Fluorescent composition comprising at least one benzoxazole compound for protecting products

Abstract

The present invention relates to the use of a fluorescent composition for protecting a product, said composition comprising a polymer matrix incorporating a compound having formula I: [Formula I]

Description

Technical Field

[0001] The present invention relates to the field of product security and authentication. More particularly, the present invention relates to fluorescent compositions for protecting and authenticating products such as identity, credit and administrative documents. Background Art

[0002] Counterfeiting and forgery are growing significantly in many sectors, such as packaging, particularly blister packs for pharmaceutical products, and in high-value-added sectors such as luxury goods, automotive, and aviation. With the rise in identity theft and the introduction of points-based driver's licenses in some countries, identity and administrative documents are also becoming targets for counterfeiting. Therefore, product safety and authentication are crucial, raising national and international security challenges.

[0003] Regarding the security of products such as identity, credit or administrative documents, several companies offer visual authentication solutions, for example using holograms or laser etching, which can be used to insert information on plastic card bodies (such as identity cards, health cards or driver's licenses).

[0004] Document EP0708935 A1 describes, for example, a holographic protective layer set. This set consists of a backing film with at least one protective varnish, a reflective or transparent layer with a diffractive microstructure, and finally an adhesive layer. Once this set of layers is transferred to the document, its security is achieved. As described in document WO2010 / 086522, this system is subsequently enhanced with perforations to make separation of the layers more difficult. However, even with perforations, this set of layers requires a large number of components to assemble, which presents additional time and cost constraints.

[0005] Document FR1650164, held by the applicant, describes the use of compounds from the 4,4-difluoro-4-boron-3a,4a-diaza-S-indacene family for the preparation of security elements for products, particularly documents, comprising a polymer into which the compounds are incorporated. While interesting, the compounds described only allow for fluorescence emission in the range from 500 nm to the infrared, thus failing to cover the entire visible spectrum.

[0006] Application US 2008 / 0081913 A1 describes compounds of the benzoxazole and benzothiazole type which have fluorescent properties and are used in particular as authentication compounds in data storage media and data storage substrates.

[0007] Products, particularly documents, can be protected by security elements, which can be categorized according to three security levels based on the means used for their detection. Thus, a Level 1 security element is one that can be detected by at least one of the five senses or by a medium that contrasts with the background. In particular, this level includes guilloche patterns, optically variable devices (such as iridescent printing), holograms, optically variable inks, markers, variable laser images, or multiple laser images.

[0008] Level 2 security elements are elements that can be detected using simple equipment, such as an ultraviolet lamp, a convex lens, or the flashlight of a mobile phone. This level has detectable elements such as microprints and fluorescent inks, as well as fluorescent fibers or chips.

[0009] Finally, Level 3 security elements are those that can be detected using sophisticated equipment, such as a fluorescence spectrophotometer or electron microscope. This category specifically includes nano-etched pigments, biometric chips, and fluorescent markers that are undetectable to the naked eye.

[0010] As a general rule, security products incorporate several security elements at different levels.

[0011] Although existing protection schemes prove interesting, some can be difficult to implement and / or inspect and there remains a need to develop alternatives, particularly in the visible spectrum.

[0012] Therefore, there is an urgent need to develop new security methods that are easy to implement, stable, have fluorescent emission, and can quickly check product authenticity. These novel methods must provide a high level of security and cannot be mutually exclusive or incompatible with existing methods.

[0013] The inventors are therefore to their credit for having achieved all or part of these aims by identifying and developing compounds which make it possible to obtain particularly advantageous fluorescent compositions for use in the field of product safety. Summary of the Invention

[0014] The present invention relates to a fluorescent composition comprising a polymer matrix incorporating a compound having formula I:

[0015] [Chemical Formula 1]

[0016]

[0017] in,

[0018] X is selected from NH, O and S;

[0019] Z is selected from OH, NHR 5 and N(R 5 )2;

[0020] R is 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-SR 4 ;

[0021] R 1 、R 2 and R 3 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-SR 4 ;

[0022] R 4 is selected from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;

[0023] R 5 is selected from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1-C6-alkoxycarbonyl, C1-C6-alkylaminocarbonyl, C1-C6-alkylaminosulfinyl, di-C1-C6-alkylaminosulfinyl, arylaminocarbonyl, arylaminosulfinyl, arylsulfonyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino;

[0024] The condition is that when R 2 Yes-NHCOR 4 When Z is not OH; and

[0025] The symbol It means that R can be substituted multiple times at any free position of the benzene nucleus.

[0026] According to another aspect, the use of the fluorescent composition according to the invention for protecting products is proposed.

[0027] According to another aspect, a method for protecting a product is proposed comprising a step of preparing a fluorescent composition as defined above and a step of protecting by applying said fluorescent composition to at least a portion of the product to be protected.

[0028] According to another aspect, compounds of formula (II) are proposed:

[0029] [Chemical Formula 2]

[0030]

[0031] in,

[0032] R 1 、R 2 and R 3 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-SR 4 ;

[0033] R 4 is selected from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;

[0034] R 5 is selected from C1-C6-alkyl, hydroxy-C1-C6-alkyl, C1-C6-alkoxycarbonyl, di-C1-C6-alkylaminosulfinyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, optionally substituted with C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; and

[0035] The conditions are:

[0036] When R 5 When R is cinnamoyl or benzoyl optionally substituted by methyl, methoxy, chloro or trifluoromethyl, 1 、R 2 and R 3Not all are three hydrogens;

[0037] When R 5 When it is benzoyl, R 1 Not meth;

[0038] When R 5 When it is benzoyl, R 2 is not methyl; and

[0039] When R 5 When it is benzoyl, R 3 Not methyl, methoxy or chlorine. DETAILED DESCRIPTION

[0040] The present invention first relates to a fluorescent composition comprising a polymer matrix incorporating a compound having formula I:

[0041] [Chemical Formula 1]

[0042]

[0043] in,

[0044] X is selected from NH, O and S;

[0045] 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 ;

[0046] R is 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(O)OH、-C(O)OR 4 、-CF3、aryloxy、-SH、-SO3H、-SR 4 ; Preferably, R is selected from hydrogen, C1-C4-alkyl, halogen, -NO2, -NH2, -NHR 4 、-N(R 4 )2, C1-C4-alkoxy; more preferably, R is selected from hydrogen, C1-C2-alkyl, halogen, C1-C4-alkoxy; more preferably, R is hydrogen;

[0047] R 1 、R 2 and R 3independently 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-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 independently selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, halogen and -NO2; even more preferably, R 1 、R 2 and R 3 independently selected from hydrogen, methyl, methoxy, bromine, chlorine and -NO2;

[0048] R 4 is selected from alkyl, cycloalkyl and aryl; preferably, R 4 is selected from C1-C6-alkyl, C3-C6-cycloalkyl and aryl;

[0049] R 5 is selected from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1-C6-alkoxycarbonyl, C1-C6-alkylaminocarbonyl, C1-C6-alkylaminosulfinyl, di-C1-C6-alkylaminosulfinyl, arylaminocarbonyl, arylaminosulfinyl, 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; preferably, R 5is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, 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-pentahalobenzoyl 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 selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted with 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; in particular, R 5 selected from benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl and cinnamoyl;

[0050] The condition is that when R 1 Yes-NHCOR 4 When Z is not OH.

[0051] It is understood in this application that when multiple priorities are given for different substituents in a Markush formula, the different priorities can be combined with each other. In other words, it should be understood that all combinations of different priorities are explicitly contemplated.

[0052] The polymer matrix of the fluorescent composition according to the present invention can be obtained from an amorphous or semi-crystalline polymer selected from the group consisting of polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamide, polyaramid, 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 a polymer selected from the group consisting of polycarbonate, polyethylene, thermoplastic polyurethane, acrylic resin, and 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 a polymer selected from the group consisting of polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamide, polyaramid, 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 derived from a polymer selected from the group consisting of polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, thermoplastic polyurethane, photopolymer resin, acrylic resin, and mixtures thereof. More specifically, the polymer matrix of the fluorescent composition can be derived from a polymer selected from the group consisting of polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, and mixtures thereof. Even more specifically, the polymer matrix of the fluorescent composition can be derived from a polymer selected from the group consisting of polycarbonate, polypropylene, polyethylene terephthalate, and mixtures thereof. Even more specifically, the polymer matrix of the fluorescent composition can be derived from polycarbonate or polyethylene terephthalate.

[0053] According to a particular embodiment, the polymer matrix is ​​a semi-crystalline polymer matrix.

[0054] Advantageously, the polymer matrix does not contain UV-resistant additives, so that the fluorescent properties can thus be optimally preserved.Similarly, it is also advantageous to use a polymer matrix that retains its transparent properties even after the shaping step.

[0055] According to the present invention, the expression "a polymer matrix incorporating a compound of Formula I" means that the compound of Formula I is intimately integrated into the polymer matrix to form a mixture. Preferably, the compound of Formula I is intimately integrated into the polymer matrix to form a homogeneous mixture without dispersion. Integration of the compound into the polymer matrix can be carried out, for example, under heat. In this case, the polymer matrix is ​​heated to its melting point, the compound of Formula I is then added to the molten mass, and the whole is then mixed. Thus, the compound can be integrated into the polymer matrix by melt processing, extrusion, calendar extrusion, spin extrusion, plastic injection molding, or dyeing.

[0056] Particularly advantageously, the inventors have observed that the compounds of formula I according to the invention can be incorporated into a polymer matrix without modifying the properties of the matrix or, above all, without modifying the properties of the incorporated compound.

[0057] In one embodiment, the compound incorporated into the polymer matrix of the fluorescent composition is a compound having Formula I, wherein X is S.

[0058] Thus, according to this embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are those having Formula Ia:

[0059] [Chemical Formula 3]

[0060]

[0061] Among them, R 1 、R 2 、R 3 and Z are as defined in Formula I.

[0062] Preferred compounds of formula Ia are those wherein R, R 1 、R 2 、R 3 and / or a compound wherein Z is defined as follows:

[0063] Z is NHR 5 or N(R 5 )2;

[0064] R is selected from hydrogen, C1-C4-alkyl, halogen, -NO2 and C1-C4-alkoxy; preferably R is hydrogen;

[0065] 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 independently selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, Cl, F and -NO 2 ; even more preferably R 1 、R 2 and R 3 independently selected from hydrogen, methyl, methoxy, Cl, F and -NO2;

[0066] R 5is selected from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1-C6-alkoxycarbonyl, di-C1-C6-alkylaminosulfinyl, arylaminocarbonyl, arylsulfonyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl and 2,3,5,6-tetrahalobenzoyl, 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 and 2,3,5,6-tetrahalobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; more preferably, R is selected 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 selected from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted with 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; in particular, R 5 Selected from benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl and cinnamoyl.

[0067] According to an alternative embodiment of this embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are those having formula Ib:

[0068] [Chemical Formula 4]

[0069]

[0070] Among them, R 1 、R 2 、R 3 and R 5 As defined in Formula I.

[0071] Preferred compounds of formula Ib are those wherein R, R 1 、R 2 、R 3 and R 5 Those defined as follows:

[0072] R is selected from hydrogen, C1-C4-alkyl, halogen, -NO2 and C1-C4-alkoxy; preferably R is hydrogen;

[0073] 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 independently selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, Cl, F and -NO2; even more preferably R 1 、R 2 and R 3 independently selected from hydrogen, methyl, methoxy, Cl, F and -NO2;

[0074] R 5 is selected from cinnamoyl, benzoyl and 2,3,5,6-tetrahalobenzoyl, 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 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 selected from cinnamoyl, benzoyl and 2,3,5,6-tetrafluorobenzoyl, optionally substituted with 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; in particular, R 5 Selected from benzoyl, 3,5-bis(trifluoromethyl)benzoyl, 4-(butylamino)-2,3,5,6-tetrafluorobenzoyl and cinnamoyl.

[0075] According to another alternative to this embodiment, the compounds incorporated into the polymer matrix of the fluorescent composition are those having formula Ic:

[0076] [Compound 5]

[0077]

[0078] Among them, R 1 、R 2 、R 3 and R 5 As defined in Formula I.

[0079] In one embodiment, the compound incorporated into the polymer matrix of the fluorescent composition is a compound having Formula I, wherein Z is NHR 5 or N(R 5 )2, preferably Z is NHR 5 .

[0080] In one embodiment, the compound incorporated into the polymer matrix of the fluorescent composition is a compound having Formula I, wherein R is hydrogen.

[0081] Particularly preferred compounds of formula I for incorporation into the polymer matrix of the present invention are those listed in Table 1 below:

[0082] [Table 1]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092] Particularly preferred compounds of formula I for incorporation 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.

[0093] Even more particularly preferred compounds of formula I for incorporation into the polymer matrix of the present invention are compounds 3, 13, 14 and 27 listed in Table 1 above.

[0094] Even more particularly preferred compounds of formula I for incorporation into the polymer matrix of the present invention are compounds 13, 14 and 27 listed in Table 1 above.

[0095] In the fluorescent composition according to the present invention, the polymer matrix incorporates an amount of a compound of Formula I required for detecting absorbance and fluorescence properties. Compounds of Formula I according to the present invention have the advantage of being able to detect these properties even when incorporated into the polymer matrix in small amounts. Thus, an amount of the compound of Formula I in the range of 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably in the range of 0.01% to 15% by weight relative to the total weight of the polymer matrix, and even more preferably in the range of 0.05% to 10% by weight relative to the total weight of the polymer matrix, is sufficient for detection. In particular, the amount of the compound of Formula I incorporated into the polymer matrix of the fluorescent composition is 0.005% to 10% by weight relative to the total weight of the polymer matrix, more specifically 0.01% to 10% by weight, 0.01% to 5% by weight, 0.01% to 1% by weight, 0.05% to 5% by weight, or 0.05% to 1% by weight relative to the total weight of the polymer matrix.

[0096] According to a particular embodiment, the fluorescent composition comprises only a polymer matrix in which the compound of formula I as defined above is integrated.

[0097] According to another specific embodiment, the fluorescent composition is essentially formed of a polymer matrix in which the compound of formula I as defined above is integrated. According to the present invention, the expression "essentially formed" means that the fluorescent composition is formed of more than 96%, 97%, 98% or more than 99% of a polymer matrix in which the compound of formula I is integrated.

[0098] 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 subformulae Ia, Ib and Ic.

[0099] According to this alternative embodiment, the amount of the second compound of formula I is from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably from 0.01% to 15% by weight relative to the total weight of the polymer matrix, and even more preferably 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 from 0.005% to 10% by weight relative to the total weight of the polymer matrix, more particularly from 0.01% to 10% by weight, 0.01% to 5% by weight, 0.01% to 1% by weight, 0.05% to 5% by weight, or 0.05% to 1% by weight relative to the total weight of the polymer matrix.

[0100] According to a particular embodiment, the fluorescent composition comprises only a polymer matrix integrating the compound having formula I as defined above and the second compound having formula I as defined above.

[0101] According to a specific embodiment, the fluorescent composition further comprises a diffraction grating or a resonance grating.

[0102] The fluorescent composition according to the invention comprises a polymer matrix in which two different compounds of formula I or one of its subformulae Ia, Ib and Ic as defined above make it possible to obtain fluorescent compositions having particularly advantageous properties.

[0103] In fact, when two different compounds of formula I or one of its subformulas Ia, Ib and Ic are mixed together, and said compounds emit at different wavelengths, then the color of the fluorescence emitted under ultraviolet irradiation can be changed. The composition then develops color only under UV (level 2), and this color is a mixture of the emission light of the two compounds of formula I.

[0104] According to a second alternative embodiment of the present invention, the fluorescent composition further comprises a compound of the 4-borono-3a,4a-diaza-S-indacene family, also known as "BODIPY", incorporated into a polymer matrix. Very specifically, according to this embodiment, BODIPY may be a compound having the following formula III:

[0105] [Compound 6]

[0106]

[0107] in,

[0108] R 1 is C1 to C6 alkyl, C5 to C6 cycloalkyl, C5 to C6 heteroalkyl, phenyl, the phenyl group is optionally substituted with one or more selected from C1 to C2 alkyl, hydroxyl, R5 COO- and halogen substituted; preferably, R 1 is phenyl optionally substituted by one or more groups selected from C1 to C2 alkyl; more preferably, R 1 is phenyl substituted by one or more groups selected from C1 to C2 alkyl; more preferably, R 1 is phenyl substituted by several groups selected from C1 to C2 alkyl; more preferably, R 1 is a phenyl group substituted by several methyl groups; more preferably, R 1 It is 2,4,6-trimethylphenyl;

[0109] R 2 and R 2 ' are independently selected from hydrogen and C1 to C2 alkyl; preferably, R2 and R2' are hydrogen;

[0110] R3 and R3' are independently selected from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, wherein the aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl are optionally substituted by one or more groups selected from C1 to C4 alkyl, aryl, hydroxyl and ferrocene, wherein the aryl is optionally substituted by one or more groups selected from aryl, C1 to C2 alkyl, halogen, hydroxyl, dimethylamino, nitro, and the aryl is optionally substituted by C1 to C2 alkyl; preferably, R 3 and R 3 'It is hydrogen;

[0111] R 4 and R 4 'Independently selected from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, the aryl, heteroaryl, cycloalkyl, alkyl and alkenyl are optionally substituted with one or more groups selected from C1 to C3 alkyl, aryl, hydroxyl and ferrocene, the aryl is optionally substituted with one or more groups selected from aryl, C1 to C2 alkyl, halogen, hydroxyl, dimethylamino, nitro, the aryl is optionally substituted with C1 to C2 alkyl; preferably R 4 and R 4 ' is an aryl group optionally substituted by one or more groups selected from C1 to C3 alkyl; more preferably, R 4 and R 4 ' is phenyl optionally substituted by one or more groups selected from C1 to C2 alkyl; more preferably, R 4 and R 4 ' is phenyl substituted by one or more groups selected from C1 to C2 alkyl; more preferably, R 4 and R 4 ' is a phenyl group substituted by several groups selected from C1 to C2 alkyl groups; more preferably, R 4 and R 4 ' is a phenyl group substituted by several methyl groups; more preferably, R4 and R 4 ' is 2,4,6-trimethylphenyl;

[0112] R 5 It is a C1 to C4 alkyl group or a C2 to C4 alkenyl group.

[0113] R 6 and R 6 'Independently selected from halogen, C1 to C4 alkoxy, C2 to C4 alkenyloxy, C1 to C4 alkyl, C2 to C4 alkenyl, CN or aryl, the aryl optionally substituted by one or more selected from C1 to C2 alkyl, hydroxy, R 5 COO- and halogen substituted; preferably, R 6 and R 6 ' is independently selected from halogen; more preferably, R 6 and R 6 ' is a fluorine atom.

[0114] According to this alternative embodiment, the amount of the compound of formula III is from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably from 0.01% to 15% by weight relative to the total weight of the polymer matrix, and even more preferably from 0.05% to 10% by weight relative to the total weight of the polymer matrix. In particular, the amount of the compound of formula III incorporated into the polymer matrix of the fluorescent composition is from 0.005% to 10% by weight relative to the total weight of the polymer matrix, more particularly from 0.01% to 10% by weight, from 0.01% to 5% by weight, from 0.01% to 1% by weight, from 0.05% to 5% by weight, and from 0.05% to 1% by weight relative to the total weight of the polymer matrix.

[0115] According to one particular embodiment, the fluorescent composition comprises only a polymer matrix in which the compound of formula I as defined above and the second compound of formula III as defined above are integrated.

[0116] According to a specific embodiment, the fluorescent composition further comprises a diffraction grating or a resonance grating.

[0117] The fluorescent composition according to this second alternative embodiment comprises a polymer matrix in which the compound of formula I as defined above and the compound of formula III as defined above make it possible to obtain a fluorescent composition having particularly advantageous properties.

[0118] In fact, when compounds from each family are mixed together and the compounds emit at different wavelengths, then the color of the fluorescence emitted under UV can be changed. However, advantageously, the performance of the fluorescent compositions according to Class 1 and Class 2 remains unchanged and unaltered when tested using a mobile phone flashlight.

[0119] The fluorescent composition thus obtained has a color on a white background and a visible color on a black background, for example, and under a mobile phone flashlight obtained from the compound of formula III. Under UV irradiation (level 2), the composition has a third color obtained by mixing the emitted light of the compounds of formula I and formula III.

[0120] According to a third alternative embodiment of the invention, the fluorescent composition further comprises a fluorescent compound, wherein the response under ultraviolet radiation is examined, which absorbs ultraviolet electromagnetic radiation, in particular with a wavelength of 300-400 nm, and then re-emits this energy by fluorescence in the visible range, in particular of 400-500 nm.

[0121] According to this alternative embodiment, the amount of the fluorescent compound that detects a response under UV radiation is from 0.005% to 20% by weight relative to the total weight of the polymer matrix, preferably from 0.01% to 15% by weight relative to the total weight of the polymer matrix. Even more preferably, the amount is from 0.05% to 10% by weight relative to the total weight of the polymer matrix. In particular, the amount of the fluorescent compound that detects a response under UV radiation in the polymer matrix of the fluorescent composition is from 0.005% to 10% by weight relative to the total weight of the polymer matrix, more particularly from 0.01% to 10% by weight, 0.01% to 5% by weight, 0.01% to 1% by weight, 0.05% to 5% by weight, or 0.05% to 1% by weight relative to the total weight of the polymer matrix.

[0122] According to a particular embodiment, the fluorescent composition comprises only a polymer matrix in which the compound of formula I as defined above and the fluorescent compound are integrated, wherein the response under UV radiation is detected.

[0123] According to a specific embodiment, the fluorescent composition further comprises a diffraction grating or a resonant grating.

[0124] The fluorescent composition according to this second alternative embodiment comprises a polymer matrix in which there is a compound of formula I as defined above and in which the fluorescent compound whose response under UV radiation is examined makes it possible to obtain fluorescent compositions having particularly advantageous properties.

[0125] The present invention therefore relates secondarily to the use of the fluorescent composition according to the invention for protecting products.

[0126] The product according to the present invention can be any type of product capable of receiving the fluorescent composition. Thus, the product can be solid or liquid. For example, it can consist of a plastic item, such as a portion of packaging material, a luxury product (such as leather goods), a cosmetic, a painting, or a document. Preferably, the product is a document.

[0127] The term "document" refers in particular to an assembly consisting of a substrate and information. The substrate can be of various types and in various forms, and can optionally comprise a polymer or a polymer mixture. For example, the substrate can be formed entirely or partially from a polymer material. Examples of documents include identification documents such as passports, identity cards, driver's licenses, or health cards, as well as credit documents such as banknotes and checks, or administrative documents such as registration certificates. Thus, a document can be presented in the form of paper, a booklet, or a card, and the information can also be printed and / or etched.

[0128] According to the present invention, the expression "protecting a product" means that the fluorescent composition is integrated into the product or product to be protected at any time during its design. Therefore, the fluorescent composition can also be used for product security during its manufacturing process, or for retroactive application or integration into a product. For example, within the context of product security for ID cards, the fluorescent composition can be retroactively applied to all or part of an ID card. This point is further elaborated in the specification.

[0129] In any case, the product is protected by using a fluorescent composition comprising a polymer matrix incorporating the above-mentioned compound of formula I, a mixture of two compounds of formula I, or a mixture of a compound of formula I and a compound of formula III, and can be authenticated due to the properties and effects provided by the fluorescent composition.

[0130] In fact, due to the unique combination of absorption wavelength and the specific fluorescence of the fluorescent composition, products protected according to the present invention can be certified. Therefore, only certified products will have the correct absorption and fluorescence emission characteristics at the same time. Certification according to the present invention means verifying the authenticity of the product by detecting the fluorescent composition or security device incorporated therein. In the case of using a composition comprising a compound with formula I and a compound with formula III, this detection of the presence or absence of coloration or fluorescence makes it possible to authenticate the product in question. Therefore, when the detection shows the presence of the fluorescent composition, the product is certified, which is in contrast to a non-certified product where the detection does not show the fluorescent composition. Due to the separate presence of the fluorescent composition comprising a compound with formula I and a compound with formula III, products protected by the fluorescent composition according to the present invention can be certified at the three security levels described below.

[0131] In practice, when using a composition comprising a compound having Formula I and a compound having Formula III, the compound of Formula III contained in the fluorescent composition can have an absorption band in the visible light range, and the color perceived by the naked eye will correspond to the complementary color of the absorbed color. For example, a compound absorbing around 500-520 nm, which corresponds to green / blue, will appear orange / red to the naked eye. This property makes it possible to achieve Class 1 safety.

[0132] With regard to fluorescence properties, the compounds of formula I according to the invention all have an excitation band in the ultraviolet (UV) range. They can therefore be excited, in particular, by UV or LED lamps emitting between 100 nm and 400 nm, making it possible to achieve safety class 2. This property makes it possible to achieve an activation / deactivation (on / off) effect, corresponding to the display of a color change of the fluorescent composition upon stimulation of the fluorescence, in particular by an LED or UV light source.

[0133] Finally, the emission wavelength can be determined using a single grating low-resolution spectrofluorometer or fluorometer (detection by photodiode or photomultiplier tube), which provides level 3 security for the security element according to the invention.

[0134] Thus, due to the combination of absorption and fluorescence properties, products and in particular security documents according to the invention will be detected at levels 2 and 3 when using a composition comprising a compound of formula I or a mixture of two compounds of formula I, and will be detected at level 3 when using a composition comprising a compound of formula I and a compound of formula III.

[0135] The fluorescent composition according to the present invention can be presented in a variety of forms adopted by a person skilled in the art depending on the product to be protected. For example, if the product is a document, the fluorescent composition can be in the form of a layer, a set of layers or a film.

[0136] According to a specific embodiment, the fluorescent composition is used in the form of a layer or layer group prepared using techniques known to those skilled in the art, such as rolling, extrusion, calendaring, or calendered extrusion. These techniques will be selected depending on the polymer matrix used. For example, if the matrix is ​​made of polycarbonate or thermoplastic polyurethane, calendared extrusion is preferred. Similarly, if the matrix is ​​made of polypropylene, the pumping extrusion principle, in particular the biaxial pumping extrusion principle, is preferred. The layer group according to the present invention can be obtained, for example, by rolling two or more layers of a polymer matrix, each layer incorporating one or more fluorescent compositions. This layer or layer group has particularly advantageous applications in document security, and more specifically in identity, credit, or management document security.

[0137] According to this embodiment, the layer or group of layers is in the form of a card. Examples of cards are, in particular, business cards, bank cards, or any other type of card made of a polymer matrix. In this case, the fluorescent composition according to the invention forms the substrate of the document itself. The card can be obtained, for example, by rolling multiple polymer layers, at least one of which comprises the fluorescent composition according to the invention.

[0138] Particularly advantageously, when using a composition comprising a compound of formula I, the layer or layer group is transparent, which allows, in addition to the above-mentioned effects, the following effects to be achieved:

[0139] - Waveguide effect: The presence of grooves in a layer or layer group creates different diffraction indices, which stimulate the fluorescence of the protective layer. Consequently, the color observed at the grooves differs from that observed in the rest of the layer or layer group. This represents a level 2 safety feature under UV illumination.

[0140] - Side effect: This effect corresponds to the complementary color of the observed absorption color, which differs on the side of the layer or layer group from the color observed on the face. Under UV irradiation, this represents level 2 safety.

[0141] Particularly advantageously, when using a composition comprising a mixture of a compound of formula I and a compound of formula III, the layer or layer group is transparent, which allows, in addition to the above-mentioned effects, the following effects to be achieved:

[0142] - Waveguide effect: The presence of grooves in a layer or layer group creates a different diffraction index, which stimulates the fluorescence of the protective layer. As a result, the color observed at the grooves is different from the color observed in the rest of the layer or layer group. This represents Level 1 security.

[0143] - Switching color effect: This effect corresponds to a change in color when a layer or group of layers is superimposed on a contrasting background, such as a dark, in particular black, background, or a light, in particular white background. Thus, the complementary colors of the absorption color on the light background and the fluorescent color on the dark background are observed, which represents safety level 1.

[0144] - Side effect: This effect corresponds to the observation of a complementary color to the absorbed color, which differs on the side of the layer or layer group from the color observed on the face. This represents level 1 safety.

[0145] - Shadow effect: This effect is associated with the presence of the compound of formula III and corresponds to the appearance of the fluorescent color in the layer and the projection of the complementary color of the absorbed color on a light background when the fluorescence is excited by LED or UV light and when viewed against a light, in particular white background. This represents a level 2 safety factor.

[0146] Advantageously, the layer has in particular a thickness of 0.050 mm to 0.800 mm, preferably a thickness of 0.200 mm to 0.600 mm, for example a thickness of about 0.400 mm. When the layer has a thickness of less than 0.100 mm, it is also referred to as a film.

[0147] According to one particular embodiment, the fluorescent composition for protecting products comprises only a polymer matrix in which the compound of formula I as defined above is integrated.

[0148] According to a further embodiment, the fluorescent composition for protecting a product is essentially formed by a polymer matrix in which a compound having formula I as defined above is integrated. According to the invention, the expression "essentially formed" means that the fluorescent composition is formed by more than 96%, 97%, 98% or more than 99% of a polymer matrix in which a compound having formula I is integrated.

[0149] According to a further embodiment, the fluorescent composition for protecting a product is formed of about 50% of a polymer matrix in which a compound having formula I as defined above is integrated.

[0150] According to one particular embodiment, the fluorescent composition for protecting products comprises only a polymer matrix integrating a mixture of two different compounds of formula I as defined above.

[0151] The fluorescent composition thus obtained has a colour resulting from the mixture of the colours of each of the two compounds of formula I and is visible only under UV illumination (grade 2).

[0152] According to a further embodiment, the fluorescent composition for protecting a product comprises only a polymer matrix in which the compound of formula I and the compound of formula III as defined above are integrated.

[0153] In fact, when the compound of formula I and the compound of formula III are mixed together and the compounds emit at different wavelengths, the color of the fluorescence emitted under UV irradiation can be changed. However, advantageously, the performance of the fluorescent composition according to Class 1 and Class 2 remains unchanged and does not change when tested using a mobile phone flashlight.

[0154] The fluorescent composition thus obtained has three colours, a first visible on a white background (grade 1), a second visible, for example, on a black background or under a mobile phone flashlight (grade 1), and a third visible under UV irradiation (grade 2).

[0155] Thus, using a composition comprising a mixture of a compound having formula I and a compound having formula III enables complexity level 2.

[0156] According to a specific embodiment, the fluorescent composition is used in the form of a fluorescent ink. According to this embodiment, the fluorescent ink is suitable for printing, particularly for screen printing, offset printing, flexographic printing, daylight offset printing, inkjet printing, digital printing, copperplate printing, and 3D printing, with offset printing and inkjet printing being preferred. Completely unexpectedly, the inventors have advantageously observed that the fluorescent ink according to the present invention can be used for printing without causing clogging of the printhead.

[0157] According to a particular embodiment, the fluorescent composition is used in the form of an aqueous ink.

[0158] According to another particular embodiment, the fluorescent composition is used in the form of a fluorescent varnish.

[0159] According to a specific 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, in particular 0.050 mm to 0.100 mm, which is used to wrap around two sides of a document, in particular an identity, credit, or administrative document. In an alternative embodiment of this embodiment, this film is applied only to one of the two sides of the document, in particular an identity document. In another alternative embodiment of this embodiment, this film is applied only to a portion of one of the two sides of the document, in particular an identity document. In another alternative embodiment of this embodiment, this film is applied only to a portion of each of the two sides of the document, in particular an identity document.

[0160] According to a further embodiment, the fluorescent composition is formed into the form of fibers. Such forming can be performed using conventional techniques for obtaining fibers, either woven or non-woven.

[0161] According to this embodiment, the fibers are preferably obtained by an extrusion spinning method using a melt spinning technique. The production of fibers by the melt spinning method primarily involves melting a mixture of a polymer and a fluorescent compound in an extruder. The molten material is then passed under pressure through a die consisting of multiple die heads. At the die output, the filaments are air-cooled, stretched, and then wound onto a substrate. A slurry can generally be applied to the lower portion of the spinning shaft.

[0162] 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 a compound of formula III can be integrated into the polymer matrix without extrusion, in particular by yarn impregnation.

[0163] The shape of the fluorescent fibers obtained using the extrusion-spinning method can be determined in particular by the shape of the die. Thus, the fibers can in particular have cylindrical, trilobal, octofoil, hollow, or multi-hollow shapes. Changing the fiber shape can be advantageous because it can alter the visual effect on a macroscopic scale. Indeed, discontinuities in the optical cross-section or refractive index within the fiber can alter the light transmission and, therefore, the effects observed on a macroscopic scale.

[0164] According to another specific embodiment, several fluorescent compositions are used to protect the same product, said fluorescent compositions differing from one another at least in the nature of 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 incorporated in the polymer matrix. This embodiment advantageously allows for better protection of the product in question.

[0165] According to a further embodiment, the polymer matrix is ​​a photocurable resin and the fluorescent composition further comprises a polar solvent to facilitate integration between the resin and the compound of formula I, a mixture of two compounds of formula I, or a mixture of a compound of formula I and a compound of formula III. The fluorescent composition thus obtained finds very specific applications in certain 3D printing technologies, for example for producing holograms, which then have a higher level of security.

[0166] Thirdly, the present invention relates to a method for protecting a product, comprising the following steps:

[0167] - preparing a fluorescent composition as defined above,

[0168] - Protecting by applying said fluorescent composition prepared in the previous step to at least one portion of said product.

[0169] Thus, the first step consists in obtaining a fluorescent composition as defined above.

[0170] According to a particular embodiment, the first step of the protection method consists in preparing a fluorescent composition comprising only a polymer matrix in which the compound of formula I as defined above is integrated.

[0171] According to a further embodiment, the first step of the protection method comprises preparing a fluorescent composition which is essentially formed by a polymer matrix in which the compound of formula I as defined above is integrated. According to the present invention, the expression "essentially formed" means that the fluorescent composition is formed by more than 96%, 97%, 98% or more than 99% of a polymer matrix in which the compound of formula I is integrated.

[0172] According to a particular embodiment, the first step of the protection method consists in preparing a fluorescent composition comprising only a polymer matrix integrating two different compounds of formula I as defined above.

[0173] According to a particular embodiment, the first step of the protection method consists in preparing a fluorescent composition comprising only a polymer matrix incorporating a compound of formula I as defined above and a compound of formula III as defined above.

[0174] According to one specific 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, comprising a polymer matrix into which 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 is incorporated to obtain the fluorescent ink. According to this embodiment, the protection step is advantageously carried out by printing the fluorescent ink on the product to be protected, such as a document.

[0175] According to one particular embodiment, the fluorescent composition is a fluorescent varnish. According to this embodiment, the protection step can be performed, for example, by coating or varnishing the product to be protected with said fluorescent varnish.

[0176] A person skilled in the art will adapt the protection step on all or part of the product to be protected according to the product to be protected and the form of the composition.

[0177] The protection step involves integrating the fluorescent composition into the product to be protected. Therefore, the protection step can be performed even during the product's manufacturing process, allowing for traceability. For example, within the context of document product security, the protection step can be performed on the finished product. Furthermore, this step can be repeated multiple times on the same product to increase its security level.

[0178] The protection step can be carried out according to techniques known to those skilled in the art, for example by rolling, printing, weaving, painting, varnishing, gluing, coating or impregnation.

[0179] According to one embodiment, the fluorescent composition according to the present invention, comprising a compound of formula I and a compound of formula III, is applied by coating onto a reflective or metallized surface. The product is then protected by applying an assembly consisting of a reflective or metallized layer coated with the fluorescent composition. Metallized surfaces are layers known to those skilled in the art and can consist, for example, of a metal layer of aluminum.

[0180] Advantageously, according to this embodiment, the fluorescent properties of the fluorescent composition interact with the reflective appearance of the reflective layer and this makes it possible to obtain a specific visual effect for product safety.At equivalent concentrations, the reflective surface increases the light intensity relative to a non-reflective surface.

[0181] The protection method according to the present invention may also include a step of shaping the fluorescent composition prior to the protection step. This shaping step can be carried out using techniques known to those skilled in the art, which allows, for example, obtaining a layer, a layer assembly, a film, or a fiber. This shaping step thus facilitates the subsequent protection step by application.

[0182] According to one particular embodiment, the first step of the method consists in preparing several fluorescent compositions that differ in the nature of the compound of formula I integrated in a polymer matrix. According to this embodiment, the protection step consists in applying the prepared compositions simultaneously or in a delayed manner and thus increasing the level of safety conferred on the product.

[0183] The method according to the present invention can be used to protect any type of product capable of receiving the fluorescent composition. For example, it can include a plastic item (such as a portion of packaging material), a luxury item (such as a leather product), or a document. Preferably, the product protected according to the method is a document.

[0184] According to a specific embodiment, the product to be protected is a document, such as an identity, credit, or administrative document. According to this embodiment, the fluorescent fixing 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 protecting composition is formed into a film and then hot-rolled or cold-rolled on all sides of the document. In another alternative embodiment, the film is applied to only one side of the document. In another alternative embodiment, the film is applied to only a portion of one of the two sides of the document, and in another alternative embodiment, the film is applied to only a portion of each side of the document.

[0185] According to a further embodiment, the polymer matrix of the fluorescent composition further incorporates a compound having formula II as defined above.

[0186] The present invention further relates to compounds of formula II:

[0187] [Chemical Formula 2]

[0188]

[0189] in,

[0190] R 1 、R 2 and R 3independently 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-SR 4 ; preferably 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 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, chlorine, fluorine and -NO2; more preferably R 1 、R 2 and R 3 are independently selected from hydrogen, methyl, methoxy, chlorine, fluorine and -NO2; even more preferably R 1 、R 2 and R 3 independently selected from hydrogen, methyl, methoxy, chlorine and fluorine;

[0191] R 4 is selected from C1-C6-alkyl, C1-C6-cycloalkyl and aryl;

[0192] R 5 is selected from C1-C6-alkyl, hydroxy-C1-C6-alkyl, C1-C6-alkoxycarbonyl, di-C1-C6-alkylaminosulfinyl, 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; preferably R 5 is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, optionally substituted by C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; more preferably R5 is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, 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-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, optionally substituted by C1-C2-alkyl, C1-C2-alkoxy, trifluoro-C1-C2-alkyl, C1-C4-alkylamino or hydroxy-C1-C2-alkylamino; even more preferably, R 5 is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, optionally substituted with methyl, methoxy, trifluoromethyl, butylamino or hydroxyethylamino; even more preferably, R 5 is selected from cinnamoyl, benzoyl, 2,3,4,5,6-pentahalogenobenzoyl and 2,3,5,6-tetrahalogenobenzoyl, optionally substituted with trifluoromethyl, butylamino or hydroxyethylamino; for example R 5 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;

[0193] and

[0194] The conditions are:

[0195] When R 5 When R is cinnamoyl or benzoyl optionally substituted by methyl, methoxy, chloro or trifluoromethyl, 1 、R 2 and R 3 Not all are three hydrogens;

[0196] When R 5 When it is benzoyl, R 1 Not meth;

[0197] When R 5 When it is benzoyl, R 2 is not methyl; and

[0198] When R 5 When it is benzoyl, R 3 Not methyl, methoxy or chlorine.

[0199] In one embodiment, compounds of Formula II are those of Formula IIa:

[0200] [Chemical Formula 7]

[0201]

[0202] where R 1 and R 5 As defined in Formula II.

[0203] Preferred compounds of formula IIa are those wherein R 1 Those which are methoxy or chloro.

[0204] In one embodiment, the compounds of formula II are those of formula lib.

[0205] [Chemical Formula 8]

[0206]

[0207] where R 2 and R 5 As defined in Formula II.

[0208] Preferred compounds of formula IIa are those wherein R 2 Those selected from methyl, methoxy, fluorine and NO2.

[0209] In one embodiment, compounds of Formula II are those of Formula IIc:

[0210] [Chemical Formula 9]

[0211]

[0212] where R 3 and R 5 As defined in Formula II.

[0213] Preferred compounds of formula III are those wherein R 3 Those are chlorine ones.

[0214] Particularly preferred compounds of the present invention having formula II are listed in Table 2 below:

[0215] [Table 2]

[0216]

[0217]

[0218]

[0219]

[0220] definition

[0221] The following definitions and explanations relate to terms and expressions used in this application, including the description and claims.

[0222] In describing the compounds according to the present invention, the terms and expressions used are to be interpreted in accordance with the definitions below, unless otherwise indicated.

[0223] The term "alkyl", alone or as part of another group, means a group having the formula C n H 2n+1 wherein n is an integer greater than or equal to 1. Preferred alkyl groups are linear or branched C1 to C6 alkyl groups.

[0224] The term "alkenyl" refers to a straight or branched unsaturated alkyl group containing one or more carbon-carbon double bonds. Suitable alkenyl groups contain 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms. Non-limiting examples of alkenyl groups are vinyl, 2-propenyl, 2-butenyl and 3-butenyl, preferably vinyl and 2-propenyl.

[0225] The term "cycloalkyl", alone or as part of another group, refers to a saturated monocyclic, bicyclic or tricyclic hydrocarbon radical having 3 to 12 carbon atoms, particularly 5 to 10 carbon atoms, and more particularly 6 to 10 carbon atoms. Suitable cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, particularly adamant-1-yl and adamant-2-yl, and 1-naphthyl. Preferred cycloalkyl radicals include cyclopropyl, cyclohexyl and cycloheptyl. A particularly preferred cycloalkyl radical is cyclohexyl.

[0226] The term "aryl", alone or as part of another group, refers to a polyunsaturated aromatic hydrocarbon radical having a single ring (phenyl) or several aromatic rings fused together (e.g., naphthyl), typically containing 5 to 12 atoms, preferably 6 to 10 atoms, wherein at least one ring is aromatic. Preferred aryl groups include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl. A particularly preferred aryl group is phenyl.

[0227] The term "heteroaryl", alone or as part of another group, means, but is not limited to, an aromatic ring or a ring system comprising one to two fused rings, typically containing 5 to 12 atoms, wherein at least one ring is aromatic, and wherein one or more carbon atoms in one or more of these rings are replaced by 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 pyridyl, pyrrolyl, furyl, thienyl. Particularly preferred heteroaryl groups are thienyl and pyridyl.

[0228] The term "halogen", alone or as part of another group, means fluorine, chlorine, bromine or iodine. Preferred halogens are chlorine and fluorine, with fluorine being particularly preferred.

[0229] The term "haloalkyl", alone or as part of another group, means an alkyl group as defined above in which one or more hydrogen atoms are replaced by a halogen group as defined above. The haloalkyl group according to the present invention may be linear or branched and includes, but is not limited to, a group having the formula C n F 2n+1 wherein n is an integer greater than or equal to 1, preferably an integer between 1 and 10. 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.

[0230] The present invention will be better understood with reference to the following examples. These examples represent certain embodiments of the present invention and in no way limit the scope of the invention. The accompanying drawings are used to illustrate the experimental results.

[0231] Example

[0232] Chemical synthesis

[0233] All temperatures are in °C and all reactions were performed at ambient temperature (AT) unless otherwise stated.

[0234] By coating with silica gel and UV254 fluorescent indicator (0.2mm thick The reaction was monitored by thin layer chromatography (TLC) on ready-to-use aluminum plates (Biotin® 60F254 Merck) or equivalent.

[0235] NMR analysis was performed on a Bruker 300 MHz, 400 MHz or 600 MHz spectrometer. Spectra were recorded in deuterated chloroform (CDCl 3 ) solutions. Chemical shifts are given in ppm, monitoring multiple proton spectra where s, sl, d, t, q, dd, td and m represent singlet, broad singlet, doublet, triplet, quaternary, doublet of doublets, triplet of doublets and multiplets (or low-resolution mass) respectively. Where applicable, the multiplicity is followed by the coupling constant value, annotated as J and expressed in Hertz (Hz).

[0236] HRMS analysis was performed in positive electrospray ionization mode (ESI+).

[0237] 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 stated, solvents were purified by distillation before use. Unless otherwise stated, reagents and starting materials were used without additional purification.

[0238] The following abbreviations are used:

[0239] HRMS: High Resolution Mass Spectrometry,

[0240] NMR: Nuclear Magnetic Resonance,

[0241] AT: ambient temperature,

[0242] THF: tetrahydrofuran.

[0243] Compound 3: N-(2-(Benzo[d]thiazol-2-yl)phenyl)-3,5-bis(trifluoromethyl)benzamide

[0244] [Figure 1]

[0245]

[0246] In a 50 mL round-bottom 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 introduced into 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 at 60°C for approximately 45 minutes, the reaction mixture was cooled to ambient temperature. 10 mL of water was added, the mixture was filtered, and the filter residue was washed with 2 × 25 mL of water, 25 mL of ethanol, and dried to obtain compound 3 (0.87 g).

[0247] 1 H NMR(CDCl3): δ13.50(1H,s),9.02(1H,dd,J=5.6,0.8Hz),8.66(2H,s),8.15(1H,s),8.07(1H,d,J=5.6Hz),7.97(1H ,dd,J=5.2,1.2Hz),7.96(1H,d,J=5.6Hz),7.6-7.55(2H,m),7.48(1H,td,J=5,0.8Hz),7.29(1H,td,J=5.2,1.2Hz)

[0248] HRMS (ESI+) m / z 467.12 (calcd. 467.41 for C 22 H12 F6N2OS+H + [M+H] + ).

[0249] Compound 4: N-(2-(Benzo[d]thiazol-2-yl)phenyl)-2,3,4,5,6-pentafluorobenzamide

[0250] [Figure 2]

[0251]

[0252] The same procedure as described above for preparing compound 3 was used, using 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 obtain compound 4 (1.51 g).

[0253] 1 H NMR(CDCl3): δ13.46(1H,s),8.94(1H,dd,J=5.6,0.4Hz),7.95-7.93(2H,m),7.74(1H,d,J=5.6Hz),7.58(1 H,td,J=5.2,0.4Hz),7.53(1H,td,J=5.2,0.8Hz),7.46(1H,td,J=5.2,0.4Hz),7.30(1H,td,J=5.2,0.8Hz).

[0254] HRMS (ESI+) m / z 421.14 (calcd. 421.36 for C 20 H9F5N2OS+H + [M+H] + ).

[0255] Compound 5: N-(2-(Benzo[d]thiazol-2-yl)phenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0256] [Figure 3]

[0257]

[0258] In a 100 mL round-bottom flask equipped with a stirrer and a temperature indicator, 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) were introduced. The resulting mixture was stirred at ambient 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 ambient temperature, filtered and the filter residue was washed with 2×30 mL of water. Then, in a 50 mL round-bottom flask equipped with a stirrer and a temperature indicator, the crude product and petroleum ether (25 mL) were introduced. The resulting mixture was heated to 50°C. After 45 minutes, the reaction mixture was cooled to ambient temperature, the mixture was filtered, and the filter residue was washed with 2×15 mL of petroleum ether to obtain compound 5 (8.7 g).

[0259] 1 H NMR(CDCl3): δ13.22(1H,s),9.99(1H,d,J=5.6Hz),7.93(1H,d,J=5.2Hz),7.91(1H,dd,J= 5.2,0.8Hz),7.84(1H,d,J=5.6Hz),7.54(1H,td,J=5.2,0.8Hz),7.51(1H,td,J=5.2,0.4Hz ), 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 (calculated 474.49 for C 24 H 19 F4N3OS+H + [M+H] + ).

[0260] Compound 8: N-(2-(Benzo[d]thiazol-2-yl)-4-methylphenyl)-4-(trifluoromethyl)benzamide

[0261] [Figure 4]

[0262]

[0263] The same procedure as described above for preparing compound 3 was used, using 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 obtain compound 8 (0.53 g).

[0264] 1 H NMR (CDCl3): δ13.47 (1H, s), 8.87 (1H, d, J = 3.2Hz), 8.37 (2H, d, J = 5.6Hz), 7.96 (2H, t, J = 5.2Hz), 7.88 (2H, d, J = 5.6Hz), 7.82(1H,d,J=5.2Hz), 7.59(1H,t,J=5.2Hz), 7.47(1H,t,J=5.2Hz), 7.06(1H,d,J=5.6Hz), 2.50(3H,s).

[0265] HRMS (ESI+) m / z 413.22 (calcd. 413.44 for C 22 H 15 F3N2OS+H + [M+H] + ).

[0266] Compound 9: N-(2-(Benzo[d]thiazol-2-yl)-4-methylphenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0267] [Table 5]

[0268]

[0269] Step 1: Using the same procedure as above for preparing compound 3, using 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, the intermediate compound (1.51 g) was obtained.

[0270] Step 2: Using the same procedure as described above for preparing compound 5, using 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, compound 9 (1.33 g) was obtained.

[0271] 1H NMR(CDCl3): δ13.10(1H,s),8.87(1H,d,J=5.6Hz),7.93(1H,d,J=5.2Hz),7.8 3(1H,d,J=5.6Hz),7.69(1H,s),7.51(1H,td,J=5.2,0.8Hz),7.43(1H,td,J=5. 0,0.8Hz),7.35(1H,dd,J=5.6,0.8Hz),4.13(1H,bs),3.54(2H,q,J=4.4Hz),2. 44(3H,s),1.67(2H,q,J=4.8Hz), 1.47(2H,h,J=5.2Hz), 1.01(3H,t,J=4.8Hz).

[0272] HRMS (ESI+) m / z 488.42 (calcd. 488.52 for C 25 H 21 F4N3OS+H + [M+H] + ).

[0273] Compound 10: N-(2-(Benzo[d]thiazol-2-yl)-4-methylphenyl)cinnamamide

[0274] [Figure 6]

[0275]

[0276] The same procedure as 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, and 0.4 mL of cinnamoyl chloride to give compound 10 (0.55 g).

[0277] 1 H NMR (CDCl3): δ12.71(1H,s),8.86(1H,d,J=5.6Hz), 8.06(1H,d,J=5.6Hz), 7.95(1H,d,J=5.2Hz), 7.81(1H,d,J=10.4Hz), 7.68(1H,d,J=0. 8Hz),7.67-7.64(2H,m),7.57(1H,td,J=5.2,0.8Hz),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).

[0278] HRMS (ESI+) m / z 371.15 (calcd. 371.47 for C 23 H 18N2OS+H + [M+H] + ).

[0279] Compound 11: N-(2-(Benzo[d]thiazol-2-yl)-4-methoxyphenyl)benzamide

[0280] [Figure 7]

[0281]

[0282] The same procedure as described above for preparing 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).

[0283] 1 H 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 (calculated 361.44 for C 21 H 16 N2O2S+H + [M+H] + ).

[0284] Compound 12: N-(2-(Benzo[d]thiazol-2-yl)-4-methoxyphenyl)-4-(trifluoromethyl)benzamide

[0285] [Table 8]

[0286]

[0287] The same procedure as described above for preparing compound 3 was used, using 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 obtain compound 12 (0.59 g).

[0288] 1H NMR(CDCl3): δ13.25(1H,s),8.98(1H,d,J=6,2Hz),8.43(2H,d,J=5.6Hz),8.34(2H,d,J=5.6Hz),8.14(1H,d,J=5.6Hz),8.02 (1H,J=3.8Hz)7.98(1H,d,J=5.8Hz),7.61(1H,t,J=4.8Hz),7.45(1H,d,J=1.6Hz),7.15(1H,dd,J=6.0,2.0Hz),3.94(3H,s).

[0289] HRMS (ESI+) m / z 429.10 calcd (429.43 for C 22 H 15 F3N2O2S+H + [M+H] + ).

[0290] Compound 13: N-(2-(Benzo[d]thiazol-2-yl)-4-methoxyphenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0291] [Figure 9]

[0292]

[0293] Step 1: Using the same procedure as above for preparing compound 3, using 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, the intermediate compound (1.63 g) was obtained.

[0294] Step 2: Using the same procedure as described above for the preparation of compound 5, using 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, compound 13 (1.43 g) was obtained.

[0295] 1H NMR(CDCl3): δ13.30(1H,s),8.92(1H,d,J=5.8Hz), 8.14(1H,d,J=5.4Hz), 7.85(1H,d,J=5.4Hz),7.78(1H,s),7.56(1H,t,J=4.8Hz),7.52(1H,t,J=4 .8Hz),7.19(1H,d,J=5.8Hz),4.12(1H,bs),3.92(3H,s),3.54(2H,q,J=4. 8Hz), 1.66 (2H, q, J = 4.8Hz), 1.45 (2H, h, J = 5.2Hz), 1.02 (3H, t, J = 4.8Hz).

[0296] HRMS (ESI+) m / z 504.17 (calcd. 504.52 for C 25 H 21 F4N3O2S+H + [M+H] + ).

[0297] Compound 14: N-(2-(Benzo[d]thiazol-2-yl)-4-methoxyphenyl)cinnamamide

[0298] [Figure 10]

[0299]

[0300] The same procedure as described above for preparing 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 obtain compound 14 (0.51 g).

[0301] 1 H NMR(CDCl3): δ12.51(1H,s),8.90(1H,d,J=6Hz),8.08(1H,d,J=5.6Hz),7.95(1H,d ,J=5.2Hz),7.95(1H,d,J=5.2Hz),7.80(1H,d,J=10.8Hz),7.64(2H,d,J=4.8Hz),7. 58(1H,t,J=5.2Hz),7.49-7.46(3H,m),7.43(1H,d,J=4.8Hz),7.39(1H,d,J=1.6Hz ),7.10(1H,dd,J=6.0,1.6Hz),6.72(1H,d,J=10.4Hz),3.91(3H,s).HRMS(ESI+)m / z 387.17 (calculated value 387.47, for C 23 H 15N2O2S+H + [M+H] + ).

[0302] Compound 16: N-(2-(Benzo[d]thiazol-2-yl)-4-fluorophenyl)-4-(trifluoromethyl)benzamide

[0303] [Figure 11]

[0304]

[0305] The same procedure as described above for preparing compound 4 was used with 0.74 g of 2-(1,3-benzothiazol-2-yl)-4-fluoroaniline, 1.1 mL of pyridine, 3 mL of THF, and 0.43 mL of trifluoromethylbenzoyl chloride to obtain compound 16 (0.78 g).

[0306] 1 H 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 (calculated 417.40 for C 21 H 12 F4N2OS+H + [M+H] + ).

[0307] Compound 27: N-(2-(Benzo[d]thiazol-2-yl)-5-chlorophenyl)benzamide

[0308] [Figure 12]

[0309]

[0310] The same procedure as described above for the preparation of compound 3 was used, using 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 chloride to obtain compound 27 (1.36 g).

[0311] 1H NMR (CDCl3): δ13.48 (1H, s), 9.17 (1H, d, J = 1.2Hz), 8.24 (2H, dd, J = 5.6Hz), 8.0 (1H, d, J = 5.2Hz), 7.95 (1H, d, J = 4.8Hz), 7. 82(1H,d,J=5.6Hz)7.66-7.61(3H,m),7.57(1H,td,J=5.0,0.8Hz),7.48(1H,td,J=5,0.8Hz),7.18(1H,dd,J=5.6,1.2Hz).

[0312] HRMS (ESI+) m / z 365.65 (calcd. 365.86 for C 20 H 13 ClN2OS+H + [M+H] + ).

[0313] Compound 29: N-(2-(Benzo[d]thiazol-2-yl)-5-chlorophenyl)-4-(butylamino)-2,3,5,6-tetrafluorobenzamide

[0314] [Figure 13]

[0315]

[0316] Step 1: Using the same procedure as above for preparing compound 3, using 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, the intermediate compound (1.45 g) was obtained.

[0317] Step 2: Using the same procedure as described above for the preparation of compound 5, using 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, compound 29 (0.93 g) was obtained.

[0318] 1H NMR (CDCl3): δ13.31(1H,s),9.09(1H,d,J=1.2Hz),7.93(1H,d,J=5.6Hz),7.84(1H,d,J=5.2Hz),7.80(1H,d,J=5.2Hz),7.52(1H,td,J=5.2,0.8Hz) ,7.45(1H,td,J=5.0,0.8Hz),7.2(1H,dd,J=5.6,1.2Hz),3.55(2H,q,J=4. 8Hz), 1.68 (2H, q, J = 5.2Hz), 1.48 (2H, h, J = 5.2Hz), 1.02 (3H, t, J = 4.8Hz).

[0319] HRMS (ESI+) m / z 508.63 (calcd. 508.94 for C 24 H 18 ClF4N3OS+H + [M+H] + ).

[0320] Compound 35: N-(2-(Benzo[d]thiazol-2-yl)-5-chlorophenyl)-2,3,5,6-tetrafluoro-4-((2-hydroxyethyl)amino)benzamide

[0321] [Figure 14]

[0322]

[0323] Step 1: Using the same procedure as above for preparing compound 3, using 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, the intermediate compound (1.45 g) was obtained.

[0324] Step 2: Using the same method as described above for preparing compound 4, 1.0 g of 2-(1,3-benzo[d]thiazol-2-yl)-5-chloroaniline, 0.66 g of potassium carbonate, 5 mL of DMF and 0.43 mL of aminoethanol were used to obtain compound 35 (0.75 g).

[0325] 1H NMR (CDCl3): δ13.34(1H,s),9.08(1H,d,J=1.2Hz),7.92(1H,d,J=5.2Hz),7.83(1H,d,J=5.6Hz),7.80(1H,d,J=6.0Hz),7.52(1 H,td,J=5.2,0.8Hz),7.44(1H,td,J=5.2,0.8Hz),7.2(1H,dd,J=5.6,1.2Hz),4.7(1H,bs),3.94(2H,t,J=3.2Hz),3.73(2H,m).

[0326] HRMS (ESI+) m / z 496.57 (calcd. 496.88 for C 22 H 14 ClF4N3OS+H + [M+H] + ).

[0327] application

[0328] Example 1: Preparation of a layered fluorescent composition and its use for protection

[0329] For this example, the compound of Formula I used was Compound 13 having the following formula:

[0330] [Chemical Formula 10]

[0331]

[0332] Compound 13 is a yellow powder, has absorption at 365 nm, and has fluorescence emission at 605 nm. 17 grams of the compound was mixed with 10 kg of polycarbonate (PC Makralon 2456) using an extruder to obtain a fluorescent composition.

[0333] Extrusion was carried out on a twin-screw extruder (Brabender) with a screw speed of 50 rpm, a hopper flow rate of 3.8 kg / h and the following temperature profile: 275°C-280°C-280°C-285°C-285°C-285°C-290°C (feed => pipeline).

[0334] A certain amount was taken from the extruded fluorescent composition and then added with polycarbonate (PC Makralon 2456) through a Fairex extruder (diameter 45) equipped with a Scamex flat die with a width of 350 mm, and then diluted 10 times by a 3-cylinder roller with an inclination of 30°.

[0335] At the calender output, the fluorescent composition was in the form of a layer 100 mm thick. After setting up the calender, the test was repeated so as to obtain a second layer of the fluorescent composition having a thickness of 400 mm.

[0336] The protective layer thus obtained is then used as a document substrate, the document being thus protected.

[0337] Visual and spectrophotometric analysis of the resulting layers showed that incorporation of the fluorescent dye into polycarbonate did not alter its properties in terms of absorption and fluorescence emission. The resulting fluorescent layer displayed properties similar to those observed when the compound was in solution.

[0338] Example 2: Preparation of a fluorescent composition in the form of a varnish and its use for protection

[0339] For this example, the compound of formula I used was compound 14 having the following formula:

[0340] [Compound 11]

[0341]

[0342] 44 mg of compound 14 were incorporated into 10 g of a solvent-based acrylic varnish (0.4% w / w).

[0343] The fluorescent varnish thus obtained was then applied on a 100 μm thick polyethylene terephthalate film using an automatic film applicator (TQC ASTM D823) and a 20 μm Meyer rod at an application rate of 50 mm / s.

[0344] The varnish deposit was measured to have a thickness of 5 μm, consistent with a solvent-based varnish having a dry extract of 33%.

[0345] The fluorescent layer is formed by a component consisting of a polyethylene terephthalate film coated with fluorescent varnish. The fluorescent layer thus obtained is a protective layer. When irradiated with an ultraviolet lamp (365nm), purple fluorescence is visible to the naked eye.

[0346] Visual and spectrophotometric analysis of the protective layer showed that the incorporation of fluorescent dyes into polycarbonate did not alter its properties in terms of absorption and fluorescence emission.

[0347] The protective layer thus obtained is used as a card substrate by virtue of its fluorescent properties.

[0348] Example 3: Preparation of a fluorescent composition in the form of an ink comprising a compound of formula I and a compound of formula III according to the present invention.

[0349] For this example, the compound of Formula I used was Compound 27 having the following formula:

[0350] [Chemical Formula 12]

[0351]

[0352] Compound 27 is in the form of a white powder, has absorption at 365 nm, and has fluorescence emission at 522 nm.

[0353] The compound of formula III used was compound 36 having the following formula:

[0354] [Chemical Formula 13]

[0355]

[0356] Compound 36 is in the form of orange powder, has absorption at 547 nm, and has fluorescence emission at 568 nm.

[0357] Preparation of fluorescent composition in ink form:

[0358] 400 mg of compound 27 was uniformly dissolved in 100 g Gloss GO type clear unexposed screen printing ink, distributed by Marabu, is suitable for printing on polycarbonate plastic surfaces.

[0359] 100 mg of compound 36 was uniformly dissolved in 100 g of the same transparent unexposed screen printing ink.

[0360] Then, the ink including Compound 27 and the ink including Compound 36 were mixed according to a weight ratio of 1:1.

[0361] The fluorescent composition thus formed was printed on a clear polycarbonate card.

[0362] result: The fluorescent composition prints perfectly.

[0363] The pattern thus printed has a transparently visible pink color when the card is placed on a white background, and has a transparently visible orange color when the card is placed on a black background.

[0364] When the card is exposed to UV light, it will emit yellow fluorescence.

[0365] Example 4: Preparation of a fluorescent composition in the form of an ink comprising a compound of formula I according to the present invention

[0366] For this example, the Family 1 compound used was Compound 3 having the following formula:

[0367] [Chemical Formula 14]

[0368]

[0369] Compound 3 is in the form of a white powder, absorbs at 365 nm, and has fluorescence emission at 513 nm.

[0370] Preparation of fluorescent composition in ink form:

[0371] 400 mg of compound 3 was uniformly dissolved in 100 g Gloss GO type transparent unexposed screen printing ink, which is distributed by Marabu and is suitable for printing on polycarbonate plastic surfaces, has a mass concentration of 0.4% (w / w).

[0372] The fluorescent composition thus formed was printed on a clear polycarbonate card using a 90 mesh size screen printing frame.

[0373] result: Fluorescent components are printed perfectly.

[0374] The printed pattern is invisible under ambient light and emits strong yellow fluorescence under ultraviolet light (365nm).

[0375] The optical properties of the dye switch between the pure dye and the screen-printed layer.

[0376] Example 5: Preparation Fluorescent composition in the form of an ink comprising a compound of formula I according to the present invention

[0377] For this example, the compound of Formula I used was Compound 13 having the following formula:

[0378] [Chemical Formula 10]

[0379]

[0380] Compound 13 is in the form of a white powder, absorbs at 365 nm, and has fluorescence emission at 605 nm.

[0381] Preparation of fluorescent composition in ink form:

[0382] 400 mg of compound 3 was uniformly dissolved in 100 g Gloss GO type transparent unexposed screen printing ink, which is distributed by Marabu and is suitable for printing on polycarbonate plastic surfaces, has a mass concentration of 0.4% (w / w).

[0383] The fluorescent composition thus formed was printed on a clear polycarbonate card using a 90 mesh size screen printing frame.

[0384] result: Fluorescent compositions print perfectly.

[0385] The printed pattern is invisible under ambient light and fluoresces red under ultraviolet light (365 nm).

[0386] The optical properties of the dye are switched between the pure dye and the screen-printed layer.

[0387] Example 6: Preparation Fluorescent composition in the form of ink comprising two compounds of formula I according to the present invention

[0388] For this example, the Family I compounds used were compounds 3 and 13, whose chemical formulas are shown below:

[0389] [Chemical Formula 14]

[0390]

[0391] Compound 3

[0392] [Chemical Formula 10]

[0393]

[0394] Compound 13

[0395] Preparation of fluorescent composition in ink form:

[0396] 400 mg of compound 3 was uniformly dissolved in 100 g Gloss GO type clear unexposed screen printing ink, distributed by Marabu, is suitable for printing on polycarbonate plastic surfaces.

[0397] 400 mg of compound 13 was uniformly dissolved in 100 g of the same transparent unexposed screen printing ink.

[0398] The two inks were mixed in a mass ratio of 3:1 (Compound 13:Compound 3 by weight) and homogenized until a uniform color was obtained.

[0399] result: Fluorescent compositions print perfectly.

[0400] The printed pattern is invisible under ambient light and emits strong orange fluorescence under ultraviolet light (365nm).

[0401] The color thus obtained is a mixture of the individual fluorescent colors of the two dyes.

Claims

1. A fluorescent composition comprising a polymer matrix incorporating a compound of formula (I): in, X is S; Z is NHR 5 ; R is 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-SR 4 ; R 1 、R 2 and R 3 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-SR 4 ; R 4 is selected from C1-C6-alkyl, C3-C6-cycloalkyl and aryl; R 5 is selected from C1-C6-alkyl, hydroxy-C1-C6-alkyl, halogen, aryl, acyl, C1-C6-alkoxycarbonyl, C1-C6-alkylaminocarbonyl, C1-C6-alkylaminosulfinyl, di-C1-C6-alkylaminosulfinyl, arylaminocarbonyl, arylaminosulfinyl, arylsulfonyl, C1-C6-alkylsulfonyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, said benzoyl and 2,3,5,6-tetrahalobenzoyl being optionally substituted with C1-C6-alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; The condition is that when R 2 Yes-NHCOR 4 When Z is not OH; and The symbol It means that R can be substituted multiple times at any free position of the benzene nucleus; Characterized in that the polymer matrix is ​​selected from polycarbonate, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polymethacrylate, polyvinyl chloride, polyamide, polyaramid, polyurethane, thermoplastic polyurethane (TPU), cyanoacrylate, rosin resin, pine resin, photopolymer resin, acrylic resin or a mixture thereof.

2. The fluorescent composition according to claim 1, characterized in that The polymer matrix is ​​selected from polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, thermoplastic polyurethane (TPU), acrylic resin, photopolymer resin or a mixture thereof.

3. The fluorescent composition according to claim 1 or 2, characterized in that The polymer matrix is ​​polycarbonate or polypropylene.

4. The fluorescent composition according to claim 1 or 2, characterized in that In the compound of formula (I), R is hydrogen.

5. The fluorescent composition according to claim 1 or 2, characterized in that The compound of formula (I) is selected 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.

6. The fluorescent composition according to claim 1 or 2, characterized in that The fluorescent composition further comprises a second compound having formula (I).

7. The fluorescent composition according to claim 1 or 2, characterized in that: The fluorescent composition further comprises a second compound having formula (III): in, R 1 is C1-C6 alkyl, C5-C6 cycloalkyl, C5-C6 heteroalkyl, phenyl, the phenyl group is optionally substituted by one or more selected from C1-C2 alkyl, hydroxyl, R5COO - and halogen-substituted groups; R 2 and R 2' independently selected from hydrogen and C1 to C2 alkyl; R 3 and R 3' independently selected from hydrogen, aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, alkynyl, said aryl, heteroaryl, cycloalkyl, alkyl, alkenyl and alkynyl being optionally substituted with one or more groups selected from C1 to C4 alkyl, further aryl, hydroxyl and ferrocene, said further aryl being optionally substituted with one or more groups selected from further aryl, C1 to C2 alkyl, halogen, hydroxyl, dimethylamino, nitro, said further aryl being optionally substituted with C1 to C2 alkyl; R 4 and R 4' independently selected from aryl, heteroaryl, cycloalkyl, alkyl, alkenyl, said aryl, heteroaryl, cycloalkyl, alkyl and alkenyl being optionally substituted with one or more groups selected from C1 to C3 alkyl, further aryl, hydroxyl and ferrocene, said further aryl being optionally substituted with one or more groups selected from further aryl, C1 to C2 alkyl, halogen, hydroxyl, dimethylamino, nitro, said further aryl being optionally substituted with C1 to C2 alkyl; R 5 is C1 to C4 alkyl or C2 to C4 alkenyl; R 6 and R 6' independently selected from halogen, C1 to C4 alkoxy, C2 to C4 alkenyloxy, C1 to C4 alkyl, C2 to C4 alkenyl, CN or aryl, the aryl being optionally substituted with one or more selected from C1 to C2 alkyl, hydroxy, R 5 COO- and halogen group substitution.

8. Use of the fluorescent composition according to any one of claims 1 to 7 for protecting products.

9. Use of the fluorescent composition according to claim 8 for protecting products, characterized in that: The product to be protected is a file.

10. Use of the fluorescent composition according to claim 8 or 9 for protecting products, characterized in that: The fluorescent composition is a fluorescent ink suitable for printing.

11. Use of the fluorescent composition according to claim 10 for protecting products, characterized in that: The printing is selected from the group consisting of screen printing, offset printing, flexographic printing, daylight offset printing, digital printing and copperplate printing.

12. Use of the fluorescent composition according to claim 11 for protecting products, wherein: The digital printing is inkjet printing or 3D printing.

13. A method for protecting a product comprising the steps of preparing a fluorescent composition as defined in any one of claims 1 to 7 and a protecting step by applying said fluorescent composition to at least a portion of the product to be protected.

14. The method for protecting products according to claim 13, characterized in that: The protecting step is performed by rolling, printing, weaving, bonding, coating or impregnation.

15. The method for protecting products according to claim 13 or 14, characterized in that: It comprises a step of shaping said fluorescent composition prior to said protecting step.

16. The method for protecting products according to claim 13, characterized in that: The fluorescent composition is a fluorescent ink and the protecting step is performed by printing.

17. The method for protecting products according to claim 13 or 14, characterized in that: The product in question is an identity, credit or administrative document.

18. Compounds of formula (II): in, R 1 、R 2 and R 3 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(O)OH、-C(O)OR 4 、-CF3、C1-C6-alkoxy、aryloxy、-SH、-SO3H、-SR 4 ; R 4 is selected from C1-C6-alkyl, C1-C6-cycloalkyl and aryl; R 5 is selected from C1-C6-alkyl, hydroxy-C1-C6-alkyl, C1-C6-alkoxycarbonyl, di-C1-C6-alkylaminosulfinyl, cinnamoyl, benzoyl, 2,3,4,5,6-pentahalobenzoyl and 2,3,5,6-tetrahalobenzoyl, wherein the benzoyl and 2,3,5,6-tetrahalobenzoyl are optionally substituted with alkyl, C1-C6-alkoxy, trifluoro-C1-C6-alkyl, C1-C6-alkylamino or hydroxy-C1-C6-alkylamino; and The conditions are: When R 5 When R is cinnamoyl or benzoyl optionally substituted by methyl, methoxy, chloro or trifluoromethyl, 1 、R 2 and R 3 Not all are three hydrogens; When R 5 When it is benzoyl, R 1 Not meth; When R 5 When it is benzoyl, R 2 is not methyl; and When R 5 When it is benzoyl, R 3 Not methyl, methoxy or chlorine.

19. The compound according to claim 18, which is 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.

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