Fluorescent composition containing at least one benzazole compound for ensuring product security

Abstract

Some existing security solutions are difficult to implement and / or verify, and the need to develop alternatives remains, particularly in the visible spectrum. Therefore, there is a real need to develop novel security measures that are easy to implement, stable, possess fluorescence, and allow for rapid verification of product authentication. These novel measures must provide a high level of security and should not be mutually exclusive or exclusive to existing measures. [Solution] The present invention relates to the use of a fluorescent composition for ensuring the security of a product, wherein the composition comprises a polymer matrix incorporating a compound having formula I. JPEG2026082885000052.jpg49170

Description

[Technical Field]

[0001] This invention relates to the field of product security and authentication. More specifically, this invention relates to fluorescent compositions for the security and authentication of products such as identification cards, trust documents, and administrative documents. [Background technology]

[0002] Counterfeiting and forgery are increasing significantly in many sectors, particularly in packaging, especially blister packaging for pharmaceuticals, and in high-value-added sectors such as luxury goods, automobiles, and aerospace. With the rise in identity theft and the introduction of points-based driving licenses in some countries, identification documents and government documents are also becoming targets for forgery. Therefore, ensuring product security and authentication is essential, and this involves security challenges both domestically and internationally.

[0003] Regarding the security of products such as identification cards, trust documents, or administrative documents, various companies offer visual authentication solutions that can be used to insert information into plastic card bodies such as ID cards, health cards, or driver's licenses, for example, by using holograms or laser etching.

[0004] Document EP0708935 A1 describes, for example, a set of holographic protective layers. This set consists of a backing film having at least one layer formed of protective varnish, a reflective or transparent layer with a diffraction-producing microstructure, and finally an adhesive layer. Once the set of layers is transferred to a document, its security is ensured. As described in document WO2010 / 086522, this system was subsequently reinforced by perforation to make the separation of the various layers more difficult. However, even with perforation, the set of layers is formed of numerous parts that need to be assembled, thus presenting further constraints in terms of time and cost.

[0005] Document FR 16 50164, held by the applicant, describes the use of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene compounds for the preparation of security elements for products, particularly for documents, wherein the security elements comprise a polymer, and the compounds are incorporated into the polymer. Interestingly, the use of the described compounds makes it possible to obtain fluorescence emission in the range from 500 nm to infrared, and therefore does not cover the entire visible spectral region.

[0006] Application US 2008 / 0081913 A1 describes benzoxazole and benzothiazole type compounds that have fluorescent properties and are particularly useful as authentication compounds in data storage media and data storage substrates.

[0007] Products, particularly documents, can be secured by security elements that can be classified according to three security levels based on the means used for their detection. Specifically, Level 1 security elements are those that can be detected by at least one of the five senses or by a contrasting background. This level particularly includes woven patterns, optically variable devices such as iridescent printing, holograms, optically variable inks, tagants, variable laser images, or multiple laser images.

[0008] Level 2 security elements are those detectable with simple devices such as ultraviolet lamps, convex lenses, or cell phone flashlights. This level includes detectable elements such as microprints, fluorescent inks, and fluorescent fibers or chips.

[0009] Finally, Level 3 security elements are those detectable by complex devices such as spectrofluorometers or electron microscopes. This category specifically includes nanoetched pigments, biometric chips, and fluorescent tagants that are undetectable to the naked eye.

[0010] Generally, secure products incorporate several security elements at different levels. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] EP0708935 A1 [Patent Document 2] WO2010 / 086522 [Patent Document 3] FR 16 50164 [Patent Document 4] US 2008 / 0081913 A1 [Overview of the project] [Problems that the invention aims to solve]

[0012] While existing security solutions have proven interesting, some can be difficult to implement and / or verify, and there remains a need to develop alternatives, particularly in the visible spectrum.

[0013] Therefore, there is a real need to develop novel security measures that are easy to implement, stable, possess fluorescence emission, and allow for rapid verification of product authentication. These novel measures must provide a high level of security and should not be mutually exclusive or exclusive to existing measures. [Means for solving the problem]

[0014] Therefore, the inventors have achieved all or part of these objectives by identifying and developing compounds that enable the acquisition of particularly advantageous fluorescent compositions for use in the field of ensuring product security.

[0015] This invention relates to a fluorescent composition comprising a polymer matrix incorporating a compound having formula I.

[0016] [Chemical formula]

[0017] [In the formula, X is selected from NH, O, and S, Z is OH, NHR 4 , 4 , 4 , , 4 , 4 , 4 , + , 5 , , and N(R 5 )2, R is 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(O)OH, -C(O)OR 4 , -CF3, C1-C6 alkoxy, aryloxy, -SH, -SO3H, -SR 4 selected from R 1 , R 2 and R 3 are independently 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(O)OH, -C(O)OR 4 , -CF3, C1-C6 alkoxy, aryloxy, -SH, -SO3H, -SR 4 selected from R 4 is selected from C1-C6 alkyl, C3-C6 cycloalkyl, and aryl, R 5This is selected from C1-C6 alkyl, hydroxyC1-C6 alkyl, halogen, aryl, acyl, C1-C6 alkyloxycarbonyl, C1-C6 alkylamino, or hydroxy-C1-C6 alkylamino, which may optionally be substituted with C1-C6 alkyl, C1-C6 alkoxy, trifluoro-C1-C6 alkyl, 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, However, R 2 ga-NHCOR 4 If that is the case, provided that Z is not an OH group, symbol

[0018] [ka]

[0019] This means that R can be substituted several times at any free position on the benzene ring.

[0020] In a further embodiment, the use of the fluorescent composition according to the present invention is proposed for ensuring the security of products.

[0021] In a further embodiment, a method for securing a product is proposed, comprising the steps of preparing the fluorescent composition defined above and securing at least a portion of the product to be secured by applying the fluorescent composition.

[0022] In a further embodiment, a compound having formula (II) is proposed.

[0023] [ka]

[0024] [In the formula, R 1 , and R 2 and R 3 These are independently hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, and -NHR. 4 , -N(R 4 )2, -N + (R 4 )3, -NHCOR 4 -CHO, -C(O)OH, -C(O)OR 4 -CF 3、 C1-C6 alkoxys, aryloxys, -SH, -SO3H, -SR 4 Selected from, R 4 These are selected from C1-C6 alkyl, C1-C6 cycloalkyl, and aryl. R 5 This is selected 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, which may optionally be substituted with C1-C6 alkyl, C1-C6 alkoxy, trifluoro-C1-C6 alkyl, C1-C6 alkylamino, or hydroxy-C1-C6 alkylamino. however, R 5 However, if R is cinnamoyl or benzoyl, which may optionally be substituted with methyl, methoxy, chloro, or trifluoromethyl, 1 , R 2 and R 3 It is not the case that all three are hydrogen. R 5 If R is benzoyl, 1 It is not methyl, R 5 If R is benzoyl, 2 It is not methyl, R 5 If R is benzoyl,3 [Provided that it is not methyl, methoxy, or chloro] [Modes for carrying out the invention]

[0025] The present invention relates, firstly, to a fluorescent composition comprising a polymer matrix incorporating a compound having formula I.

[0026] [ka]

[0027] [In the formula, X is selected from NH, O, and S, and preferably X is S. Z is OH, NHR 5 , and N(R 5 ) Selected from 2, preferably Z is NHR 5 or N(R 5 )2, and moreover, Z is NHR 5 And, R represents hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, and -NHR. 4 , -N(R 4 )2, -N + (R 4 )3, -NHCOR 4 -CHO, -C(O)OH, -C(O)OR 4 -CF3, aryloxy, -SH, -SO3H, -SR 4 Selected from, preferably, R is hydrogen, C1-C4 alkyl, halogen, -NO2, -NH2, -NHR 4 , -N(R 4 )2, selected from C1-C4 alkoxys, more preferably R is hydrogen, selected from C1-C2 alkyl, halogen, and C1-C4 alkoxys, more preferably R is hydrogen. R 1 , R 2 and R 3These are independently hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, and -NHR. 4 , -N(R 4 )2, -N + (R 4 )3, -NHCOR 4 -CHO, -C(O)OH, -C(O)OR 4 -CF3, C1~C6 alkoxy, aryloxy, -SH, -SO3H, -SR 4 Selected from, preferably R 1 , R 2 and R 3 R is independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen, and -NO2, more preferably R 1 , R 2 and R 3 R is independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, halogen and -NO2, more preferably R 1 , R 2 and R 3 R is independently selected from hydrogen, C1-C2 alkyl, C1-C2 alkoxy, halogen and -NO2, and more preferably R 1 , R 2 and R 3 These are independently selected from hydrogen, methyl, methoxy, bromo, chloro and -NO2, R 4 is selected from alkyl, cycloalkyl and aryl, preferably R 4 These are selected from C1-C6 alkyl, C3-C6 cycloalkyl and aryl groups. R 5is selected 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-tetrahydrogenobenzoyl, which may be 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 selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahydrogenobenzoyl, which may be 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 selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrafluorobenzoyl, which may be 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 selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrafluorobenzoyl, which may be optionally substituted by methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino, for example R 5 is selected from benzoyl, 4-(trifluoromethyl)benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 2,3,4,5,6-pentafluorobenzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl, cinnamoyl and 4-((2-hydroxyethyl)amino)benzoyl, particularly R 5It is selected from benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl and cinnamoyl, However, R 1 ga-NHCOR 4 [If this is the case, the condition is that Z is not OH.]

[0028] In this application, if several levels of selection are given for different substituents in a Markush formula, it is understood that these different levels of selection can be combined with each other. In other words, it is understood that all combinations of different levels of selection are explicitly assumed.

[0029] The polymer matrix of the fluorescent composition according to the present invention can be obtained from amorphous or semi-crystalline polymers selected from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamides, polyaramids, ethylene vinyl acetate, polyurethane, thermoplastic polyurethane, cyanoacrylate, rosin resin, pine resin, photopolymerizable resin, acrylic resin, and mixtures thereof. Preferably, the polymer matrix of the fluorescent composition can be obtained from polymers selected from polycarbonate, polyethylene, thermoplastic polyurethane, acrylic resin, photopolymerizable resin, and mixtures thereof, and more preferably, the polymer matrix is ​​a polycarbonate or polypropylene matrix. For example, the polymer matrix of the fluorescent composition according to the present invention can be obtained from polymers selected from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamides, polyaramids, polyurethane, thermoplastic polyurethane (TPU), cyanoacrylate, rosin resin, pine resin, photopolymerizable resin, acrylic resin, and mixtures thereof. In particular, the polymer matrix of the fluorescent composition can be obtained from polymers selected from polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, thermoplastic polyurethane, photopolymerizable resin, acrylic resin, and mixtures thereof. More specifically, the polymer matrix of the fluorescent composition can be obtained from polymers selected from polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, and mixtures thereof. Even more specifically, the polymer matrix of the fluorescent composition can be obtained from polymers selected from polycarbonate, polypropylene, polyethylene terephthalate, and mixtures thereof. More specifically, the polymer matrix of the fluorescent composition can also be obtained from polycarbonate or polyethylene terephthalate.

[0030] According to certain embodiments, the polymer matrix is ​​a semi-crystalline polymer matrix.

[0031] Advantageously, the polymer matrix does not contain anti-UV additives, allowing for optimal maintenance of fluorescence properties. Similarly, it is advantageous to use a polymer matrix that maintains its transparency even after the molding process.

[0032] The expression "polymer matrix incorporating a compound having formula I" means, according to the present invention, that the compound having formula I is closely integrated into the polymer matrix to form a mixture. Preferably, the compound having formula I is closely integrated into the polymer matrix to form a homogeneous mixture without dispersions. The integration of the compound into the polymer matrix can be carried out, for example, at high temperatures. In this embodiment, the polymer matrix is ​​heated to its melting point, then the compound having formula I is added to the molten mass, and the whole is mixed. Thus, the compound can be integrated into the polymer matrix by a melting process, extrusion, calendering, spinning extrusion, plastic injection, or dyeing.

[0033] Particularly advantageous, the inventors have confirmed that compounds having formula I according to the present invention can be incorporated into polymer matrices without altering the performance of the matrix, or in particular, the performance of the incorporated compound.

[0034] In one embodiment, the compound incorporated into the polymer matrix of the fluorescent composition is a compound having formula I, where X is S.

[0035] Therefore, according to this embodiment, the compound incorporated into the polymer matrix of the fluorescent composition has formula Ia.

[0036] [ka]

[0037] [In the formula, R, R 1 , R 2 , R3 and Z is as defined in formula I.

[0038] Preferred compounds having formula Ia 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 selected from hydrogen, methyl, methoxy, Cl, F and -NO2, R 5 is 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 5R is selected from cinnamoyl, benzoyl, and 2,3,5,6-tetrahalogenobenzoyl, which may optionally be substituted with C1-C6 alkyl, C1-C6 alkoxy, trifluoro-C1-C6 alkyl, C1-C6 alkylamino, or hydroxy-C1-C6 alkylamino, and more preferably R 5 R is selected from cinnamoyl, benzoyl, and 2,3,5,6-tetrafluorobenzoyl, which may optionally be substituted with C1-C4 alkyl, C1-C4 alkoxy, trifluoro-C1-C4 alkyl, C1-C4 alkylamino, or hydroxy-C1-C4 alkylamino, and more preferably R 5 is selected from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, which may optionally be substituted with methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino, for example R 5 The following are selected from benzoyl, 4-(trifluoromethyl)benzoyl, 3,5-bis(trifluoromethyl)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 The is selected from benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl, and cinnamoyl.

[0039] According to an alternative embodiment of this embodiment, the compound incorporated into the polymer matrix of the fluorescent composition has formula Ib.

[0040] [ka]

[0041] [In the formula, R, R 1 , R 2 , R 3 and R 5 This is as defined in Equation I.

[0042] Preferred compounds having formula Ib are R, R 1 , R 2 , R 3 and R 5 However, it is defined as follows: R is selected from hydrogen, C1-C4 alkyl, halogen, -NO2, and C1-C4 alkoxy, and preferably R is hydrogen. R 1 , R 2 and R 3 The following are independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen and -NO2, preferably R 1 , R 2 and R 3 The elements are independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, halogen, and -NO2, more preferably R 1 , R 2 and R 3 The elements are independently selected from hydrogen, C1-C2 alkyl, C1-C2 alkoxy, Cl, F, and -NO2, and more preferably R 1 , R 2 and R 3 These are independently selected from hydrogen, methyl, methoxy, Cl, F, and -NO2. R 5 The is selected from cinnamoyl, benzoyl and 2,3,5,6-tetrahalogenobenzoyl, which may optionally be substituted with C1-C6 alkyl, C1-C6 alkoxy, trifluoro-C1-C6 alkyl, C1-C6 alkylamino or hydroxy-C1-C6 alkylamino, preferably R 5 R is selected from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, which may optionally be substituted with C1-C4 alkyl, C1-C4 alkoxy, trifluoro-C1-C4 alkyl, C1-C4 alkylamino or hydroxy-C1-C4 alkylamino, and more preferably R 5is selected from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, which may optionally be substituted with methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino, for example R 5 The following are selected from benzoyl, 4-(trifluoromethyl)benzoyl, 3,5-bis(trifluoromethyl)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 The is selected from benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl, and cinnamoyl.

[0043] According to a further alternative embodiment of this embodiment, the compound incorporated into the polymer matrix of the fluorescent composition has formula Ic.

[0044] [ka]

[0045] [In the formula, R, R 1 , R 2 , R 3 and R 5 This is as defined in Equation I.

[0046] In one embodiment, the compound incorporated into the polymer matrix of the fluorescent composition is such that Z is NHR 5 or N(R 5 )2, preferably Z is NHR 5 It is a compound having formula I.

[0047] In one embodiment, the compound incorporated into the polymer matrix of the fluorescent composition is a compound having formula I, where R is hydrogen.

[0048] Particularly preferred compounds having formula I incorporated into the polymer matrix of the present invention are listed in Table 1 below.

[0049] [Table 1A]

[0050] [Table 1B]

[0051] [Table 1C]

[0052] [Table 1D]

[0053] [Table 1E]

[0054] [Table 1F]

[0055] [Table 1G]

[0056] [Table 1H]

[0057] [Table 1I]

[0058] Particularly preferred compounds having formula I incorporated into the polymer matrix of the present invention are compounds 3, 4, 5, 8, 9, 10, 11, 12, 13, 14, 16, 27, 29, and 35 listed in Table 1 above.

[0059] More particularly preferred compounds having formula I incorporated into the polymer matrix of the present invention are compounds 3, 13, 14, and 27 listed in Table 1 above.

[0060] More particularly preferred compounds having formula I incorporated into the polymer matrix of the present invention are compounds 13, 14, and 27 listed in Table 1 above.

[0061] In the fluorescent composition according to the present invention, the polymer matrix incorporates a compound having formula I in an amount necessary for detecting absorbance and fluorescence properties. The compounds having formula I according to the present invention have the advantage of enabling detection of the aforementioned properties even when they are incorporated into the polymer matrix in small amounts. Therefore, an amount of the compound having formula I in the range of 0.005% to 20% by mass relative to the total mass of the polymer matrix is ​​sufficient for detection, preferably in the range of 0.01% to 15% by mass relative to the total mass of the polymer matrix, and more preferably in the range of 0.05% to 10% by mass relative to the total mass of the polymer matrix. In particular, the amount of the compound having formula I incorporated into the polymer matrix of the fluorescent composition is between 0.005% to 10% by mass relative to the total mass of the polymer matrix, more specifically between 0.01% to 10% by mass, between 0.01% to 5% by mass, between 0.01% to 1% by mass, between 0.05% to 5% by mass, and between 0.05% to 1% by mass relative to the total mass of the polymer matrix.

[0062] According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound having formula I as defined above.

[0063] According to further specific embodiments, the fluorescent composition is essentially formed from a polymer matrix integrating compounds having formula I as defined above. The expression "essentially formed" means that, according to the present invention, the fluorescent composition is formed from a polymer matrix integrating more than 96%, more than 97%, more than 98%, or more than 99% of compounds having formula I.

[0064] According to a first alternative embodiment of the present invention, the fluorescent composition further comprises a second compound having formula I as defined above, or one of its sub-formulas Ia, Ib, and Ic.

[0065] According to this alternative embodiment, the amount of the second compound having formula I is between 0.005% by mass and 20% by mass relative to the total mass of the polymer matrix, preferably in the range of 0.01% by mass and 15% by mass relative to the total mass of the polymer matrix, and more preferably in the range of 0.05% by mass and 10% by mass relative to the total mass of the polymer matrix. In particular, the amount of the second compound having formula I incorporated into the polymer matrix of the fluorescent composition is between 0.005% by mass and 10% by mass, between 0.01% by mass and 5% by mass, between 0.01% by mass and 1% by mass, between 0.05% by mass and 5% by mass, and between 0.05% by mass and 1% by mass relative to the total mass of the polymer matrix.

[0066] According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound having formula I as defined above and a second compound having formula I as defined above.

[0067] According to certain embodiments, the fluorescent composition also includes a diffraction grating or a resonance grating.

[0068] Two different compounds can be used to obtain a fluorescent composition with particularly advantageous properties by a fluorescent composition according to the present invention, which includes a polymer matrix having formula I, or one of its subformulas Ia, Ib, and Ic, as defined above.

[0069] In fact, when two different compounds having formula I, or one of its subformulas Ia, Ib, and Ic, are mixed together, and the compounds emit light at different wavelengths, it is possible to change the fluorescence color emitted under UV irradiation. The composition becomes colored only under UV light (level 2), and this color is the mixed color of the emission of the two compounds having formula I.

[0070] According to a second alternative embodiment of the present invention, the fluorescent composition also comprises a 4-bora-3a,4a-diaza-s-indacene compound, also referred to as "BODIPY," wherein the BODIPY is incorporated into a polymer matrix. More specifically, according to this embodiment, the BODIPY compound may have the following formula III.

[0071] [ka]

[0072] [In the formula, R 1 The C1-C6 alkyl, C5-C6 cycloalkyl, C5-C6 heteroalkyl, and phenyl groups are C1-C2 alkyl, hydroxy, and R 5 They may optionally be substituted with one or more groups selected from COO- and halogens, preferably R 1 is a phenyl which may optionally be substituted with one or more groups selected from C1-C2 alkyl groups, more preferably R 1 is a phenyl compound substituted with one or more groups selected from C1-C2 alkyl groups, more preferably R 1 is a phenyl compound substituted with multiple groups selected from C1-C2 alkyl groups, more preferably R 1is a phenyl substituted with multiple methyl groups, more preferably R 1 It is 2,4,6-trimethylphenyl, R 2 and R 2' These are independently selected from hydrogen and C1-C2 alkyl, preferably R 2 and R 2' It is hydrogen, R 3 and R 3' The group is independently selected from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, and alkynyl, and the aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, and alkynyl may be optionally substituted with one or more groups selected from C1-C4 alkyl, aryl, hydroxy, and ferrocene, and the aryl group may be optionally substituted with one or more groups selected from aryl, C1-C2 alkyl, halogen, hydroxy, dimethylamino, and nitro, and the aryl may be optionally substituted with C1-C2 alkyl, preferably R 3 and R 3' It is hydrogen, R 4 and R 4' The group is independently selected from aryl, heteroaryl, cycloalkyl, alkyl, and alkenyl groups, and the aryl, heteroaryl, cycloalkyl, alkyl, and alkenyl groups may optionally be substituted with one or more groups selected from C1-C3 alkyl, aryl, hydroxy, and ferrocene groups, and the aryl group may optionally be substituted with one or more groups selected from aryl, C1-C2 alkyl, halogen, hydroxy, dimethylamino, and nitro groups, and the aryl group may optionally be substituted with C1-C2 alkyl groups, preferably R 4 and R 4' is an aryl which may optionally be substituted with one or more groups selected from C1-C3 alkyl groups, more preferably R 4 and R 4'is a phenyl which may optionally be substituted with one or more groups selected from C1-C2 alkyl groups, more preferably R 4 and R 4' is a phenyl compound substituted with one or more groups selected from C1-C2 alkyl groups, more preferably R 4 and R 4' is a phenyl substituted with multiple groups selected from C1-C2 alkyl groups, more preferably R 4 and R 4' is a phenyl substituted with multiple methyl groups, more preferably R 4 and R 4' It is 2,4,6-trimethylphenyl, R 5 These are C1-C4 alkyl or C2-C4 alkenyl compounds. R 6 and R 6' The elements are independently selected from halogens, C1-C4 alkoxys, C2-C4 alkenyloxys, C1-C4 alkyls, C2-C4 alkenyls, CN, or aryls, wherein the aryls are C1-C2 alkyls, hydroxys, R 5 They may optionally be substituted with one or more groups selected from COO- and halogens, preferably R 6 and R 6' The halogens are independently selected from halogens, and more preferably, R 6 and R 6' [This is a fluorine atom.]

[0073] According to this alternative embodiment, the amount of the compound having formula III is between 0.005% by mass and 20% by mass relative to the total mass of the polymer matrix, preferably in the range of 0.01% by mass and 15% by mass relative to the total mass of the polymer matrix, and more preferably in the range of 0.05% by mass and 10% by mass relative to the total mass of the polymer matrix. In particular, the amount of the compound having formula III incorporated into the polymer matrix of the fluorescent composition is between 0.005% by mass and 10% by mass, between 0.01% by mass and 5% by mass, between 0.01% by mass and 1% by mass, between 0.05% by mass and 5% by mass, and between 0.05% by mass and 1% by mass relative to the total mass of the polymer matrix.

[0074] According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound having formula I as defined above and a second compound having formula III as defined above.

[0075] According to certain embodiments, the fluorescent composition also includes a diffraction grating or a resonance grating.

[0076] This second alternative embodiment of the fluorescent composition, which includes a polymer matrix integrating a compound having formula I as defined above and a compound having formula III as defined above, makes it possible to obtain a fluorescent composition with particularly advantageous properties.

[0077] In fact, by mixing compounds of each class together, and if the compounds emit light at different wavelengths, it is possible to change the fluorescent color emitted under UV light. However, advantageously, the ability to detect the fluorescent composition at Level 1 and Level 2 using a mobile phone flashlight remains unchanged and unaltered.

[0078] The fluorescent composition thus obtained has a color on a white background, as well as a color obtained from a compound having formula III, which is visible, for example, on a black background and under a mobile phone flashlight. Under UV irradiation (level 2), the composition has a third color obtained from a mixture of the luminescence of compounds having formulas I and III.

[0079] According to a third alternative embodiment of the present invention, the fluorescent composition further comprises a fluorescent compound whose response under UV irradiation is observed, which absorbs ultraviolet electromagnetic radiation, particularly between 300 nm and 400 nm wavelengths, and then re-emits this energy by fluorescence in the visible region, particularly between 400 nm and 500 nm.

[0080] According to this alternative embodiment, the amount of fluorescent compound that shows a response under UV irradiation is between 0.005% by mass and 20% by mass relative to the total mass of the polymer matrix, preferably in the range of 0.01% by mass and 15% by mass relative to the total mass of the polymer matrix, and more preferably in the range of 0.05% by mass and 10% by mass relative to the total mass of the polymer matrix. In particular, in the polymer matrix of the fluorescent composition, the amount of fluorescent compound that shows a response under UV irradiation is between 0.005% by mass and 10% by mass relative to the total mass of the polymer matrix, more specifically between 0.01% by mass and 10% by mass, between 0.01% by mass and 5% by mass, between 0.01% by mass and 1% by mass, between 0.05% by mass and 5% by mass, and between 0.05% by mass and 1% by mass relative to the total mass of the polymer matrix.

[0081] According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating a compound having formula I as defined above and a fluorescent compound whose response under UV irradiation is confirmed.

[0082] According to certain embodiments, the fluorescent composition also includes a diffraction grating or a resonance grating.

[0083] This second alternative embodiment of the fluorescent composition, which includes a polymer matrix integrating a compound having formula I as defined above and a fluorescent compound whose response under UV irradiation is confirmed, makes it possible to obtain a fluorescent composition with particularly advantageous properties.

[0084] Therefore, the present invention relates secondly to the use of the fluorescent composition according to the present invention for ensuring the security of products.

[0085] The product according to the present invention may be any type of product that can accept the fluorescent composition. Therefore, the product may be solid or liquid. For example, the product may consist of plastic articles such as packaging material components, luxury goods such as leather products, cosmetics, paintings, or documents. Preferably, the product is a document.

[0086] The term "document" specifically refers to a set formed by a base material and information. The base material can be of various types and take various forms, and may include polymers or polymer mixtures. This base material may, for example, be formed entirely or partially from polymer materials. Examples of documents include not only identification documents such as passports, ID cards, driver's licenses, or health cards, but also trust documents such as banknotes and checks, or administrative documents such as registration certificates. Thus, documents can be presented in the form of paper, booklets, or cards, and information can likewise be printed and / or etched.

[0087] The phrase "securing the product" means, according to the present invention, that the fluorescent composition is integrated into or on the product to be secured at any point in its design. Therefore, the fluorescent composition can be used to secure the product during its manufacture, or similarly, applied to or integrated into the product thereafter. For example, within the scope of securing a document-type product, the fluorescent composition can subsequently be applied to all or part of the document. This point will be further developed in the description.

[0088] In any case, the product may be secured by using a fluorescent composition comprising a polymer matrix incorporating a compound having formula I, a mixture of two compounds having formula I, or a mixture of a compound having formula I and a compound having formula III, and may be certified by the properties and effects provided by the fluorescent composition.

[0089] In fact, products secured by the present invention can be authenticated by a unique combination of the absorption wavelength of the fluorescent composition and specific fluorescence. Therefore, only genuine products will simultaneously possess the correct absorption and fluorescence characteristics. Authentication according to the present invention means confirming the authenticity of a product by detecting the fluorescent composition or security measures incorporated into the product. When using compositions containing compounds having formula I and compounds having formula III, this detection of the presence or absence of color or fluorescence allows for the authentication or non-authentication of the product. Therefore, in contrast to non-genuine products in which the fluorescent composition is not revealed by detection, products that reveal the presence of the fluorescent composition by detection are genuine. Products according to the present invention secured by a fluorescent composition can be authenticated at the three security levels described below by the sole presence of the fluorescent composition containing compounds having formula I and compounds having formula III.

[0090] In fact, when using a composition containing compounds having formula I and compounds having formula III, the compound having formula III in the fluorescent composition may have an absorption band in the visible range, and the color perceived by the naked eye corresponds to the complementary color of the absorption color. For example, a compound with absorption at approximately 500-520 nm corresponds to green / blue and appears as an orange / red hue to the naked eye. This property makes it possible to achieve Level 1 security.

[0091] In relation to fluorescence properties, all compounds having formula I according to the present invention have an excitation band in the ultraviolet (UV) region. Therefore, they can be excited by UV or LED lamps emitting light particularly between 100 nm and 400 nm, thereby achieving level 2 security. This property makes it possible to obtain an activation / deactivation (on / off) effect corresponding to the display of a color change following fluorescence stimulation of the fluorescent composition by an LED or UV light source.

[0092] Ultimately, the emission wavelength can be determined using a single-lattice low-resolution spectrofluorometer or a fluorometer (detection by a photodiode or photomultiplier tube), thereby assigning security level 3 to the security element according to the present invention.

[0093] Therefore, the product, in particular the secure document according to the present invention, is detectable at levels 2 and 3 when using a composition containing a compound having formula I or a mixture of two compounds having formula I, based on a combination of absorption and fluorescence properties, and is detectable at three security levels when using a composition containing a compound having formula I and a compound having formula III.

[0094] The fluorescent composition according to the present invention can be presented in several forms that can be adapted by those 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.

[0095] According to certain embodiments, the fluorescent composition is used in the form of a layer or set of layers prepared using techniques known to those skilled in the art, such as rolling, extrusion, calendering, or calendering extrusion. These techniques are selected depending on the polymer matrix used. For example, when the matrix is ​​made of polycarbonate or thermoplastic polyurethane, calendering extrusion is preferred. Also, for example, when the matrix is ​​made of polypropylene, the pumping extrusion principle is preferred, and the pumping extrusion principle with bi-drawing is particularly preferred. A set of layers according to the present invention can be obtained, for example, by rolling two or more layers of a polymer matrix, each incorporating one or more fluorescent compositions. Such layers or sets of layers find particularly advantageous applications in securing documents, more specifically, identity cards, trust documents, or administrative documents. According to this particular embodiment, the layers or set of layers are in the form of a card. Examples of cards include business cards, bank cards, or any other type of card made of a polymer matrix. In this case, the fluorescent composition according to the present invention itself forms the base material of the document. The card can be obtained, for example, by rolling several layers of a polymer in which at least one of them is the fluorescent composition according to the present invention.

[0096] Particularly advantageous is that when a composition containing a compound having formula I is used, the layer or set of layers is transparent, thereby making it possible to obtain the following effects in addition to the effects described above. - Waveguide effect: The presence of grooves in a layer or set of layers results in different diffraction rates, stimulating fluorescence in the secured layer. Therefore, the color observed in the grooves differs from the color observed in the rest of the layer or set of layers. Under UV irradiation, this represents level 2 security. - Side effect: This effect corresponds to the observation that the complementary color of the absorbed color differs from the color observed on the surface on the side of a layer or set of layers. Under UV irradiation, this represents a level 2 security.

[0097] Particularly advantageous is that when a composition comprising a mixture of a compound having formula I and a compound having formula III is used, the layer or set of layers is transparent, thereby making it possible to obtain the following effects in addition to the effects described above. - Waveguide effect: The presence of grooves in a layer or set of layers results in different diffraction rates, stimulating fluorescence in the secured layer. Therefore, the color observed in the grooves is different from the color observed in the rest of the layer or set of layers. This represents Level 1 security. - Switch Color Effect: This effect corresponds to the color change that occurs when a layer or set of layers is superimposed on a contrasting background (e.g., a dark, especially black, background, or a light, especially white background). In this way, the complementary color of the absorbed color on the light background and the fluorescent color on the dark background are observed. This represents Level 1 security. - Side Effect: This effect corresponds to the observation that the complementary color of the absorbed color differs from the color observed on the surface on the side of the layer or set of layers. This represents Level 1 security. - Shadow effect: This effect, associated with the presence of compounds having formula III, corresponds to the display of both the fluorescent color in the layer and the projection of the complementary color of the color absorbed by the bright background when fluorescence is stimulated by LED or UV light and observed against a bright, especially white, background. This represents Level 2 security.

[0098] Advantageously, the layer has a thickness in the range of 0.050 mm to 0.800 mm, preferably in the range of 0.200 mm to 0.600 mm, for example, about 0.400 mm. If the layer has a thickness of less than 0.100 mm, it is also referred to as a film.

[0099] According to a particular embodiment, the fluorescent composition used to ensure the security of the product comprises only a polymer matrix integrating a compound having formula I as defined above.

[0100] According to further specific embodiments, the fluorescent composition used to secure the product is essentially formed from a polymer matrix integrating a compound having formula I as defined above. The expression "essentially formed" means that, according to the present invention, the fluorescent composition is formed from a polymer matrix integrating more than 96%, more than 97%, more than 98%, or more than 99% of a compound having formula I.

[0101] According to a further specific embodiment, the fluorescent composition used to ensure the security of the product is formed by a polymer matrix integrating about 50% of the compound having formula I as defined above.

[0102] According to a particular embodiment, the fluorescent composition used to ensure the security of the product comprises only a polymer matrix that integrates a mixture of two different compounds having the formula I defined above.

[0103] The fluorescent composition thus obtained has a color derived from the mixture of the respective colors of two compounds having formula I, and is visible only under UV irradiation (level 2).

[0104] According to further specific embodiments, the fluorescent composition used to ensure the security of the product comprises only a polymer matrix integrating the compound having formula I and the compound having formula III as defined above.

[0105] In fact, by mixing a compound having formula I and a compound having formula III together, and if the compounds emit light at different wavelengths, it is possible to change the fluorescence color emitted under UV irradiation. However, advantageously, the ability to detect the fluorescent composition at level 1 and level 2 using a mobile phone flashlight remains unchanged.

[0106] The fluorescent composition thus obtained has three colors: a first color (level 1) that is visible against a white background, a second color (level 1) that is visible against a black background or under the flashlight of a mobile phone, for example, and a third color (level 2) under UV irradiation.

[0107] Therefore, it is possible to complicate Level 2 by using a composition containing a mixture of compounds having formula I and compounds having formula III.

[0108] According to certain embodiments, the fluorescent composition is used in the form of a fluorescent ink. According to these embodiments, the fluorescent ink is an ink suitable for printing, particularly screen printing, offset printing, flexographic printing, heliography, inkjet printing, digital printing, copperplate printing, and 3D printing, and is preferably an ink suitable for offset printing and inkjet printing. Quite surprisingly, the inventors have advantageously observed that the fluorescent ink according to the present invention can be used for printing without causing printhead clogging.

[0109] According to certain embodiments, the fluorescent composition is used in the form of an aqueous ink.

[0110] According to a further specific embodiment, the fluorescent composition is used in the form of a fluorescent varnish.

[0111] According to a particular embodiment, the fluorescent composition is used in the form of a film, i.e., a layer having a thickness of less than 0.100 mm, particularly in the range of 0.050 mm to 0.100 mm, which is used to wrap both sides of a document, particularly an identification card, trust document, or administrative document. In an alternative embodiment of this embodiment, such a film is applied to only one of the two sides of the document, particularly an identification card. In another alternative embodiment of this embodiment, such a film is applied to only a portion of one of the two sides of the document, particularly an identification card. In yet another alternative embodiment of this embodiment, such a film is applied to only a portion of each of the two sides of the document, particularly an identification card.

[0112] According to further specific embodiments, the fluorescent composition is formed into the form of fibers. This forming can be carried out using techniques conventionally used to obtain fibers, which are either woven fibers or nonwoven fibers.

[0113] According to this embodiment, the fibers are preferably obtained by melt processing spinning technology via extrusion spinning. The production of fibers by melt processing spinning consists of first melting a mixture of polymer and fluorescent compound in an extruder. The molten material is then fed under pressure into a die consisting of multiple heads. At the die output, the filament is air-cooled and stretched, and then wound onto a substrate. Generally, sizing can be applied to the lower part of the spinning shaft.

[0114] According to one embodiment, a compound having formula I, a mixture of two compounds having formula I, or a mixture of a compound having formula I and a compound having formula III can be integrated into a polymer matrix without using extrusion, particularly by thread impregnation.

[0115] The shape of fluorescent fibers obtained by the extrusion spinning method can be determined in particular by the shape of the die head. Therefore, the fibers can be cylindrical, trefoil, octave, hollow, or multi-hollow. Changing the shape of the fibers can be advantageous in that it allows for alteration of the visual effect on a macroscopic scale. Indeed, discontinuities in the cross-section or refractive index of light within the fiber alter light transmission, and therefore alter the effect observed on a macroscopic scale.

[0116] According to further specific embodiments, several fluorescent compositions are used to secure the same product, and these fluorescent compositions differ from one another by at least the properties of a compound having formula I, a mixture of two compounds having formula I, or a mixture of a compound having formula I and a compound having formula III, integrated into a polymer matrix. This embodiment advantageously allows for better security of the product.

[0117] According to further specific embodiments, the polymer matrix is ​​a photopolymerizable resin, and the fluorescent composition also includes a polar solvent to facilitate integration between the resin and a compound having formula I, a mixture of two compounds having formula I, or a mixture of a compound having formula I and a compound having formula III. The fluorescent composition thus obtained finds very specific applications in certain 3D printing technologies, such as the manufacture of holograms, which will have a higher level of security.

[0118] Thirdly, the present invention relates to a method for ensuring the security of a product, comprising the following steps. - A step of preparing the fluorescent composition defined above, - A step of ensuring security by applying the fluorescent composition prepared in a preceding step to at least a portion of the product.

[0119] Therefore, the first step consists of obtaining the fluorescent composition defined above.

[0120] According to a particular embodiment, the first step of the security method is to prepare a fluorescent composition comprising only a polymer matrix in which a compound having formula I as defined above is integrated.

[0121] According to a further specific embodiment, the first step of the security method comprises preparing a fluorescent composition essentially formed from a polymer matrix integrating a compound having formula I as defined above. The expression "essentially formed" means, according to the present invention, that the fluorescent composition is formed from a polymer matrix integrating more than 96%, more than 97%, more than 98%, or more than 99% of a compound having formula I.

[0122] According to a particular embodiment, the first step of the security method is to prepare a fluorescent composition comprising only a polymer matrix in which two different compounds having the formula I defined above are integrated.

[0123] According to a particular embodiment, the first step of the security method is to prepare a fluorescent composition comprising only a polymer matrix integrating a compound having formula I as defined above and a compound having formula III as defined above.

[0124] 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, and the ink comprises a polymer matrix, the polymer matrix incorporating a compound having formula I, a mixture of two different compounds having formula I, or a mixture of a compound having formula I and a compound having formula III, so as to obtain a fluorescent ink. According to this embodiment, the security step is advantageously performed by printing the fluorescent ink onto a product to be secured, such as a document.

[0125] According to a particular embodiment, the fluorescent composition is a fluorescent varnish. According to this embodiment, the security assurance step can be performed, for example, by coating or varnishing the product to be secured with the fluorescent varnish.

[0126] The security process for all or part of the product to be secured can be adapted by those skilled in the art, depending not only on the product to be secured but also on the form of the composition.

[0127] The security assurance process involves integrating a fluorescent composition into the product to be secured. Therefore, the security assurance process can be performed either during or after the product's manufacturing. For example, within the scope of securing document-type products, the security assurance process can be performed on the finished product. Furthermore, this process can be repeated several times on the same product to improve its security level.

[0128] The security process may be carried out in accordance with techniques known to those skilled in the art, such as rolling, printing, weaving, varnishing, lacquering, bonding, coating, or impregnation.

[0129] According to certain embodiments, the fluorescent composition according to the present invention, comprising a compound having formula I and a compound having formula III, is applied by coating it onto a reflective or metallized surface. The product is secured by applying a set consisting of a reflective or metallized layer coated with the fluorescent composition. The metallized surface is a layer known to those skilled in the art and may consist of, for example, an aluminum metal layer.

[0130] Advantageously, according to this embodiment, the fluorescent properties of the fluorescent composition interact with the reflective appearance of the reflective layer, thereby making it possible to obtain a specific visual effect for ensuring the security of the product. At equivalent concentrations, the reflective surface increases the light intensity more than the non-reflective surface.

[0131] The security method according to the present invention may also include a step of molding a fluorescent composition prior to the security step. The molding step can be carried out according to techniques known to those skilled in the art, thereby making it possible to obtain, for example, layers, sets of layers, films, or fibers. This molding step facilitates the subsequent security step by application.

[0132] According to a particular embodiment, the first step of the method comprises preparing several fluorescent compositions that differ in their properties depending on the compound having formula I integrated into a polymer matrix. According to this embodiment, the security assurance step comprises applying the prepared compositions simultaneously or later, thereby improving the level of security given to the product.

[0133] The method according to the present invention can be used to secure any type of product that can accept the fluorescent composition. For example, the product may consist of plastic articles such as components of packaging materials, luxury goods such as leather products, or documents. Preferably, the product secured according to the described method is a document.

[0134] According to a particular embodiment, the product to be secured is a document such as an identification card, trust document, or administrative document. According to this embodiment, the fluorescent security composition can be applied to at least a portion of the surface of the product. According to an alternative embodiment of this embodiment, the fluorescent security composition is hot or cold rolled onto all surfaces of the document after being formed from a film. In a further alternative embodiment, the film is applied to only one surface of the document. In another alternative embodiment, the film is applied to only a portion of one of the two surfaces of the document, and in yet another alternative embodiment, the film is applied to only a portion of each of the two surfaces of the document.

[0135] According to further specific embodiments, the polymer matrix of the fluorescent composition also incorporates a compound having formula II as defined above.

[0136] The present invention further relates to compounds having formula II.

[0137] [ka]

[0138] [In the formula, R 1 , and R 2 and R 3 These are independently hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, aryl, vinyl, ethynyl, halogen, -NO2, -NH2, and -NHR. 4 , -N(R 4 )2, -N + (R 4 ) 3、 -NHCOR 4、-CHO, -C(O)OH, -C(O)OR 4、 -CF3, C1-C6 alkoxy, aryloxy, -SH, -SO3H, -SR 4 Selected from, preferably R 1 , and R 2 and R 3 The following are independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen and -NO2, preferably R 1 , and R 2 and R 3 R is independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, halogen and -NO2, more preferably R 1 , and R 2 and R 3 R is independently selected from hydrogen, C1-C2 alkyl, C1-C2 alkoxy, chloro, fluoro and -NO2, more preferably R 1 , and R 2 and R 3 is independently selected from hydrogen, methyl, methoxy, chloro, fluoro and -NO2, and more preferably R 1 , and R 2 and R 3 These are independently selected from hydrogen, methyl, methoxy, chloro, and fluoro. R 4 These are selected from C1-C6 alkyl, C1-C6 cycloalkyl, and aryl. R 5 is selected 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, preferably R 5R is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, which may optionally be substituted with C1-C6 alkyl, C1-C6 alkoxy, trifluoro-C1-C6 alkyl, C1-C6 alkylamino or hydroxy-C1-C6 alkylamino, and more preferably R 5 R is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, which may optionally be substituted with C1-C4 alkyl, C1-C4 alkoxy, trifluoro-C1-C4 alkyl, C1-C4 alkylamino or hydroxy-C1-C4 alkylamino, and more preferably R 5 R is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyltetrahalogenobenzoyl, which may optionally be substituted with C1-C2 alkyl, C1-C2 alkoxy, trifluoro-C1-C2 alkyl, C1-C4 alkylamino or hydroxy-C1-C2 alkylamino, and more preferably R 5 R is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, which may optionally be substituted with methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino, and more preferably R 5 This is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, which may optionally be substituted with trifluoromethyl, butylamino or hydroxyethylamino, for example R 5 These are selected from benzoyl, 4-(trifluoromethyl)benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 2,3,4,5,6-pentafluorobenzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl, cinnamoyl and 4-((2-hydroxyethyl)amino)benzoyl. however, R5 When it is cinnamoyl or benzoyl, which may be optionally substituted by methyl, methoxy, chloro or trifluoromethyl, R 1 , R 2 and R 3 are not all hydrogen, R 5 When R is benzoyl, R 1 is not methyl, R 5 When R is benzoyl, R 2 is not methyl, R 5 When R is benzoyl, R 3 is not methyl, methoxy or chloro].

[0139] In one embodiment, the compound having formula II is one having formula IIa

[0140]

Chemical formula

[0141] [wherein, R 1 and R 5 are as defined in formula II].

[0142] Preferred compounds having formula IIa are those wherein R<​​​​​​​​​​​​​​​​​​​​​​​​Preferred compounds having formula IIa are R 2 However, it is selected from methyl, methoxy, fluoro, and NO2.

[0147] In one embodiment, the compound having formula II has formula IIc.

[0148] [ka]

[0149] [In the formula, R 3 and R 5 This is as defined in Equation II.

[0150] Preferred compounds having formula III are R 3 However, it is chloroform.

[0151] Particularly preferred compounds having formula II of the present invention are listed in Table 2 below.

[0152] [Table 2A]

[0153] [Table 2B]

[0154] [Table 2C]

[0155] [Table 2D]

[0156] definition The following definitions and explanations relate to terms and expressions used in this application, including in the specification and claims.

[0157] For the description of the compounds according to the present invention, the terms and expressions used shall be construed in accordance with the following definitions, unless otherwise specified.

[0158] The term "alkyl", alone or as part of another group, refers to a hydrocarbon group having the formula C n H 2n+1 where n is an integer of 1 or more. Preferred alkyl groups are straight-chain or branched C1-C6 alkyl groups.

[0159] The term "alkenyl" refers to a straight-chain or branched unsaturated alkyl group containing one or more carbon-carbon double bonds. Suitable alkenyl groups contain from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms. Non-limiting examples of alkenyl groups include ethenyl (vinyl), 2-propenyl (allyl), 2-butenyl and 3-butenyl, with ethenyl and 2-propenyl being preferred.

[0160] The term "cycloalkyl", alone or as part of another group, refers to a saturated mono-, di- or tri-cyclic hydrocarbon group having 3 to 12 carbon atoms, particularly 5 to 10 carbon atoms, more specifically 6 to 10 carbon atoms. Suitable cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloctyl, norbornyl, adamantyl, particularly adamant-1-yl and adamant-2-yl, 1-decalinyl. Preferred cycloalkyl groups include cyclopropyl, cyclohexyl, and cycloheptyl. A particularly preferred cycloalkyl group is cyclohexyl.

[0161] The term "aryl" refers to a polyunsaturated aromatic hydrocarbon group having a single ring (phenyl) or several aromatic rings (e.g., naphthyl) fused together, typically containing 5 to 12 atoms, preferably 6 to 10 atoms, either alone or as part of another group, where at least one of the rings is aromatic. Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenanthracenyl, and pyrenyl. A particularly preferred aryl group is phenyl.

[0162] The term "heteroaryl" refers to an aromatic ring or cyclic system, either alone or as part of another group, that typically contains 5 to 12 atoms and includes 1 to 2 rings fused together, where at least one of the rings is aromatic, and one or more carbon atoms in one or more of these rings are substituted with oxygen, nitrogen, and / or sulfur atoms, the nitrogen and sulfur heteroatoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. Preferred but non-limiting heteroaryl groups are pyridinyl, pyrrolyl, furanyl, and thiophenyl. Particularly preferred heteroaryl groups are thiophenyl and pyridinyl.

[0163] The term "halo" refers to fluoro, chloro, bromo, or iodine, either alone or as part of another group. Preferred halos are chloro and fluoro, with fluoro being particularly preferred.

[0164] The term "haloalkyl" refers to the alkyl group defined above, in which one or more hydrogen atoms are substituted with the halo group defined above, either alone or as part of another group. The haloalkyl group according to the present invention may be linear or branched, but is not limited to such configurations, and is a group of formula C where n is an integer of 1 or more, preferably an integer between 1 and 10. n F 2n+1It contains a group having the following characteristics. Preferred haloalkyl groups include trifluoromethyl, difluoromethyl, fluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, nonafluoro-n-butyl, 1,1,1-trifluoro-n-butyl, 1,1,1-trifluoro-n-pentyl, and 1,1,1-trifluoro-n-hexyl, with trifluoromethyl being particularly preferred.

[0165] The present invention will be better understood by referring to the following examples. These examples are representative of specific embodiments of the present invention and are not intended to limit the scope of the invention. The figures serve to illustrate the experimental results. [Examples]

[0166] chemical synthesis All temperatures are expressed in °C, and unless otherwise specified, all reactions were carried out at room temperature (AT).

[0167] The reaction was monitored by thin-layer chromatography (TLC) performed on a pre-fabricated aluminum sheet coated with silica gel and UV254 fluorescent indicator (0.2 mm thick Kieselgel® 60 F254 Merck) or an equivalent.

[0168] NMR analysis was performed using a Bruker 300 MHz, 400 MHz, or 600 MHz spectrometer. Spectra were recorded in deuterated chloroform (CDCl3) solution. Chemical shifts were recorded in ppm, based on the monitored multiplicity proton spectrum, where s, sl, d, t, q, dd, td, and m represent singleline, broad singleline, doubleline, tripleline, quadrupleline, double doubleline, triple doubleline, and multiline (or low-resolution mass), respectively. Following the multiplicity, there is a coupled constant value, noted as J, where applicable, expressed in Hertz (Hz).

[0169] HRMS analysis was performed in positive electrospray ionization mode (ESI+).

[0170] Solvents, reagents, and starting materials were purchased from well-known chemical suppliers such as Sigma Aldrich, Acros Organics, Fluorochem, Eurisotop, VWR International, Sopachem, and Polymer. Unless otherwise specified, solvents were purified by distillation before use. Unless otherwise specified, reagents and starting materials were used without further purification.

[0171] The following abbreviations were used. HRMS: High resolution mass spectrometry; NMR: nuclear magnetic resonance; AT: room temperature, THF: Tetrahydrofuran.

[0172] Compound 3: N-(2-(benzo[d]thiazole-2-yl)phenyl)-3,5-bis(trifluoromethyl)benzamide

[0173] [ka]

[0174] In a 50 mL round-bottom flask equipped with a stirrer and thermometer, 0.5 g of 2-(1,3-benzothiazole-2-yl)aniline and 0.9 mL of pyridine were added to 7 mL of tetrahydrofuran. Next, 0.44 g of 3,5-bis(trifluoromethyl)benzoyl chloride was added, and the solution was heated to 60°C. After stirring at 60°C for about 45 minutes, the reaction mixture was cooled to room temperature. 10 mL of water was added, the mixture was filtered, and the filtration residue was washed twice with 25 mL of water and 25 mL of ethanol, and dried to obtain compound 3 (0.87 g). 1H NMR (CDCl3): δ 13.50 (1H, s), 9.02 (1H, dd, J = 5.6, 0.8 Hz), 8.66 (2H, s), 8.15 (1H, s), 8.07 (1H, 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, 0.8 Hz), 7.29 (1H, td, J = 5.2, 1.2 Hz) HRMS (ESI+) m / z 467.12 (467.41 C 22 H 12 F6N2OS+H + [M +H] + (Calculated value).

[0175] Compound 4: N-(2-(benzo[d]thiazole-2-yl)phenyl)-2,3,4,5,6-pentafluorobenzamide

[0176] [ka]

[0177] Compound 4 (1.51 g) was obtained using 1.0 g of 2-(1,3-benzothiazole-2-yl)aniline, 1.8 mL of pyridine, 13 mL of THF, and 0.7 mL of pentafluorobenzoyl chloride, following the same procedure as described above for the preparation of compound 3. 1 H NMR (CDCl3): δ 13.46 (1H, s), 8.94 (1H, dd, J = 5.6, 0.4 Hz), 7.95-7.93 (2H, m), 7.74 (1H, d, J = 5.6 Hz), 7.58 (1H, td, J = 5.2, 0.4 Hz), 7.53 (1H, td, J = 5.2, 0.8 Hz), 7.46 (1H, td, J = 5.2, 0.4 Hz), 7.30 (1H, td, J = 5.2, 0.8 Hz). HRMS (ESI+) m / z 421.14 (421.36 C 20 H9F5N2OS+H + [M +H] + (Calculated value).

[0178] Compound 5: N-(2-(benzo[d]thiazole-2-yl)phenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0179] [ka]

[0180] Potassium carbonate (4.6 g), N-(2-(benzo[d]thiazole-2-yl)phenyl)-2,3,4,5,6-pentafluorobenzamide (7.00 g), and dimethylformamide (25 mL) were added to a 100 mL round-bottom flask equipped with a stirrer and thermometer. The resulting mixture was stirred at room temperature. Then, butylamine (2.43 g) was 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 twice with 30 mL of water. Then, the starting material and petroleum ether (25 mL) were added to a 50 mL round-bottom flask equipped with a stirrer and thermometer. The resulting mixture was heated to 50 °C, and after 45 minutes, the reaction mixture was cooled to room temperature, filtered, and the filtration residue was washed twice with 15 mL of petroleum ether to obtain compound 5 (8.7 g). 1H NMR (CDCl3): δ 13.22 (1H, s), 9.99 (1H, d, J = 5.6 Hz), 7.93 (1H, d, J =5.2 Hz), 7.91 (1H, 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 = 5.2 Hz). HRMS (ESI+) m / z 474.21 (474.49 C 24 H 19 F4N3OS+H + [M +H] + (Calculated value).

[0181] Compound 8: N-(2-(benzo[d]thiazole-2-yl)-4-methylphenyl)-4-(trifluoromethyl)benzamide

[0182] [ka]

[0183] Compound 8 (0.53 g) was obtained using 0.61 g of 2-(1,3-benzothiazole-2-yl)-5-methylaniline, 0.8 mL of pyridine, 8 mL of THF, and 0.75 mL of trifluoromethylbenzoyl chloride, using the same procedure as described above for the preparation of compound 3. 1H NMR (CDCl3): δ 13.47 (1H, s), 8.87 (1H, 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 C 22 H 15 F3N2OS+H + [M +H] + (Calculated value).

[0184] Compound 9: N-(2-(benzo[d]thiazole-2-yl)-4-methylphenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0185] [ka]

[0186] Step 1: Using 1.06 g of 2-(1,3-benzothiazole-2-yl)-4-methylaniline, 1.8 mL of pyridine, 9 mL of THF, and 0.7 mL of pentafluorobenzoyl chloride, an intermediate compound (1.51 g) was obtained using the same procedure as above for the preparation of compound 3. Step 2: Compound 9 (1.33 g) was obtained using the same procedure as above for the preparation of compound 5, with 1.55 g of 2-(1,3-benzo[d]thiazole-2-yl)-4-methylaniline, 0.95 g of potassium carbonate, 6 mL of DMF, and 0.5 mL of butylamine. 1H NMR (CDCl3): δ 13.10 (1H, s), 8.87 (1H, d, J = 5.6 Hz), 7.93 (1H, d, J = 5.2 Hz), 7.83 (1H, d, J = 5.6 Hz), 7.69 (1H, s), 7.51 (1H, td, J = 5.2, 0.8 Hz), 7.43 (1H, td, J = 5.0, 0.8 Hz), 7.35 (1H, 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 C 25 H 21 F4N3OS+H + [M +H] + (Calculated value).

[0187] Compound 10: N-(2-(benzo[d]thiazole-2-yl)-4-methylphenyl)cinnamamide

[0188] [ka]

[0189] Compound 10 (0.55 g) was obtained using 0.5 g of 2-(1,3-benzothiazole-2-yl)-4-methylaniline, 0.8 mL of pyridine, 4 mL of THF, and 0.4 mL of cinnamoyl chloride, using the same procedure as described above for the preparation of compound 3. 1H NMR (CDCl3): δ 12.71 (1H, s), 8.86 (1H, d, J = 5.6 Hz), 8.06 (1H, d, J = 5.6 Hz), 7.95 (1H, d, J = 5.2 Hz), 7.81 (1H, d, J = 10.4 Hz), 7.68 (1H, d, J = 0.8 Hz), 7.67 - 7.64 (2H, m), 7.57 (1H, td, J = 5.2, 0.8 Hz), 7.49 - 7.42 (4H, m), 7.34 (1H, dd, J = 5.6, 1.2 Hz), 6.73 (1H, d, J = 10.4 Hz), 2.43 (3H, s). HRMS (ESI+) m / z 371.15 (371.47 C 23 H 18 N2OS+H + [M +H] + (Calculated value).

[0190] Compound 11: N-(2-(benzo[d]thiazole-2-yl)-4-methoxyphenyl)benzamide

[0191] [ka]

[0192] Compound 11 (1.05 g) was obtained using 1 g of 2-(1,3-benzothiazole-2-yl)-4-methoxyaniline, 1.6 mL of pyridine, 5 mL of THF, and 0.4 mL of benzoyl chloride, using the same procedure as described above for the preparation of compound 3. 1H NMR (CDCl3): δ 13.10 (1H, s), 8.99 (1H, d, J = 6 Hz), 8.23 ​​(2H, dd, J = 5.2, 1.2 Hz), 8.01 (1H, d, J = 5.6 Hz), 7.94 (1H, d, J = 5.6 Hz), 7.63 - 7.59 (3H, m) 7.55 (1H, td, J = 5.2, 0.8 Hz), 7.46 (1H, 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 C 21 H 16 N2O2S+H + [M +H] + (Calculated value).

[0193] Compound 12: N-(2-(benzo[d]thiazole-2-yl)-4-methoxyphenyl)-4-(trifluoromethyl)benzamide

[0194] [ka]

[0195] Compound 12 (0.59 g) was obtained using 0.47 g of 2-(1,3-benzothiazole-2-yl)-4-methoxyaniline, 0.6 mL of pyridine, 6 mL of THF, and 0.5 mL of trifluoromethylbenzoyl chloride, using the same procedure as described above for the preparation of compound 3. 1H NMR (CDCl3): δ 13.25 (1H, s), 8.98 (1H, d, J = 6,2 Hz), 8.43 (2H, d, J = 5.6 Hz), 8.34 (2H, d, J = 5.6 Hz), 8.14 (1H, d, J = 5.6 Hz), 8.02 (1H, J = 3.8 Hz) 7.98 (1H, d, J = 5.8 Hz), 7.61 (1H, t, J = 4.8 Hz), 7.45 (1H, d, J = 1.6 Hz), 7.15 (1H, dd, J = 6.0, 2.0 Hz), 3.94 (3H, s). HRMS (ESI+) m / z 429.10 (429.43 C 22 H 15 F3N2O2S+H + [M +H] + (Calculated value).

[0196] Compound 13: N-(2-(benzo[d]thiazole-2-yl)-4-methoxyphenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0197] [ka]

[0198] Step 1: Using 1.32 g of 2-(1,3-benzothiazole-2-yl)-4-methoxyaniline, 2.1 mL of pyridine, 12 mL of THF, and 0.8 mL of pentafluorobenzoyl chloride, an intermediate compound (1.63 g) was obtained using the same procedure as above for the preparation of compound 3. Step 2: Compound 13 (1.43 g) was obtained using the same procedure as above for the preparation of compound 5, with 1.63 g of 2-(1,3-benzo[d]thiazole-2-yl)-4-methoxyaniline, 1.0 g of potassium carbonate, 6 mL of DMF, and 0.52 mL of butylamine. 1H NMR (CDCl3): δ 13.30 (1H, s), 8.92 (1H, d, J = 5.8 Hz), 8.14 (1H, d, J = 5.4 Hz), 7.85 (1H, d, J = 5.4 Hz), 7.78 (1H, s), 7.56 (1H, t, J = 4.8 Hz), 7.52 (1H, t, J = 4.8 Hz), 7.19 (1H, 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 = 4.8 Hz). HRMS (ESI+) m / z 504.17 (504.52 C 25 H 21 F4N3O2S+H + [M +H] + (Calculated value).

[0199] Compound 14: N-(2-(benzo[d]thiazole-2-yl)-4-methoxyphenyl)cinnamamide

[0200] [ka]

[0201] Compound 14 (0.51 g) was obtained using the same procedure as described above for the preparation of Compound 3, with 0.50 g of 2-(1,3-benzothiazole-2-yl)-4-methoxyaniline, 0.77 mL of pyridine, 3 mL of THF, and 0.34 mL of trifluoromethylbenzoyl chloride. 1H NMR (CDCl3): δ 12.51 (1H, s), 8.90 (1H, d, J = 6 Hz), 8.08 (1H, d, J = 5.6 Hz), 7.95 (1H, 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 C 23 H 15 N2O2S+H + [M +H] + (Calculated value).

[0202] Compound 16: N-(2-(benzo[d]thiazole-2-yl)-4-fluorophenyl)-4-(trifluoromethyl)benzamide

[0203] [ka]

[0204] Compound 16 (0.78 g) was obtained using 0.74 g of 2-(1,3-benzothiazole-2-yl)-4-fluoroaniline, 1.1 mL of pyridine, 3 mL of THF, and 0.43 mL of trifluoromethylbenzoyl chloride, using the same procedure as described above for the preparation of compound 4. 1H NMR (CDCl3): δ 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 C 21 H 12 F4N2OS+H + [M +H] + (Calculated value).

[0205] Compound 27: N-(2-(benzo[d]thiazole-2-yl)-5-chlorophenyl)benzamide

[0206] [ka]

[0207] Compound 27 (1.36 g) was obtained using 2 g of 2-(1,3-benzothiazole-2-yl)-5-chloroaniline, 3.1 mL of pyridine, 3 mL of THF, and 3.6 mL of benzoyl chloride, using the same procedure as described above for the preparation of compound 3. 1 H NMR (CDCl3): δ 13.48 (1H, s), 9.17 (1H, d, J = 1.2 Hz), 8.24 (2H, dd, J = 5.6 Hz), 8.0 (1H, d, J = 5.2 Hz), 7.95 (1H, d, J = 4.8 Hz), 7.82 (1H, d, J = 5.6 Hz) 7.66 - 7.61 (3H, m), 7.57 (1H, 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 C 20 H 13 ClN2OS+H + [M +H] + (Calculated value).

[0208] Compound 29: N-(2-(benzo[d]thiazole-2-yl)-5-chlorophenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0209] [ka]

[0210] Step 1: Using 2.00 g of 2-(1,3-benzothiazole-2-yl)-5-chloroaniline, 3.1 mL of pyridine, 10 mL of THF, and 3.3 mL of pentafluorobenzoyl chloride, an intermediate compound (1.45 g) was obtained using the same procedure as above for the preparation of compound 3. Step 2: Compound 29 (0.93 g) was obtained using the same procedure as above for the preparation of compound 5, with 1.45 g of 2-(1,3-benzo[d]thiazole-2-yl)-5-chloroaniline, 0.88 g of potassium carbonate, 5 mL of DMF, and 0.46 mL of butylamine. 1 H NMR (CDCl3): δ 13.31 (1H, s), 9.09 (1H, d, J = 1.2 Hz), 7.93 (1H, d, J =5.6 Hz), 7.84 (1H, d, J = 5.2 Hz), 7.80 (1H, d, J = 5.2 Hz), 7.52 (1H, td, J = 5.2, 0.8 Hz), 7.45 (1H, 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 = 4.8 Hz). HRMS (ESI+) m / z 508.63 (508.94 C 24 H 18 ClF4N3OS+H + [M +H] + (Calculated value).

[0211] Compound 35: N-(2-(benzo[d]thiazole-2-yl)-5-chlorophenyl)-2,3,5,6-tetrafluoro-4-{(2-hydroxyethyl)amino}benzamide

[0212] [ka]

[0213] Step 1: Using 2.00 g of 2-(1,3-benzothiazole-2-yl)-5-chloroaniline, 3.1 mL of pyridine, 10 mL of THF, and 3.3 mL of pentafluorobenzoyl chloride, an intermediate compound (1.45 g) was obtained using the same procedure as above for the preparation of compound 3. Step 2: Compound 35 (0.75 g) was obtained using the same procedure as above for the preparation of Compound 4, with 1.0 g of 2-(1,3-benzo[d]thiazole-2-yl)-5-chloroaniline, 0.66 g of potassium carbonate, 5 mL of DMF, and 0.43 mL of aminoethanol. 1 H NMR (CDCl3): δ 13.34 (1H, s), 9.08 (1H, d, J = 1.2 Hz), 7.92 (1H, d, J =5.2 Hz), 7.83 (1H, d, J = 5.6 Hz), 7.80 (1H, d, J = 6.0 Hz), 7.52 (1H, td, J = 5.2, 0.8 Hz), 7.44 (1H, td, J = 5.2, 0.8 Hz), 7.2 (1H, dd, J = 5.6, 1.2 Hz), 4.7 (1H, bs), 3.94 (2H, t, J = 3.2 Hz), 3.73 (2H, m). HRMS (ESI+) m / z 496.57 (496.88 C 22 H 14ClF4N3OS+H + [M +H] + (Calculated value).

[0214] Application examples (Example 1) Preparation of layered fluorescent compositions and their use for security purposes In this example, the compound having formula I used is compound 13 having the following formula.

[0215] [ka]

[0216] Compound 13 is in the form of a yellow powder, has absorption at 365 nm, and emits fluorescence at 605 nm. 17 g of compound was kneaded with 10 kg of polycarbonate (PC Makralon 2456) using an extruder to obtain a fluorescent composition. Extrusion is performed using a twin-screw extruder (Brabender), with a screw rotation speed of 50 rom, a hopper flow rate of 3.8 kg / hour, and the temperature profile is as follows: 275°C-280°C-280°C-285°C-285°C-285°C-290°C (supply => line). A small amount of the extruded fluorescent composition is taken and then diluted 10-fold by adding polycarbonate (PC Makralon 2456) through a Fairex extruder (45mm diameter) equipped with a 350mm wide Scamex flat die, followed by three cylinder rollers with a 30° incline. At the calendar output, the fluorescent composition is in the form of a 100 mm thick layer. After setting the calendar, the test was reproduced to obtain a second layer of 400 mm thick from the fluorescent composition. The secure layer thus obtained is then used as the base material for a document, and the document is therefore secure. Visual and spectroscopic analysis of the resulting layers demonstrated that the incorporation of fluorescent dyes into polycarbonate did not alter its performance in terms of absorption and fluorescence emission. The resulting fluorescent layers exhibited properties similar to those observed when the compound was in solution.

[0217] (Example 2) Preparation of varnish-type fluorescent compositions and their use for security purposes In this embodiment, the compound having formula I used is compound 14 having the following formula.

[0218] [ka]

[0219] 44 mg of compound 14 is integrated into 10 g of solvent-based acrylic varnish (0.4% by mass / mass). The fluorescent varnish obtained in this manner is then coated onto a 100 μm thick polyethylene terephthalate film at an application speed of 50 mm / second using an automatic applicator (automatic film applicator, TQC ASTM D 823) and a 20 μm Meyer rod. The measured varnish deposit had a thickness of 5 μm with a solvent-based varnish containing 33% dry extract. A set consisting of polyethylene terephthalate film coated with fluorescent varnish forms a fluorescent layer. The resulting fluorescent layer is a secure layer. When irradiated with a UV lamp (365 nm), purple fluorescence is visible to the naked eye. Visual and spectroscopic analysis of the securely protected layer demonstrated that the incorporation of fluorescent dyes into polycarbonate does not alter its performance in terms of absorption and fluorescence emission. The secure layer obtained in this way is used as a card substrate due to its fluorescent properties.

[0220] (Example 3) Preparation of an ink-type fluorescent composition containing a compound having formula I and a compound having formula III according to the present invention. In this embodiment, the compound having formula I used is compound 27 having the following formula.

[0221] [ka]

[0222] Compound 27 is in the form of a white powder, has absorption at 365 nm, and emits fluorescence at 522 nm.

[0223] The compound having formula III to be used is compound 36 having the following formula.

[0224] [ka]

[0225] Compound 36 is in the form of an orange powder, has absorption at 547 nm, and emits fluorescence at 568 nm.

[0226] Preparation of fluorescent compositions in ink form: Dissolve 400 mg of compound 27 uniformly in 100 g of Mara® Gloss Go type transparent unexposed screen printing ink, sold by Marabu, which is suitable for printing on polycarbonate resin surfaces. Dissolve 100 mg of compound 36 uniformly in 100 g of the same transparent, unexposed screen printing ink. Next, ink-containing compound 27 and ink-containing compound 36 are mixed in a 1:1 mass ratio. The fluorescent composition thus formulated is printed onto a transparent polycarbonate card.

[0227] Results: The fluorescent compositions were printed perfectly. The pattern printed in this manner has a pink color that is visible due to transparency when the card is placed on a white background, and an orange color that is visible due to transparency when the card is placed on a black background. When the card is exposed to UV light, a yellow fluorescence is visible.

[0228] (Example 4) Preparation of a fluorescent composition in ink form containing a compound having formula I according to the present invention In this example, the Class I compound used is compound 3 having the following formula.

[0229] [ka]

[0230] Compound 3 is in the form of a white powder, has absorption at 365 nm, and exhibits fluorescence emission at 513 nm.

[0231] Preparation of fluorescent compositions in ink form: 400 mg of compound 3 is uniformly dissolved in 100 g of Mara® Gloss Go type transparent unexposed screen printing ink, sold by Marabu, which is suitable for printing on polycarbonate resin surfaces. Therefore, the mass concentration of the ink is 0.4% (mass / mass). The fluorescent composition thus formulated is printed onto a transparent polycarbonate card using a screen printing frame with a mesh size of 90.

[0232] Results: The fluorescent compositions were printed perfectly. The patterns printed in this manner are invisible under ambient light and exhibit strong yellow fluorescence under UV light (365 nm). The optical properties of the dye are replaced between the pure dye and the screen-printed layer.

[0233] (Example 5) Preparation of a fluorescent composition in ink form containing a compound having formula I according to the present invention In this example, the compound having formula I used is compound 13 having the following formula.

[0234] [ka]

[0235] Compound 13 is in the form of a white powder, has absorption at 365 nm, and emits fluorescence at 605 nm.

[0236] Preparation of fluorescent compositions in ink form: 400 mg of compound 3 is uniformly dissolved in 100 g of Mara® Gloss Go type transparent unexposed screen printing ink, sold by Marabu, which is suitable for printing on polycarbonate resin surfaces. Therefore, the mass concentration of the ink is 0.4% (mass / mass). The fluorescent composition thus formulated is printed onto a transparent polycarbonate card using a screen printing frame with a mesh size of 90.

[0237] Results: The fluorescent compositions were printed perfectly. The printed pattern is invisible under ambient light and exhibits red fluorescence under UV light (365 nm). The optical properties of the dye are replaced between the pure dye and the screen-printed layer.

[0238] (Example 6) Preparation of a fluorescent composition in ink form containing two compounds having formula I according to the present invention In this embodiment, the Class I compounds used are compounds 3 and 13, shown in the following formulas.

[0239] [ka]

[0240] [ka]

[0241] Preparation of fluorescent compositions in ink form: Dissolve 400 mg of compound 3 uniformly in 100 g of Mara® Gloss Go type transparent unexposed screen printing ink, sold by Marabu, which is suitable for printing on polycarbonate resin surfaces. Dissolve 400 mg of compound 13 uniformly in 100 g of the same transparent, unexposed screen printing ink. These two inks are mixed in a mass ratio of 3:1 (compound 13:compound 3 - mass ratio) and homogenized until a uniform color is obtained.

[0242] Results: The fluorescent compositions were printed perfectly. The patterns printed in this manner are invisible under ambient light and exhibit strong orange fluorescence under UV light (365 nm). The color obtained in this way is related to the mixed color of the fluorescent colors of the two dyes.

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