) was then added and the solution was heated to 60 ° C. After stirring for about 45 minutes at 60 ° C, the reaction mixture was cooled to room temperature. 10 mL of water was added and the mixture was filtered, the filter residue was washed with 2 x 25 mL of water, 25 mL of ethanol and dried to give compound 3 (0.87 g). ¹ H NMR (CDCls): d 13.50 (1 H, s), 9.02 (1 H, dd, J = 5.6, 0.8 Hz), 8.66 (2H, s), 8.15 (1 H, s), 8.07 (1 H , d, J = 5.6 Hz), 7.97 (1H, dd, J = 5.2, 1.2 Hz), 7.96 (1H, d, J = 5.6 Hz), 7.6 - 7.55 (2H, m), 7.48 (1H , td, J = 5, 0.8Hz), 7.29 (1H, td, J = 5.2, 1.2Hz) HRMS (ESI +) m / z 467.12 (467.41 calculated for C22Hi2F6N20S + H ⁺ [M + H] ⁺ ).

[0148] Compound 4: N- (2- (benzo [d] thiazol-2-yl) phenyl) -2,3,4,5,6-pentafluorobenzamide

[0149] [Diagram 2]

The same procedure as that described above for the preparation of compound 3 was used with 1.0 g of 2- (1, 3-benzothiazol-2-yl) aniline, 1, 8 mL of pyridine, 13 mL of THF and 0.7 mL of pentafluorobenzoyl chloride to give compound 4 (1.51 g).

¹ H NMR (CDCls): d 13.46 (1H, s), 8.94 (1H, dd, J = 5.6, 0.4Hz), 7.95-7.93 (2H, m), 7.74 (1H, d, J = 5.6 Hz), 7.58 (1 H, td, J = 5.2, 0.4 Hz), 7.53 (1 H, td, J = 5.2, 0.8 Hz), 7.46 (1 H, td, J = 5.2, 0.4 Hz), 7.30 ( 1 H, td, J = 5.2, 0.8 Hz).

HRMS (ESI +) m / z 421.14 (421.36 calculated for C20H9F5N2OS + H ^· [M + H] ^+).

[0151] Compound 5: N- (2- (benzo [d] thiazol-2-yl) phenyl) -4- (butylamino) -2, 3,5,6- tetrafluorobenzamide

[0152] [Diagram 3]

[0153] Potassium carbonate (4.6 g), N- (2- (benzo [d] thiazol -2-yl) phenyl) -2,3,4,5,6-pentafluorobenzamide (7.00 g) and dimethylformamide (25 mL). The resulting mixture was stirred at room temperature. Butylamine (2.43 g) was then added and the mixture was heated to 95 ° C. After 1 hour, the reaction mixture was cooled to room temperature, filtered and the filtration residue was washed with 2 x 30 mL of water. Then, in a 50 mL round-bottomed flask equipped with a stirrer and a temperature indicator were introduced the crude product and petroleum ether (25 mL). The resulting mixture was heated to 50 ° C, after 45 minutes the reaction mixture was cooled to room temperature, and the mixture was filtered and the filter residue was washed with 2 x 15 mL of petroleum ether and dried to give compound 5 (8.7 g).

¹ H NMR (CDCls): d 13.22 (1 H, s), 9.99 (1 H, d, J = 5.6 Hz), 7.93 (1 H, d, J = 5.2 Hz), 7.91 (1 H, dd, J = 5.2, 0.8 Hz), 7.84 (1H, d, J = 5.6 Hz), 7.54 (1H, td, J = 5.2, 0.8 Hz), 7.51 (1H, td, J = 5.2, 0.4 Hz), 7.44 (1H, td, J = 5.2, 0.4 Hz), 7.42 (1H, td, J

5.2, 0.4 Hz), 4.14 (1H, bs), 3.55 (2H, t, H = 4.8 Hz), 1.68 (2H, q, J = 4.8 Hz), 1.48 (2H, h, J = 5.2 Hz), 1.02 (3H, t, J = 5.2Hz).

HRMS (ESI +) m / z 474.21 (474.49 calcd for C24H19F4N3OS + H ^· [M + H] ^+). [0154] Compound 8: N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) -4-

(trifluoromethyl) benzamide

[0155] [Diagram 4]

The same procedure as that described above for the preparation of compound 3 was used with 0.61 g of 2- (1, 3-benzothiazol-2-yl) -5-methylaniline, 0.8 mL of pyridine, 8 mL of THF and 0.75 mL of trifluoromethylbenzoyl chloride to give compound 8 (0.53 g).

¹ H NMR (CDCls): d 13.47 (1 H, s), 8.87 (1 H, d, J = 3.2 Hz), 8.37 (2H, d, J = 5.6 Hz), 7.96 (2H, t, J = 5.2 Hz), 7.88 (2H, d, J = 5.6 Hz), 7.82 (1H, d, J = 5.2 Hz), 7.59 (1H, t, J = 5.2 Hz), 7.47 (1H, t, J = 5.2 Hz), 7.06 (1H, d, J = 5.6 Hz), 2.50 (3H, s).

HRMS (ESI +) m / z 413.22 (413.44 calcd for C22H15F3N2OS + H ^· [M + H] ^+).

[0157] Compound 9: N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) -4-

(butylamino) -2,3,5,6-tetrafluorobenzamide

[0158] [Diagram 5] Step 1: The same procedure as that described above for the preparation of compound 3 was used with 1.06 g of 2- (1, 3-benzothiazol-2-yl) - 4-methylaniline, 1.8 mL of pyridine, 9 mL of THF and 0.7 mL of pentafluorobenzoyl chloride to give the intermediate compound (1.51 g). Step 2: The same procedure as that described above for the preparation of compound 5 was used with 1.55 g of 2- (1, 3-benzo [d] thiazol-2-yl) -4-methylaniline, 0.95 g of potassium carbonate, 6 mL of DMF and 0.5 mL of butylamine to give compound 9 (1.33 g).

¹ H NMR (CDCls): d 13.10 (1 H, s), 8.87 (1 H, d, J = 5.6 Hz), 7.93 (1 H, d, J = 5.2 Hz), 7.83 (1 H, d, J = 5.6 Hz), 7.69 (1 H, s), 7.51 (1 H, td, J = 5.2, 0.8 Hz), 7.43 (1 H, td, J = 5.0, 0.8 Hz), 7.35 (1 H, dd, J = 5.6, 0.8 Hz), 4.13 (1H, bs), 3.54 (2H, q, J = 4.4 Hz), 2.44 (3H, s), 1.67 (2H, q, J = 4.8 Hz), 1.47 (2H , h, J = 5.2 Hz), 1.01 (3H, t, J = 4.8 Hz).

HRMS (ESI +) m / z 488.42 (488.52 calculated for C25H21 F4N3OS + H ^· [M + H] ^+). [0160] Compound 10: N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) cinnamamide

[0161] [Diagram 6]

The same procedure as that described above for the preparation of compound 3 was used with 0.5 g of 2- (1, 3-benzothiazol-2-yl) -4-methylaniline, 0.8 mL of pyridine, 4 mL of THF 0.4 mL of cinnamoyl chloride to give compound 10 (0.55 g).

¹ H NMR (CDCls): d 12.71 (1 H, s), 8.86 (1 H, d, J = 5.6 Hz), 8.06 (1 H, d, J = 5.6 Hz), 7.95 (1 H, d, J = 5.2 Hz), 7.81 (1 H, d, J = 10.4 Hz), 7.68 (1 H, d, J = 0.8 Hz), 7.67 - 7.64 (2H, m), 7.57 (1 H, td, J = 5.2 , 0.8 Hz), 7.49 - 7.42 (4H, m), 7.34 (1H, dd, J = 5.6, 1.2Hz), 6.73 (1H, d, J = 10.4Hz), 2.43 (3H, s).

HRMS (ESI +) m / z 371.15 (371.47 calculated for C23H18N OS + H ⁺ [M + H] ⁺ ).

[0163] Compound 11: N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) benzamide

[0164] [Diagram 7]

The same procedure as that described above for the preparation of compound 3 was used with 1 g of 2- (1, 3-benzothiazol-2-yl) -4-methoxyaniline, 1.6 mL of pyridine, 5 mL of THF and 0.4 mL of benzoyl chloride to give compound 11 (1.05 g). ¹ H NMR (CDCls): d 13.10 (1H, s), 8.99 (1H, d, J = 6Hz), 8.23 (2H, dd, J = 5.2, 1.2Hz), 8.01 (1H, d, J = 5.6 Hz), 7.94 (1 H, d, J = 5.6 Hz), 7.63 - 7.59 (3H, m) 7.55 (1 H, td, J = 5.2, 0.8 Hz), 7.46 (1 H, td, J = 4.8, 0.8 Hz), 7.41 (1H, d, J = 2 Hz), 7.12 (1H, dd, J = 6, 1.2 Hz), 3.92 (3H, s).

HRMS (ESI +) m / z 361.12 (361.44 calculated for C21H16N2O2S + H ⁺ [M + H] ⁺ ). [0166] Compound 12: N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) -4-

(trifluoromethyl) benzamide

[0167] [Diagram 8] The same procedure as that described above for the preparation of compound 3 was used with 0.47 g of 2- (1, 3-benzothiazol-2-yl) -4-methoxyaniline, 0.6 mL of pyridine, 6 mL of THF and 0.5 mL of trifluoromethylbenzoyl chloride to give compound 12 (0.59 g). ¹ H NMR (CDCls): d 13.25 (1H, s), 8.98 (1H, d, J = 6.2Hz), 8.43 (2H, d, J = 5.6Hz), 8.34 (2H, d, J = 5.6 Hz), 8.14 (1 H, d, J = 5.6 Hz), 8.02 (1 H, J = 3.8 Hz) 7.98 (1 H, d, J = 5.8 Hz), 7.61 (1 H, t, J = 4.8 Hz), 7.45 (1H, d, J = 1.6Hz), 7.15 (1H, dd, J = 6.0, 2.0Hz), 3.94 (3H, s).

HRMS (ESI +) m / z 429.10 (429.43 calculated for C22H15F3N2O2S + H ^· [M + H] ⁺ ). [0169] Compound 13: N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) -4-

(butylamino) -2,3,5,6-tetrafluorobenzamide

[0170] [Diagram 9]

[0171] Step 1: The same procedure as that described above for the preparation of compound 3 was used with 1.32 g of 2- (1, 3-benzothiazol-2-yl) - 4-methoxyaniline, 2.1 mL of pyridine, 12 mL of THF and 0.8 mL of pentafluorobenzoyl chloride to give the intermediate compound (1.63 g).

Step 2: The same procedure as that described above for the preparation of compound 5 was used with 1.63 g of 2- (1, 3-benzo [d] thiazol-2-yl) -4-methoxyaniline, 1.0 g of potassium carbonate, 6 mL of DMF and 0.52 mL of butylamine to give compound 13 (1.43 g).

¹ H NMR (CDCls): d 13.30 (1 H, s), 8.92 (1 H, d, J = 5.8 Hz), 8.14 (1 H, d, J = 5.4 Hz), 7.85 (1 H, d, J = 5.4 Hz), 7.78 (1 H, s), 7.56 (1 H, t, J = 4.8 Hz), 7.52 (1 H, t, J = 4.8 Hz), 7.19 (1 H, d, J = 5.8 Hz ), 4.12 (1H, bs), 3.92 (3H, s), 3.54 (2H, q, J = 4.8 Hz), 1.66 (2H, q, J = 4.8 Hz), 1.45 (2H, h, J = 5.2 Hz), 1.02 (3H, t, J = 4.8Hz). HRMS (ESI +) m / z 504.17 (504.52 calcd for C25H21F4NsO2S + H ⁺ [M + H] ⁺ ). [0172] Compound 14 N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) cinnamamide

[0173] [Diagram 10] The same procedure as that described above for the preparation of compound 3 was used with 0.50 g of 2- (1, 3-benzothiazol-2-yl) -4-methoxyaniline, 0.77 mL of pyridine, 3 mL of THF and 0.34 mL of trifluoromethylbenzoyl chloride to give compound 14 (0.51 g).

¹ H NMR (CDCls): d 12.51 (1 H, s), 8.90 (1 H, d, J = 6 Hz), 8.08 (1 H, d, J = 5.6 Hz), 7.95 (1 H, d, J = 5.2 Hz), 7.95 (1H, d, J = 5.2 Hz), 7.80 (1H, d, J = 10.8 Hz), 7.64

(2H, d, J = 4.8 Hz), 7.58 (1H, t, J = 5.2 Hz), 7.49 - 7.46 (3H, m), 7.43 (1H, d, J = 4.8 Hz), 7.39 (1H , d, J = 1.6 Hz), 7.10 (1H, dd, J = 6.0, 1.6 Hz), 6.72 (1H, d, J = 10.4 Hz), 3.91 (3H, s).

HRMS (ESI +) m / z 387.17 (387.47 calcd for C23H15N 02S + H ⁺ [M + H] ⁺ ). [0175] Compound 16: N- (2- (benzo [d] thiazol-2-yl) -4-fluorophenyl) -4-

(trifluoromethyl) benzamide

[0176] [Figure 11]

The same procedure as that described above for the preparation of compound 3 was used with 0.74 g of 2- (1, 3-benzothiazol-2-yl) -4- fluoroaniline, 1.1 mL of pyridine, 4 mL of THF and 0.43 mL of trifluoromethylbenzoyl chloride to give compound 16 (0.78 g).

¹ H NMR (CDCls): d 13.37 (1H, s), 9.06 (1H, dd, J = 6, 3.2 Hz), 8.34 (2H, d, J = 5.6 Hz), 7.99 (2H, t, J = 6.2 Hz), 7.88 (2H, d, J = 5.2 Hz), 7.64 - 7.62 (2H, m) 7.52 (1H, t, J = 5.0 Hz), 7.28 (1H, td, J = 5.6, 2.0 Hz).

HRMS (ESI +) m / z 417.13 (417.40 calcd for C21H12F4N20S + H ⁺ [M + H] ⁺ ).

[0178] Compound 27: N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) benzamide

[0179] [Diagram 12] The same procedure as that described above for the preparation of compound 3 was used with 2 g of 2- (1, 3-benzothiazol-2-yl) -5-chloroaniline, 3.1 mL of pyridine, 3 mL of THF and 3.6 mL of benzoyl choride to give compound 27 (1.36 g).

¹ H NMR (CDCls): d 13.48 (1 H, s), 9.17 (1 H, d, J = 1.2 Hz), 8.24 (2H, dd, J = 5.6 Hz), 8.0 (1 H, d, J = 5.2 Hz), 7.95 (1 H, d, J = 4.8 Hz), 7.82 (1 H, d, J = 5.6 Hz) 7.66 - 7.61 (3H, m), 7.57 (1 H, td, J = 5.0, 0.8 Hz), 7.48 (1H, td, J = 5, 0.8 Hz), 7.18 (1H, dd, J = 5.6, 1.2 Hz).

HRMS (ESI +) m / z 365.65 (365.86 calculated for C20H13CIN OS + H ⁺ [M + H] ⁺ ).

[0181] Compound 29: N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) -4- (butylamino) -2,3,5,6-tetrafluorobenzamide

[0182] [Figure 13] [0183] Step 1: The same procedure as that described above for the preparation of compound 3 was used with 2.00 g of 2- (1, 3-benzothiazol-2-yl) - 5-chloroaniline, 3.1 mL of pyridine, 10 mL of THF and 3.3 mL of pentafluorobenzoyl chloride to give the intermediate compound (1.45 g).

Step 2: The same procedure as previously described for the preparation of compound 5 was used with 1.45 g of 2- (1, 3-benzo [d] thiazol-2-yl) -5-chloroaniline, 0.88 g of potassium carbonate, 5 mL of DMF and 0.46 mL of butylamine to give compound 29 (0.93 g). ¹ H NMR (CDCls): d 13.31 (1 H, s), 9.09 (1 H, d, J = 1.2 Hz), 7.93 (1 H, d, J = 5.6 Hz), 7.84 (1 H, d, J = 5.2 Hz), 7.80 (1 H, d, J = 5.2 Hz), 7.52 (1 H, td, J = 5.2, 0.8 Hz), 7.45 (1 H, td, J = 5.0, 0.8 Hz), 7.2 ( 1H, dd, J = 5.6, 1.2 Hz), 3.55 (2H, q, J = 4.8 Hz), 1.68 (2H, q, J = 5.2 Hz), 1.48 (2H, h, J = 5.2 Hz), 1.02 (3H, t, J = 4.8Hz).

HRMS (ESI +) m / z 508.63 (508.94 calculated for C24H18CIF4N ₃ OS + H ⁺ [M + H] ⁺ ). [0184] Compound 35: N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) -2, 3,5,6-tetrafluoro-4 - ((2-hydroxyethyl) amino) benzamide

[0185] [Figure 14]

Step 1: The same procedure as that described above for the preparation of compound 3 was used with 2.00 g of 2- (1, 3-benzothiazol-2-yl) - 5-chloroaniline, 3.1 mL of pyridine, 10 mL of THF and 3.3 mL of pentafluorobenzoyl to give the intermediate compound (1.45 g).

Step 2: The same procedure as that described above for the preparation of compound 5 was used with 1.0 g of 2- (1, 3-benzo [d] thiazol-2-yl) -5-chloroaniline, 0.66 g of potassium carbonate, 4 mL of DMF and 0.43 mL of aminoethanol to give compound 35 (0.75 g).

¹ H NMR (CDCls): d 13.34 (1 H, s), 9.08 (1 H, d, J = 1.2 Hz), 7.92 (1 H, d, J = 5.2 Hz), 7.83 (1 H, d , J = 5.6 Hz), 7.80 (1 H, d, J = 6.0 Hz), 7.52 (1 H, td, J = 5.2, 0.8 Hz), 7.44 (1 H, td, J = 5.2, 0.8 Hz), 7.2 (1H, dd, J = 5.6, 1.2Hz), 4.7 (1H, bs), 3.94 (2H, t, J = 3.2Hz), 3.73 (2H, m). HRMS (ESI +) m / z 496.57 (496.88 calcd for C22H14CIF4N ₃ OS + H ⁺ [M + H] ⁺ ).

APPLICATIONS

[0187] Example 1: Preparation of a fluorescent composition in the form of a layer and its use for securing

For this example, the compound of formula I used is compound 13 of formula below:

[0189] [Chem. 10]

[0190] Compound 13 is in the form of a yellow powder and absorbs at 365 nm and has fluorescence emission at 605 nm. 17 grams of compound are mixed with 10 kg of polycarbonate (PC Makralon 2456) via an extruder so as to obtain the fluorescent composition. The extrusion is carried out on a twin-screw extruder (Brabender) with a screw rotation speed of 50 revolutions / min, a hopper flow rate of 3.8 kg / h and the following temperature profile: 275 ° C -280 ° C -280 ° C -285 ° C -285 Ό -285 ° C -290 ° C (power supply => filial).

From the extruded fluorescent composition, a quantity is taken and then diluted 10 times by adding polycarbonate (PC Makralon 2456) through a Fairex extruder (diameter 45) equipped with Scamex flat dies with a width of 350 mm, followed by a 3-roll calender with an inclination of 30 °.

On leaving the calender, the fluorescent composition is then in the form of a layer 100 mm thick. After adjusting the calender, the test was repeated so as to obtain a second layer 400 mm thick from the fluorescent composition. The secure layers thus obtained are then used as document support, said document thus being secure.

Visual and spectrophotometric analyzes of the layers obtained show that the incorporation of the fluorescent dye into the polycarbonate does not affect its performance in terms of absorption and fluorescence emission. The fluorescent layers obtained show properties similar to those observed when the compound is in solution.

[0191] Example 2: Preparation of a fluorescent composition in the form of a varnish and its use for securing.

For this example, the compound of formula I used is compound 14 is used of formula below:

[0193] [Chem. 11]

44 mg of compound 14 are integrated into 10 g of solvent-based acrylic varnish (0.4% w / w). The fluorescent varnish thus obtained is then coated on a polyethylene film 100 mih thick terephthalate using an automatic film applicator (TQC ASTM D 823) and a 20 μm Meyer bar with an application speed of 50 mm / s.

The measured varnish deposit has a thickness of 5 μm in accordance with a solvent-based varnish at 33% dry extract.

The assembly consisting of the polyethylene terephthalate film coated with the fluorescent varnish forms a fluorescent layer. The fluorescent layer thus obtained is a secure layer. When illuminated with a UV lamp (365 nm), a purple fluorescence appears to the naked eye. Visual and spectrophotometric analysis of the secure layer shows that the incorporation of the fluorescent dye into the polycarbonate does not affect its performance in terms of fluorescence absorption and emission.

The resulting secure layer, through its fluorescence properties, is used as a backing for a card. [0195] Example 3: Preparation of a fluorescent composition in ink form comprising a compound of formula I according to the invention and a compound of formula III.

[0196] For this example, the compound of formula I used is compound 27 of formula below: [0197] [Chem. 12]

[0198] Compound 27 is in the form of a white powder, absorbs at 365 nm, has fluorescence emission at 522 nm.

[0199] The compound of formula III used is compound 36 of formula below: [0200] [Chem. 13] Compound 36 is in the form of an orange powder, absorbs at 547 nm, has fluorescence emission at 568 nm.

Preparation of the fluorescent composition in ink form: 400 mg of compound 27 are uniformly dissolved in 100 g of transparent virgin screen printing ink of the Mara® Gloss GO type distributed by the Marabu company, compatible with printing on a plastic surface. in polycarbonate. 100 mg of compound 36 are uniformly dissolved in 100 g of the same transparent virgin screen printing ink. The ink containing the compound 27 and the ink containing the compound 36 are then mixed in a ratio of 1: 1 by weight.

The fluorescent composition thus formulated is printed on a transparent polycarbonate card.

[0203] Results: The fluorescent composition printed perfectly. The pattern thus printed has a pink color visible by transparency when said card is placed on a white background, and an orange color visible by transparency when said card is placed on a black background.

When the card is illuminated under UV, a yellow fluorescence is visible.

[0204] Example 4: Preparation of a fluorescent composition in ink form comprising a compound of formula I according to the invention

For this example, the compound of family I used is compound 3 of formula below:

[0206] [Chem. 14] Compound 3 is in the form of a white powder, absorbs at 365 nm, has fluorescence emission at 513 nm.

Preparation of the fluorescent composition in ink form: 400 mg of compound 3 are uniformly dissolved in 100 g of transparent virgin screen printing ink of the Mara® Gloss GO type distributed by the Marabu company, compatible with printing on a plastic surface. in polycarbonate. The mass concentration of the ink is therefore 0.4% (w / w).

The fluorescent composition thus formulated is printed on a transparent polycarbonate card using a 90 mesh screen printing frame.

[0209] Results: The fluorescent composition printed perfectly.

The pattern thus printed is invisible under ambient lighting and has an intense yellow fluorescence under UV lighting (365 nm).

The optical properties of the dye are transposed between the pure dye and the screen printed layer.

[0210] Example 5: Preparation of a fluorescent composition in ink form comprising a compound of formula I according to the invention

[0211] For this example, the compound of formula I used is compound 13 of formula below: [0212] [Chem. 10] [0213] Compound 13 is in the form of a white powder, absorbs at 365 nm, has fluorescence emission at 605 nm.

[0214] Preparation of the fluorescent composition in ink form: 400 mg of compound 3 are uniformly dissolved in 100 g of transparent virgin screen printing ink of the Mara® Gloss GO type distributed by the Marabu company, compatible with printing on a plastic surface. in polycarbonate. The mass concentration of the ink is therefore 0.4% (w / w).

[0215] Results: The fluorescent composition printed perfectly.

The pattern thus printed is invisible under ambient lighting and has a red fluorescence under UV lighting (365 nm).

G0216Ί Example 6: Preparation of a fluorescent composition in ink form comprising two compounds of formula I according to the invention

[0217] For this example, the compounds of family I used are compounds 3 and 13, the formulas of which are presented below: [0218] [Chem. 14] Compound 3

[0219] [Chem. 10] Compound 13

[0220] Preparation of the fluorescent composition in the form of ink:

400 mg of compound 3 are uniformly dissolved in 100 g of transparent virgin screen printing ink of the Mara® Gloss GO type distributed by the Marabu company, which is compatible with printing on a polycarbonate plastic surface. 400 mg of compound 13 are uniformly dissolved in 100 g of the same transparent virgin screen printing ink.

These two inks are mixed with a mass ratio of 3: 1 (compound 13: compound 3 - by weight) and homogenized until a uniform shade is obtained.

[0221] Results: The fluorescent composition printed perfectly. The pattern thus printed is invisible under ambient lighting and has an intense orange fluorescence under UV lighting (365 nm).

The color thus obtained refers to the mixture of the respective fluorescence colors of the two dyes.

Claims

Claims [Claim 1] A fluorescent composition comprising a polymer matrix incorporating a compound of formula I:

[Chem. 1] in which,

X is selected from NH, O and S;

Z is selected from OH, NHR ⁵ and N (R ⁵ ) 2;

R is selected from hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH ₂ , -NHR ⁴ , -N (R ⁴ ) ₂ , -N ⁺ (R ⁴ ) ₃ , -NHCOR ⁴ , -CHO, - C (0) 0H, -C (0) 0R ⁴ , -CFs, C1-C6-alkoxy, aryloxy, -SH, -SOsH, -SR ⁴ ;

R ⁴ is selected from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;

R ⁵ is chosen from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1 -C6-alkyloxycarbonyl, C1 -C6-alkylaminocarbonyl, C1 -C6-alkylaminothionyl, di-C1-C6-alkylaminothionyl , arylaminocarbonyl, arylaminothionyl, arylsulfonyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted with C1-C6-alkyl, C1- C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; with the proviso that Z is not OH when R ² is -NHCOR ⁴ ; and in which the symbol means that R can be substituted one more than once at any free position of the benzene ring.

[Claim 2] A fluorescent composition according to claim 1, characterized in that the polymer of the matrix is chosen from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, poly (chloride). vinyl), polyamides, polyaramides, vinyl ethylene acetate (EVA), polyurethane, thermoplastic polyurethane (TPU), cyanoacrylate, rosin resins, pine resins, light-curing resins or their mixtures.

[Claim 3] A fluorescent composition according to any one of claims 1 and 2, characterized in that X is S in the compound of formula I.

[Claim 4] A fluorescent composition according to any one of claims 1 to 3, characterized in that Z is NHR ⁵ or N (R ⁵ ) 2 in the compound of formula I.

[Claim 5] A fluorescent composition according to any one of claims 1 to 4, characterized in that R is hydrogen in the compound of formula I.

[Claim 6] Fluorescent composition according to any one of claims 1 to 5, characterized in that the compound of formula I is chosen from:

N- (2- (benzo [d] thiazol-2-yl) phenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) phenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) phenyl) -3,5-bis (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) phenyl) -2,3,4,5,6-pentafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) phenyl) -4- (butylamino) -2,3,5,6-tetrafluorobenzamide; N- (2- (benzo [d] thiazol-2-yl) phenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) benzamide N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -4-fluorophenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-fluorophenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-fluorophenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) -4-fluorophenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -4-nitrophenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-nitrophenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-nitrophenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) -4-nitrophenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -5-methoxyphenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -5-methoxyphenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -5-methoxyphenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) -5-methoxyphenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -3-chlorophenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -3-chlorophenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -3-chlorophenyl) -4- (butylamino) -2,3,5,6- tetrafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) -3-chlorophenyl) cinnamamide; and

N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) -2,3,5,6-tetrafluoro-4 - ((2-hydroxyethyl) amino) benzamide.

[Claim 7] A fluorescent composition according to any one of claims 1 to 6, characterized in that the fluorescent composition further comprises a second compound of formula I.

[Claim 8] A fluorescent composition according to any one of claims 1 to 6, characterized in that the fluorescent composition further comprises a second compound of formula III:

[Chem. 6] 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 chosen from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted by one or more groups chosen from alkyl C1 to C4, 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 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 with 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.

R ⁶ and R ^{6 '} are independently selected from halogens, C1 to C4 alkoxy, C2 to C4 alkenyloxy, C1 to C4 alkyl, C2 to C4 alkenyl, CN or aryl, said aryl being optionally substituted by one or more groups selected from C1 to C2 alkyl, hydroxy, R ⁵ COO- and halogen.

[Claim 9] Use of a fluorescent composition according to any one of claims 1 to 8 for securing a product.

[Claim 10] Use of a fluorescent composition according to claim 9, characterized in that the product to be secured is a document.

[Claim 11] Use of a fluorescent composition according to any one of claims 9 and 10, characterized in that the fluorescent composition is a fluorescent ink suitable for printing.

[Claim 12] Use of a fluorescent composition according to claim 11, characterized in that the printing is chosen from screen printing, offset printing, flexography, heliography, inkjet printing, digital printing, intaglio printing and 3D printing.

[Claim 13] A method of securing a product comprising a step of preparing a fluorescent composition as defined according to any one of claims 1 to 8 and a step of securing by applying said fluorescent composition to at least part of the product to be secured.

[Claim 14] A method of securing a product according to claim 13, characterized in that the securing step is carried out by lamination, by printing, by weaving, by gluing, by coating or by impregnation.

[Claim 15] A method of securing a product according to one of claims 13 or 14, characterized in that it comprises a step of shaping the fluorescent composition before the securing step.

[Claim 16] A method of securing a product according to claim 13, characterized in that the fluorescent composition is a fluorescent ink and in that the securing step is carried out by printing.

[Claim 17] A security method according to one of claims 13 to 16, characterized in that the product is an identity, fiduciary or administrative document.

[Claim 18] Compound of formula (II):

[Chem. 2] wherein, wherein, R ¹ , and R ² and R ³ are independently selected from hydrogen, C1 -C6-alkyl, C3-

C6-cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, -NHR ⁴ , -N (R ⁴ ) 2, - N ⁺ (R ⁴ ) ₃ , -NHCOR ⁴ , -CHO, -C (0 ) OH, -C (0) 0R ⁴ , -CFS, C1 -C6-alkoxy, aryloxy, -SH, -SOsH, -SR ⁴ ;

R ⁴ is selected from C1 -C6-alkyl, C1 -C6-cycloalkyl and aryl; R ⁵ is chosen from C1-C6-alkyl, hydroxy-C1 -C6-alkyl, C1 -C6-alkyloxycarbonyl, di-C1 -C6-alkylaminothionyl, C1 -C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5 , 6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted by alkyl, C1 -C6-alkoxy, trifluoro-C1 -C6-alkyl, C1 -C6-alkylamino or hydroxy-C1 -C6-alkylamino; and with the condition that:

R ² is not methyl when R ⁵ is benzoyl; and

R ³ is not methyl, methoxy or chloro when R ⁵ is benzoyl.

[Claim 19] A compound according to claim 18 selected from: N- (2- (benzo [d] thiazol-2-yl) phenyl) -3,5-bis (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) phenyl) -2,3,4,5,6-pentafluorobenzamide;

N- (2- (benzo [d] thiazol-2-yl) phenyl) -4- (butylamino) -2,3,5,6-tetrafluorobenzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methylphenyl) cinnamamide; N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide; N- (2- (benzo [d] thiazol-2-yl) -4-methoxyphenyl) cinnamamide;

N- (2- (benzo [d] thiazol-2-yl) -4-fluorophenyl) -4- (trifluoromethyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) benzamide; N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) -4- (butylamino) -2, 3,5,6-tetrafluorobenzamide; and N- (2- (benzo [d] thiazol-2-yl) -5-chlorophenyl) -2,3,5,6-tetrafluoro-4 - ((2-hydroxyethyl) amino) benzamide.