JP4986451B2 - Marking agent - Google Patents

Description

  The present invention relates to a marking agent containing a fluorescent dye, which is invisible under visible light.

  A marking agent containing a fluorescent dye as a marking substance is invisible under normal visible light, but can be visually recognized by emitting the fluorescent dye by irradiating excitation light such as ultraviolet rays. Utilizing this property, it is used for identification of articles and human bodies, detection of substances, etc. for the purpose of crime prevention and crime investigation.

  For example, the recent improvement in copying performance of color copiers and printers has facilitated counterfeiting by copying securities such as stock certificates and gift certificates, ID cards, and banknotes. As one of techniques for preventing forgery by copying, a method using a marking agent containing a fluorescent dye is known. For example, an invisible pattern is formed by using a marking agent, and a method of performing authenticity determination by making it visible with a black light or the like (for example, Patent Document 1), or using a fluorescent ink as an identification code such as a machine-readable barcode The fluorescent ink portion is formed on the anti-counterfeit printed material (Patent Document 2), and visible light is emitted from the fluorescent ink portion by the lamp of the copying machine, so that a copy with a hue different from the printed information can be obtained. A method for doing so (for example, Patent Document 3) has been proposed.

  Another problem is that it is not easy to identify a criminal in a short time after a crime occurs. For example, molester crimes in public places such as trains and buses, which have been increasing in recent years, are examples. Even if they are arrested as suspects, most of them are dependent on the suspects, and it is extremely difficult to identify them. Moreover, even if it is arrested as a suspect, even if it is an atonement, it is impossible to prove it on the spot, which is a social problem such as an atonement trial. In addition, robberies and theft cases must be cleared in the initial investigation. It is also necessary to mark the suspect's possessions (cars, bicycles, motorcycles, etc.) during a job search. In addition, by marking the item (car, motorcycle, bicycle, etc.) with a number or the like, the owner after the theft can be easily confirmed.

  In these investigation processes, as one of techniques for identifying a criminal, a method using a marking agent containing a fluorescent dye has been proposed. That is, a marking agent is sprayed on and attached to a criminal, clothing, or vehicle, and the criminal or vehicle is specified by the marking substance (for example, Patent Document 4). When a fluorescent dye is used as a marking substance, it does not show fluorescence under sunlight and can be confirmed only by using an excitation light source such as black light. Therefore, it has adhered compared to the case of using a colorant, adhesive or fragrance. However, it is difficult for the criminal to notice. Therefore, there is an advantage that the criminal who notices the adhesion of the marking substance is less likely to remove the marking substance by changing clothes or washing clothes or the body.

Marking agents are also used to detect latent fingerprints. Latent fingerprints were impressed in the form of fingerprint ridges when substances secreted from the fingertips attached to the criminal remains. For detection of latent fingerprints, conventionally, a powder such as alumina powder is used as a marking substance, and the powder is attached to moisture and fat in secretions and detected using a color difference between the object and the powder. , Using a coloring reagent for the marking substance and reacting with the amino acid and salt in the secretion to produce a color, or using iodine or cyanoacrylate monomer for the marking substance in the sealed container For example, a gas method is used in which the fat content of the water reacts with the vapor thereof to cause coloration. On the other hand, a method using a fluorescent dye as a coloring reagent in the liquid method has been proposed (for example, Patent Document 5).
JP 2003-1935 A JP 7-57065 A JP 2002-326443 A JP 2000-298777 A Japanese Patent Laid-Open No. 2-16166

  However, conventional marking agents are insufficient in heat resistance and light resistance, and when exposed to sunlight for a long time or placed in a high temperature environment, the emission intensity is greatly reduced, making it difficult to identify. There is a problem that when the emission intensity of the fluorescent dye is insufficient and the background color of the marking object is a dark color such as black, blue, or green, it is difficult to identify the emission. Further, when used for counterfeiting, there is a problem that special ink used as a marking agent is expensive. Further, when used for identifying the criminal or the vehicle, there is a problem that the fluorescent dye is easily removed by rubbing or washing because the adhesion of the fluorescent pigment to the criminal or the vehicle is weak. Further, when used for fingerprint detection, there is a problem that the detection sensitivity fluctuates because the adhesion force to the fingerprint ridge is weak, and the fluorescent dye adheres to portions other than the fingerprint ridge so that the fingerprint ridge becomes unclear.

  Therefore, the present invention solves the above-described problems, has excellent heat resistance and light resistance, has high emission intensity, and has improved adhesion to marking objects such as articles, human bodies, and detected substances at low cost. It was aimed to provide a marking agent.

As a result of diligent efforts to solve the above-mentioned problems, the present inventors have found that a marking agent containing an organic EL dye as a fluorescent dye has superior characteristics as compared with conventional marking agents, and have completed the present invention. It is. That is, the marking agent of the present invention is a marking agent containing one or more fluorescent dyes and a solvent, and the fluorescent dye is composed of an organic EL dye, and the organic EL dye contains a 5-membered ring compound having a conjugated system. A compound, wherein the five-membered ring compound contains one or more hetero atoms, selenium atoms, or boron atoms.

  As the organic EL dye used in the marking agent of the present invention, a condensed polycyclic compound composed of the 5-membered ring compound and a 6-membered ring compound having a conjugated system can be used.

  Moreover, an azole derivative or an imidazole derivative can also be used for the condensed polycyclic compound.

ここで、式中、R₁、R₂、R₃、R₄は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基、あるいはスルホニル基などの置換基を有してもよい芳香族炭化水素基又は炭化水素基又は複素環基又はヘテロ原子を環内に含む芳香族基を示し、Xは置換基を有していてもよい窒素原子又は硫黄原子又は酸素原子又はセレン原子を示し、R'は芳香環を含んでも良いアルキル基又はアルケニル基等の脂肪族炭化水素基あるいは芳香族炭化水素基、An^-は、Cl^-、Br^-、I^-等のハロゲン化物イオン、CF₃SO₃ ^-、BF₄ ^-、PF₆ ^-を示す。 Moreover, the compound shown by either 1 type of the following general formula (1), (2) or (3) can be used for the said azole derivative.

Here, in the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each independently an aromatic group that may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group. A hydrocarbon group, a hydrocarbon group, a heterocyclic group or an aromatic group containing a hetero atom in the ring, X represents a nitrogen atom, a sulfur atom, an oxygen atom or a selenium atom which may have a substituent; R ′ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group such as an alkyl group or an alkenyl group which may contain an aromatic ring, An ⁻ is a halide ion such as Cl ⁻ , Br ⁻ or I ⁻ , CF ₃ SO _{3 ^{-, BF 4 -, PF 6}} - shows the.

ここで、式中、R₁、R₂、R₃、R₄、R₅は、それぞれ、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基、あるいはスルホニル基などの置換基を有しても良い芳香族炭化水素基又は炭化水素基又は複素環基又はヘテロ原子を環内に含む芳香族基を示し、R₁、 R₂、R₃、R₄、R₅は同じでも異なっていても良く、R'、R''は芳香環を含んでも良いアルキル基又はアルケニル基等の脂肪族炭化水素基あるいは芳香族炭化水素基、An^-は、Cl^-、Br^-、I^-等のハロゲン化物イオン、CF₃SO₃ ^-、BF₄ ^-、PF₆ ^-を示す。 Moreover, the compound represented by any 1 type of the following general formula (4), (5), (6), (7) or (8) can be used for the said imidazole derivative.

Here, in the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each have an aromatic group that may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group. An aromatic hydrocarbon group or a hydrocarbon group, a heterocyclic group or an aromatic group containing a hetero atom in the ring, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and R ', R''is an aliphatic hydrocarbon group or an aromatic hydrocarbon group such as is also alkyl or alkenyl group contains an aromatic ring, an ^{- is, Cl -, Br -, I} - , etc. halide ion, CF ₃ SO ₃ ⁻ , BF ₄ ⁻ and PF ₆ ⁻ are shown.

  In the marking agent of the present invention, the organic EL dye has a reactive group that reacts with the marking object, and a covalent bond group or an anionic group can be used as the reactive group.

  Moreover, 1 type selected from the group which consists of a carboxyl group, a sulfonyl group, a sulfate group, a phosphate group, and those combinations can be used for an anionic group.

  The covalent bond group may be one selected from the group consisting of an isocyanate group, an epoxy group, a halogenated alkyl group, a triazine group, a carbodiimide group, and an active esterified carbonyl group.

  The marking agent of the present invention can be detected using, for example, the following method. That is, the method for detecting a marking agent according to the present invention is a method for detecting a marking agent attached to a marking object, wherein the marking agent includes one or more fluorescent dyes and a solvent, and the fluorescent dye is an organic EL dye. The organic EL dye is a compound containing a five-membered ring compound having a conjugated system, and the five-membered ring compound contains one or more heteroatoms, selenium atoms, or boron atoms. The adhering marking agent is irradiated with excitation light to cause the fluorescent dye to emit light, and light emitted from the fluorescent dye is detected by the naked eye or a detector.

  Furthermore, the detection method of the present invention is a method in which the marking agent contains two or more types of fluorescent dyes having different emission colors, and two or more types of emission colors and / or mixed colors thereof are detected by irradiation with excitation light. Can be used.

  The marking agent of the present invention can be attached to a marking object using, for example, the following spray device. That is, the spray device of the present invention is a spray device in which a spray solution is accommodated in a container equipped with spray means, and the spray solution contains one or more fluorescent dyes and a solvent, The organic EL dye is a compound containing a 5-membered ring compound having a conjugated system, and the 5-membered ring compound uses a marking agent containing one or more hetero atoms, selenium atoms, or boron atoms. It is characterized by that.

  The marking agent of the present invention includes a fluorescent dye containing a 5-membered ring compound having a conjugated system, and the 5-membered ring compound uses an organic EL dye containing one or more heteroatoms, selenium atoms, or boron atoms, Even if it is rubbed, scratched, rubbed, etc., and further washed with a detergent or the like, it has a large adhesive force that cannot be easily peeled off from the marking object. In addition, organic EL dyes are excellent in water resistance, heat resistance, and light resistance and have little decrease in light emission intensity over time. Moreover, since a high quantum yield is exhibited in a dry state, the emission intensity is large and can be easily confirmed even at a low concentration.

  The marking agent of the present invention is a marking agent containing one or more fluorescent dyes and a solvent, the fluorescent dye is composed of an organic EL dye, and the organic EL dye is a compound containing a 5-membered ring compound having a conjugated system. The five-membered ring compound contains one or more heteroatoms, selenium atoms, or boron atoms.

  The objects of the marking agent of the present invention include articles and human bodies that are targets of crime prevention and crime investigation such as counterfeiting and theft. For example, important documents such as banknotes, checks, stock certificates, various certificates, articles such as automobiles, motorcycles, bicycles, arts, furniture, branded goods, clothes, body surface parts such as human skin, hair, nails, latent Examples include retained substances such as fingerprints. Furthermore, regarding the materials that make up the object, paper such as high-quality paper, OCR paper, carbonless paper, art paper, plastics such as vinyl chloride, polyester, polyethylene terephthalate, and polypropylene, metals, glass, ceramics, And natural fibers such as wool, cotton, silk and hemp, synthetic fibers such as regenerated cellulose fibers, polyvinyl alcohol fibers, polyamide fibers and polyester fibers, and proteins in human skin and body fluids.

  The organic EL dye contained in the marking agent of the present invention includes those having a reactive group such as a covalent bond group or an anionic group that reacts with the marking object, and those having no reactive group. Either type penetrates and adheres to the deep part of the surface of the substrate to be marked, so it cannot be easily peeled off even if it is rubbed or scratched. In addition, the covalent bond group or the anionic group forms a chemical bond with the functional group present on the surface of the marking object, and thus adheres firmly to the substrate. Here, the functional group present on the surface of the marking object is a protein amino group, imino group, thiol group, hydroxyl group or the like if the surface of the human body, hydroxyl group, amino group or thiol group or the like if clothing. It is. In the case of a latent fingerprint, it is a functional group of a substance secreted from the fingertip, such as an amino group, an amino group, an imino group, a thiol group, or a hydroxyl group of an amino acid or protein.

  Here, the covalent bond group is preferably a functional group that reacts with the amino group, imino group, thiol group or hydroxyl group of the marking object to form an amide bond, an imide bond, a urethane bond, an ester bond, or a guanidine bond. . The functional groups include, for example, isothiocyanate groups, isocyanate groups, epoxy groups, sulfonyl halide groups, acyl chloride groups, halogenated alkyl groups, glyoxal groups, aldehyde groups, triazine groups, carbodiimide groups, and active esterified carbonyl groups. Etc. can be used. Preferably, any one selected from an isothiocyanate group, an isocyanate group, an epoxy group, a halogenated alkyl group, a triazine group, a carbodiimide group, and an active esterified carbonyl group is preferably used. More preferably, any one selected from an isothiocyanate group, an isocyanate group, an epoxy group, a halogenated alkyl group, a triazine group, a carbodiimide group, and an active esterified carbonyl group is preferably used. This is because an amide bond can be formed with the amino group of the marking object, and it can be directly bonded to the imino group. More preferred are a triazine group, a carbodiimide group, or an active esterified carbonyl group. Further, when these organic EL dyes have a carboxylic acid group, it is possible to directly modify the amino group and imino group present in the marking object in the presence of a carbodiimide derivative or a triazine derivative.

For example, by using N-hydroxy-succinimide, the following formula (1)
As shown in I), when DCC is used as a condensing agent, the organic EL dye and the marking object are bonded by an amide bond via an N-hydroxy-succinimide ester. Further, as shown in the formula (II) in Scheme 1, a triazine derivative can be used for the active esterified carbonyl group. As the carbodiimide group, a carbodiimide reagent such as N, N′-dicyclohexylcarbodiimide (DCC) or 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide can be used. The organic EL dye and the marking object can be bound by an amide bond via a carbodiimide body (formula (III)). In addition, an organic EL dye having a carbodiimide group or a triazine group previously introduced into the molecule can be directly bonded to the amino group or imino group of the marking target (formula (V)). Here, R is an aromatic hydrocarbon group or a hydrocarbon group which may have a substituent such as a hydrocarbon group, an aromatic group, a cyclic aromatic group containing a hetero atom, or a cyclic hydrocarbon group containing a hetero atom. Or the heterocyclic group or the aromatic group which contains a hetero atom in a ring is shown.

  As the anionic group, any of a carboxyl group, a sulfonyl group, a sulfate group, a phosphate group, and a combination thereof that electrostatically binds to a positively charged group such as an amino group or imino group of a protein can be used. It is preferable to use a sulfonyl group. The organic EL dye having an anionic group includes a 5-membered ring compound having a conjugated system constituting the organic EL dye and / or a compound having an anionic group in a 6-membered ring compound. Furthermore, a compound in which an anionic group is introduced into the organic EL dye via a connecting portion described below is also included. In this case, for example, an organic EL dye into which a sulfonyl group is introduced via an active ester by the method of the above formula (V) can be used.

  Moreover, the marking agent of this invention can also contain both anionic group and covalent bond as a reactive group. For this purpose, a 5-membered ring compound and / or a 6-membered ring compound having a conjugated system constituting an organic EL dye is added to the above-mentioned anionic groups, that is, a carboxyl group, a sulfonyl group, a sulfate group, a phosphate group, and combinations thereof. Any one or more of the above and the above-mentioned covalent bond groups, that is, isothiocyanate group, isocyanate group, epoxy group, halogenated sulfonyl group, acyl chloride group, halogenated alkyl group, glyoxal group, aldehyde group, triazine group, carbodiimide And those containing one or more of a group and an active esterified carbonyl group.

The organic EL dye having a reactive group includes those in which a reactive group is directly bonded to the organic EL dye and those in which the reactive group is bonded to the organic EL dye through a connecting portion. A compound represented by the general formula A ₁ -A ₂ (1) can be used for the connecting portion. Here, A ₁ is a first linking group that binds to the organic EL dye (color forming portion), and A ₂ is a second linking group that binds to a reactive group and also serves as a spacer group. The first linking group may be any one selected from the group consisting of a substituted or unsubstituted alkyl group, an ether group, a thioether group, a substituted or unsubstituted imino group, an amide group, and an ester group. preferable. The second linking group is preferably an alkylene group or an alkylene group containing a hetero atom in the main chain. As the alkylene group, a methylene group, an ethylene group, or a trimethylene group is preferably used. As the alkylene group containing a hetero atom in the main chain, an ethylene oxide group is preferably used and the number of repetitions is preferably 1 to 5.

  Further, as the fluorescent dye used in the marking agent of the present invention, an intercalator proposed by the present inventor in International Patent Application / JP2005 / 016847 can also be used. In particular, it can be suitably used for marking human body skin, hair, nails and other body surface parts, and residual substances such as latent fingerprints. The intercalator has a structure in which an organic EL dye is bonded to one side or both sides of a binding portion that binds to double-stranded DNA via a linking portion.

  Here, a monocyclic or polycyclic aromatic group which may contain a hetero atom, preferably a polycyclic aromatic group, and more preferably a condensed aromatic group having high planarity can be used for the bonding part. Specific examples include anthracene group, phenanthrene group, pyrene group, fluorene group, biphenylene group, naphthalenediimide group, naphthaleneimide group, acridine group, phenyldiimide group, benzothiazole group, benzimidazole group, quinoline group, phenanthridine. Any one selected from the group consisting of a group and an indole group, more preferably an anthracene group, an acridine group or a naphthalene diimide group can be used. The naphthalenediimide group includes 1,8,4,5-naphthalenediimide and 2,3,6,7-naphthalenediimide.

  In addition, a peptide compound composed of one amino acid selected from the group consisting of lysine, arginine, histidine and ornithine can also be used for the binding part. In addition, acridine can be introduced into the peptide compound.

A compound represented by the above general formula A ₁ -A ₂ (1) can be used for the connecting portion. The second binding group A ₂ it is sufficient to bind to the binding unit.

  The organic EL dye used in the present invention is sandwiched in a solid state between a pair of an anode and a cathode, and can emit light by energy when holes injected from the anode and electrons injected from the cathode are recombined. If it is a pigment | dye, it will not specifically limit. For example, polycyclic aromatic compounds such as tetraphenylbutadiene and perylene, cyclopentadiene derivatives, oxadiazole derivatives, coumarin derivatives, distyrylpyrazine derivatives, acridone derivatives, quinacdrine derivatives, stilbene derivatives, phenothiazine derivatives, pyrazinopyridine derivatives, azole derivatives, Imidazole derivatives, carbazole derivatives, thiophene derivatives, and the like can be used.

  Specific examples of the organic EL dye include rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylbutadiene, tetraphenylcyclobutadiene, and pentaphenylcyclobutadiene as polycyclic aromatic compounds. it can. Examples of the cyclopentadiene derivative include 1,2,3,4-tetraphenyl-1,3-cyclopentadiene and 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene. As the oxadiazole derivatives, 2- (4′-t-butylphenyl) -5- (4′-biphenyl) 1,3,4-oxadiazole, 2,5-bis (4-diethylaminophenyl) 1, Mention may be made of 3,4-oxadiazole. Examples of coumarin derivatives include coumarin 1, coumarin 6, coumarin 7, and coumarin 30. Examples of the distyrylpyrazine derivatives include 2,5-bis- (2- (4-biphenyl) ethenyl) pyrazine, 2,5-bis- (4-ethylsteryl) pyrazine, and 2,9-bis- (4-methoxysteryl). ) Pyrazine can be mentioned. Examples of acridone derivatives include acridone and its derivatives. Examples of quinacrine derivatives include quinacrine and derivatives thereof. Examples of the stilbene derivative include 1,1,4,4-tetraphenyl-1,3-butadiene and 4,4'-bis (2,2-diphenylvinyl) biphenyl. As the azole derivative, imidazole derivative, carbazole derivative, and thiophene derivative, those described in the general formula in this specification can be used.

  Preferred organic EL dyes used in the marking agent of the present invention are compounds containing a 5-membered ring compound having a conjugated system, wherein the 5-membered ring compound contains one or more heteroatoms, selenium atoms, or boron atoms. Can be mentioned. More specifically, a monocyclic compound composed of a 5-membered ring compound having a conjugated system and a condensed polycyclic compound composed of a 6-membered ring compound having a conjugated system with the 5-membered ring compound can be exemplified. This is because even in the solid state, the quantum yield is large and strong fluorescence is exhibited. The 5-membered ring compound is preferably an azole derivative or an imidazole derivative. Furthermore, the azole derivative or imidazole derivative preferably has one or more quaternary ammonium groups. It is because water solubility can be improved.

ここで、式中、R₁、 R₂、 R₃、 R₄、 R₆、 R₇は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基、あるいはスルホニル基などの置換基を有しても良い芳香族炭化水素基又は炭化水素基又は複素環基又はヘテロ原子を環内に含む芳香族基を示す。R₁、 R₂、 R₃、 R₄、 R₆、 R₇は同じでも異なっていてもよい。R'は芳香環を含んでも良いアルキル基又はアルケニル基等の脂肪族炭化水素基あるいは芳香族炭化水素基、An^-は、Cl^-、Br^-、I^-等のハロゲン化物イオン、CF₃SO₃ ^-、BF₄ ^-、PF₆ ^-を示す。なお、以下の一般式においても、特に断らない限り同様である。 Below, the specific example of a condensed polycyclic compound is demonstrated.
(Monoazole derivative 1)

Here, in the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , and R ₇ each independently have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group. An aromatic group containing an aromatic hydrocarbon group, a hydrocarbon group, a heterocyclic group or a hetero atom in the ring. R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ may be the same or different. R ′ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group such as an alkyl group or an alkenyl group which may contain an aromatic ring, An ⁻ is a halide ion such as Cl ⁻ , Br ⁻ or I ⁻ , CF ₃ SO _{3 ^{-, BF 4 -, PF 6}} - shows the. The same applies to the following general formulas unless otherwise specified.

ここで、式中、R₈、R₉は、それぞれ、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基、スルホニル基などの置換基を有しても良い芳香族炭化水素基又は炭化水素基又は複素環基又はヘテロ原子を環内に含む芳香族基を示す。R₈、R₉は同じでも異なっていてもよい。なお、以下の一般式においても、特に断らない限り同様である。また、nは１以上の整数、好ましくは１〜５であり、以下の一般式中でも同様である。 (Monoazole derivative 2)

Here, in the formula, R ₈ and R ₉ are each an aromatic hydrocarbon group, a hydrocarbon group or a complex which may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group. An aromatic group containing a ring group or a hetero atom in the ring is shown. R ₈ and R ₉ may be the same or different. The same applies to the following general formulas unless otherwise specified. N is an integer of 1 or more, preferably 1 to 5, and the same applies to the following general formulas.

(Diazole derivative 1)

(Diazole derivative 2)

ここで、式中、R₁、 R₂、 R₃、 R₄は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基、あるいはスルホニル基などの置換基を有しても良い芳香族炭化水素基又は炭化水素基又は複素環基又はヘテロ原子を環内に含む芳香族基を示す。R₁、 R₂、 R₃、 R₄、 R₆、 R₇は同じでも異なっていてもよい。R₂、 R₃は、置換基を有しても良い芳香族炭化水素基を用いることが好ましい。また、Xは、置換基を有しても良い窒素原子、硫黄原子、酸素原子、セレン原子又はボロン原子であり、特に断らない限り以下の一般式中でも同様である。 (Diazole derivative 3)

Here, in the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each independently an aromatic group that may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group. An aromatic group containing a hydrocarbon group, a hydrocarbon group, a heterocyclic group, or a hetero atom in the ring. R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ may be the same or different. R ₂ and R ₃ are preferably aromatic hydrocarbon groups which may have a substituent. X is a nitrogen atom, sulfur atom, oxygen atom, selenium atom or boron atom which may have a substituent, and the same applies to the following general formulas unless otherwise specified.

(Diazole derivative 4)

ここで、N→Oは、窒素原子が酸素原子に配位結合している状態を示す。 (Diazole derivative 5)

Here, N → O indicates a state in which a nitrogen atom is coordinated to an oxygen atom.

(Diazole derivative 6)

(Diazole derivative 7)

(Diazole derivative 8)

ここで、式中、R₁₀、R₁₁は、それぞれ、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基、あるいはスルホニル基などの置換基を有しても良い芳香族炭化水素基又は炭化水素基又は複素環基又はヘテロ原子を環内に含む芳香族基を示す。R₁₀、R₁₁は同じでも異なっていてもよい。また、R₁₂は、置換基を有してもよいオレフィン基又はパラフィン基であり、nは１から３の整数、好ましくは１である。なお、以下の一般式においても、特に断らない限り同様である。

Here, in the formula, R ₁₀ and R ₁₁ are each an aromatic hydrocarbon group or a hydrocarbon group which may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group, or An aromatic group containing a heterocyclic group or a hetero atom in the ring is shown. R ₁₀ and R ₁₁ may be the same or different. R ₁₂ is an olefin group or a paraffin group which may have a substituent, and n is an integer of 1 to 3, preferably 1. The same applies to the following general formulas unless otherwise specified.

(Diazole derivative 9)

  Although it will not specifically limit if it is said diazole derivative, The oxadiazolo pyridine derivative represented by the following general formula can be used suitably.

  The oxadiazolopyridine derivative contains an N-hydroxy-succinimide ester using N, N′-dicyclohexylcarbodiimide (DCC) as a condensing agent, for example, by the reaction shown in the following scheme 2 after the carboxylic acid derivative is synthesized. It is preferable to use an active ester derivative.

(Triazole derivative 1)

(Triazole derivative 2)

(Triazole derivative 3)

(Triazole derivative 4)

As the 5-membered ring compound, the following derivatives containing a thiophene group can also be used.
(Thiophene derivative 1)

(Thiophene derivative 2)

ここで、式中、R₁₂,R₁₃,R₁₄はそれぞれ独立に、水素原子、直鎖、分岐または環状のアルキル基、置換または未置換のアリール基、あるいは置換または未置換のアラルキル基を表し、Ar₁およびAr₂は置換または未置換のアリール基を表し、さらに、Ar₁とAr₂は結合している窒素原子と共に含窒素複素環を形成してもよい。また、Y₁およびY₂は水素原子、ハロゲン原子、直鎖、分岐または環状のアルキル基、直鎖、分岐または環状のアルコキシ基、置換または未置換のアリール基、置換または未置換のアラルキル基、あるいは置換または未置換のアミノ基を表す。 (Thiophene derivative 3)
In the case of a thiophene derivative, it is a non-condensed compound, and a 2,3,4,5-tetraphenylthiophene derivative represented by the following general formula can also be used.

In the formula, each of R ₁₂ , R ₁₃ and R ₁₄ independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. , Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, and Ar ₁ and Ar ₂ may form a nitrogen-containing heterocycle together with the nitrogen atom to which Ar ₁ and Ar ₂ are bonded. Y ₁ and Y ₂ are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, Alternatively, it represents a substituted or unsubstituted amino group.

ここで、式中、Ar₁〜Ar₆はそれぞれ独立に、置換または未置換のアリール基を表し、さらに、Ar₁とAr₂、Ar₃とAr₄およびAr₅とAr₆は結合している窒素原子と共に含窒素複素環を形成していても良い。 (Thiophene derivative 4)
In addition, 2,3,4,5-tetraphenylthiophene derivatives represented by the following general formula can also be used.

Here, in the formula, Ar _{1 to} Ar ₆ each independently represents a substituted or unsubstituted aryl group, and Ar ₁ and Ar ₂ , Ar ₃ and Ar _4, and Ar ₅ and Ar ₆ are bonded to each other. A nitrogen-containing heterocyclic ring may be formed together with the nitrogen atom.

  Further, imidazole can be used as the five-membered ring compound and an imidazole derivative represented by the following general formula can be used.

(Imidazole derivative 1)

(Imidazole derivative 2)

(Imidazole derivative 3)

(Imidazole derivative 5)

ここで、イミダゾール骨格は中央のベンゼン環R₈, R₉, R₁₀, R₁₁ の任意の位置に複数ユニットが結合していても良い。また、R₁₂は、置換基を有してもよいオレフィン基又はパラフィン基であり、nは１から３の整数、好ましくは１である。

Here, the imidazole skeleton may have a plurality of units bonded to any position of the central benzene ring R ₈ , R ₉ , R ₁₀ , R ₁₁ . R ₁₂ is an olefin group or a paraffin group which may have a substituent, and n is an integer of 1 to 3, preferably 1.

(Carbazole derivative)
Moreover, the carbazole derivative shown with the following general formula can also be used.

  Moreover, it is a 5-membered ring compound which has a conjugated system, and the monocyclic compound containing 1 or more types of hetero atoms, a selenium atom, or a boron atom can also be used. Although not particularly limited, for example, an azole derivative represented by the following general formula can be used.

ここで、式中、R₁、 R₄、 R₅は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシル基、シアノ基、あるいはスルホニル基などの置換基を有しても良い芳香族炭化水素基又は炭化水素基又は複素環基又はヘテロ原子を環内に含む芳香族基を示す。R₁、 R₄、 R_５は同じでも異なっていてもよい。

Here, in the formula, R ₁ , R ₄ and R ₅ are each independently an aromatic hydrocarbon group which may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group. Or the aromatic group which contains a hydrocarbon group, a heterocyclic group, or a hetero atom in a ring is shown. R ₁ , R ₄ and R ₅ may be the same or different.

  As the marking agent of the present invention, the condensed polycyclic compounds and monocyclic compounds described above can be used, and preferably a diazole derivative or an imidazole derivative represented by the following general formula can be preferably used.

  Furthermore, among the above diazole derivatives and imidazole derivatives, diazolopyridine derivatives (1), (3) or imidazolopyridine derivatives (4), (5), (6) can be suitably used.

  The marking agent of the present invention contains at least the above organic EL dye and a solvent as a fluorescent dye. Furthermore, if necessary, various additives such as a surfactant, a charge imparting agent, and a pH adjuster which are added to a normal marking agent can be used.

  The organic EL dye can be used as an ink in a state dispersed in a solvent or in a state dissolved in a solvent. In the case of dispersing in a solvent, it is preferable to use a solvent in which the organic EL dye is insoluble or hardly soluble. As this solvent, for example, a hydrocarbon solvent such as hexane or petroleum ether can be used. Here, the organic EL dye is preferably dispersed in the form of crystal particles having a particle size of 100 to 1000 nm. In the crystal particle state, the storage stability is good, and a more transparent hue is obtained.

Moreover, when making it melt | dissolve in a solvent, it is preferable to use the mixed solvent of water or water and a water-soluble solvent from an environmental point. Examples of water-soluble solvents include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethers such as tetrahydrofuran, dioxane, and ethylene glycol methyl ether, ethylene Examples thereof include polyhydric alcohols such as glycol, propylene glycol and glycerin. The mixing ratio of water and the water-soluble solvent can be determined in consideration of the adhesion to the marking object and the drying property.
When used for fingerprint detection, acetone, methanol, and ethanol are not preferable because they dissolve lipids in fingerprint secretions and blur fingerprint ridges. It is preferable to use water as a solvent for fingerprint detection.

  Moreover, the density | concentration of the fluorescent pigment | dye in a marking agent can be suitably set according to a use, for example, is 10 to 0.01 weight%, More preferably, it is 5 to 0.5 weight%. This is because if the amount exceeds 10% by weight, the effect of concentration quenching becomes large, and if the amount is not saved more than 0.01% by weight, the emission intensity becomes insufficient. In the case of retained substances such as residual fingerprints and body fluids, it is 10 to 0.001% by weight, more preferably 5 to 0.05% by weight.

  Since the marking agent of the present invention uses an organic EL dye as a fluorescent dye, it penetrates and adheres to the deep surface of the marking object. Furthermore, the thing which has a reactive group improves the adhesive force, when a reactive group couple | bonds with a marking target object. Therefore, the binder resin added to the conventional marking agent is unnecessary. However, a binder resin can be added to further improve the adhesion. As the binder resin, a known binder resin used for an ink composition such as a vinyl resin, an acrylic resin, an amino resin, a polyester resin, a phenol resin, a cellulose resin, and a copolymer thereof may be used. it can. Furthermore, if a binder resin having an amino group is used, it is chemically bonded to the active ester that is a reactive group, so that the marking agent can be more firmly attached to the marking object. Examples of the binder resin having an amino group include synthetic polymers such as polyethyleneimine, polyvinylamine, and polyallylamine, and amino acid polymers such as polyornithine and polylysine.

  In order to attach the marking agent of the present invention to a marking object, the marking agent is sprayed or dropped on the marking object, or the marking object is immersed in the marking agent, or an inkjet printer or a dot impact printer. A method of forming a recognition code such as a desired pattern, character, number, barcode, or shape on a marking object using a stamp printer or the like can be used. When spraying on the marking object, a spray device including a marking agent can be used. As the spray device, a spray device in which a spray solution and a filling gas are accommodated in a container provided with a spray means can be used. As the spraying means, for example, a push button with a nozzle that is provided in a container and ejects the solution by being pushed down by a pressing operation can be used. The marking agent of the present invention is used as a solution for spraying, and LPG, nitrogen gas or the like is used as a filling gas. The spray device includes a small portable spray device and, for example, a fixed spray device which is fixed to a store entrance / exit or a ceiling and can be sprayed by remote control.

  It is also effective to place a container containing a fluorescent dye in front of an explosive device such as an air bag outside the entrance of a store, etc., and spray or diffuse the marking agent to the criminal instantly by explosion. . At this time, when the apparatus is activated, the door is locked in conjunction with it, and it is possible to prevent standing up.

  Moreover, the marking agent of this invention can also be made to adhere to a marking target object using a transfer sheet. A method for forming an invisible recognition code using a transfer sheet including a fluorescent dye-containing layer is known. For example, JP-A-7-68946 discloses a phosphor having a release layer and a recognition code formed on a substrate. A method is disclosed in which a transfer sheet in which a layer and an ultraviolet-cutting heat-sensitive transfer layer are sequentially laminated is used and transferred to a marking object by heat sublimation heat transfer or heat melt transfer. If a transfer sheet having a phosphor layer formed using the marking agent of the present invention is used, it is possible to transfer the recognition code to the marking object.

  In the present invention, two or more fluorescent dyes having different emission colors can be used. By irradiating with excitation light, two or more kinds of luminescent colors and / or mixed colors thereof can be detected. In order to form a full-color image, fluorescent dyes that emit light in three colors of blue, green, and red can be used.

  In order to detect the marking agent of the present invention, the marking object to which the marking agent is attached is irradiated with excitation light from an excitation light source, the organic EL dye is emitted, and the emitted light is detected by the naked eye or a detector. As the excitation light source, a light source capable of emitting near ultraviolet rays of 250 to 400 nm is preferable, and for example, black light or LED can be used. The detector can be an image photographing means such as a CCD camera.

A detection method using a detector will be described.
The marking agent attached to the marking object is irradiated with an excitation light source, and the emitted light is photographed with a CCD camera. The captured image is image-processed, and the wavelength distribution of light emission is calculated. For the calculation of the wavelength distribution, a known image processing method used in the color measuring device can be used. As a result, it is possible to easily analyze the color information such as the fluorescence wavelength when one kind of fluorescent dye is used, and the mixed color or multi-color wavelength distribution and light emission intensity when a plurality of fluorescent dyes are mixed and used. it can. In addition, when a plurality of fluorescent dyes are used, the mixed color or multicolor wavelength distribution or emission intensity varies depending on the mixing ratio, so that the mixing ratio of the fluorescent dyes can also be analyzed. Thus, by using the detector, the marking agent can be identified with higher accuracy not only from the presence or absence of the marking agent but also from the color information of the marking agent.

The marking agent of the present invention can be used for various applications. Several preferred applications are described below.
Application 1.
The marking agent of the present invention can be used as a marking agent for preventing counterfeiting of important documents such as banknotes, checks, stock certificates, and various certificates. The marking agent of the present invention is printed with a recognition code such as a desired pattern, character, number, barcode or shape on a substrate by, for example, an inkjet printer, a dot impact printer, a stamp printer, or the like to obtain a printed matter. These recognition codes may be directly printed on the substrate, or a method of forming a thermal transfer sheet having a fluorescent dye-containing layer and recording the recognition code and transferring the recognition code from the thermal transfer sheet to the substrate may be used. it can. The method for forming the thermal transfer sheet having the fluorescent dye-containing layer is not particularly limited, and a known method can be used. An important document such as a banknote can be irradiated with light from an excitation light source such as a black light to visualize a print area, and authenticity can be determined based on the presence or absence of a recognition code.

  In addition, a well-known organic pigment and an inorganic pigment can be added as needed. By using these pigments together, it is possible to form a printing region that exhibits the hue of the pigment under natural light and exhibits a hue that changes according to the mixing ratio of the pigment and the organic EL dye under a projector such as black light. it can. This makes it more difficult to imitate.

The following methods can be used for counterfeiting or illegal copying using a color copying machine.
In a color copying machine, an original is irradiated with light from a light source lamp, and exposure scanning is performed. Reflected light from the original is extracted by a color separation filter (R, G, B) through a reflecting mirror and an imaging lens, and the three primary color components of cyan, magenta and yellow are extracted, and each color toner corresponding to the three primary color components is extracted. In some cases, the color reproduction of the original is performed with four-color toner to which black is added. However, when a printed matter having a printing region containing an organic EL dye is copied, the organic EL dye emits visible light by light from a light source lamp (for example, a xenon lamp or a halogen lamp). As a result of the color separation filter also detecting the reflected light from the organic EL dye, only a copy having a hue different from the hue from the original can be obtained. If the printing area including the marking agent of the present invention is character information such as “copy material”, for example, it is possible to display not only the difference in hue but also the character information.

Application Example 2
The marking agent of the present invention can also be used as a crime prevention marking agent attached to a suspect and / or vehicle that may or may not escape using a portable spray device or a stationary spray device.
For example, when a woman is a molester in a car such as a train or bus, the hand of the suspect can be marked by lightly spraying a criminal's hand with a portable spray device containing a marking agent. After arrest, you can increase the possibility of being brought into your own self-sufficiency by checking the fluorescence with black light. It is also easy to dismiss the suspicion of being mistaken and arrested. Since the fluorescent dye used here forms a chemical bond with the protein on the body surface, it cannot be removed with a detergent or the like. In addition, because it is excellent in heat resistance and light resistance and has little change over time, even if it is missed on the spot, it can be arrested at a station or in a car at a later date. At this time, it is possible to adopt as scientific evidence by analyzing the fluorescent dye contained in the spray device owned by the woman and the fluorescent dye attached to the suspect. In addition, when the money is taken away, the criminal can be marked by spraying it on the hands, face, etc., and the suspect can be confirmed with the black light in the initial investigation (emergency deployment etc.). It is possible to improve the clearance rate at

  Also, in financial institutions such as banks and post offices, and stores such as precious metal stores and convenience stores, for example, fixed spray devices are installed at entrances and counters, etc., and criminals who escape by remote control by pressing a switch at hand It is possible to mark by spraying. Further, in order to prevent the criminal from standing in the store, the pigment can be attached by a blast generated by an air bag or the like when exiting. For example, in front of an air bag explosion device, a container that is directly or indirectly cleaved by the impact of a blast and encloses a fluorescent dye is placed, and the marking agent is removed from the container cleaved by the explosion impact of the explosion device. Can be spread in a timely manner and attached to the criminal.

  In addition, since marking on bills is possible, the evidence was confirmed and used by spraying from the side of the bill immediately before delivery, or from the side with a fixed spray device or portable spray device if it is a bundle of bills It can be used for confirmation of cases. For example, a portable black light is installed in stores, banks, general stores, etc., and it is easy to identify banknotes that have been robbed by illuminating them, and collect a lot of useful information for police investigations. Is possible. In addition, by installing and identifying black lights in many stores, it is possible to easily guess the range of action of the criminal. When labeling a bill bundle, it can also be applied to ransom.

  In addition, the crime is prevented by advertising the portable spray device and the fixed spray device containing these security marking agents or by letting the public know that they are equipped. It is also possible.

Application Example 3
Further, the marking agent of the present invention can be used as a marking agent for fingerprint detection. For example, a fingerprint is detected by the following method.
The marking agent solution is sprayed on the surface of the specimen, or the specimen is immersed in the marking agent solution for a predetermined time and taken out from the liquid, and then the specimen is washed with pure water. After the specimen surface is dried, an excitation light source such as black light is irradiated and a fluorescent image of the fingerprint portion is taken with a CCD camera.

  In addition, a method of supporting a fluorescent dye on aluminum powder conventionally used for fingerprint detection can also be used. For example, a fluorescent dye is added and dissolved in a dispersion in which aluminum powder is dispersed in chloroform, and then chloroform is distilled off to obtain an aluminum powder carrying the fluorescent dye. The aluminum powder is dispersed in water and the dispersion is sprayed over a wide area where there will be latent fingerprints. Thereafter, the excess aluminum powder is removed with a small amount of mist-like water, leaving only the aluminum powder adhered to the fingerprint portion. This makes it possible to detect fingerprints using both aluminum powder and fluorescent dye. According to this method, by spraying a liquid in which aluminum powder is dispersed, a wide range of fingerprints can be detected and the time required for fingerprint detection can be shortened compared to a method using solid aluminum powder. . Conventionally, a brush is used to leave the aluminum powder in the fingerprint portion, but this operation requires considerable skill. However, the aluminum powder other than the fingerprint portion can be easily removed simply by spraying mist-like water, so that it can be clearly revealed without damaging the fingerprint ridge. In addition, since a fluorescent dye is used, detection with higher sensitivity is possible.

  For this application, it is preferable to use a marking agent containing an organic EL dye having a reactive group. The organic EL dye can bind to the protein in the fingerprint secretion to clearly reveal the fingerprint ridge. Since even a minute amount of protein reacts, fingerprints can be detected with high sensitivity. Further, since the marking agent of the present invention is excellent in heat resistance and light resistance, it is possible to store a specimen marked with a fingerprint for a long period of time.

Application Example 4
Further, the marking agent of the present invention can also be used as a marking agent for detecting blood stains.
Blood stains are extremely important physical evidence in criminal investigations and criminal trials. The blood stain test includes a blood stain preliminary test for confirming whether the blood is blood, a human blood certification test for determining whether the blood is human blood, and a blood type test for examining the blood type. Here, the preliminary test includes a luminol method and a leucomalachite method, both of which confirm the presence or absence of blood stains by a color change when luminol or leucomalachite is oxidized by hemoglobin. However, since luminol emits light when it is positive, it is easy to detect even during nighttime investigations, but its specificity for hemoglobin is not sufficient. In addition, while leucomalachite is more specific than luminol, it has a problem that the color change from colorless to green is difficult to check at night and can only be used for daytime investigations.

  Among the marking agents of the present invention, if a marking agent containing an organic EL dye having a reactive group is used, the organic EL dye binds to hemoglobin in the blood stain, so the presence or absence of the blood stain is highly sensitive regardless of day or night. Can be detected. For example, a blood stain-like portion is extracted onto a filter paper containing distilled water, the blood stain-like portion is transferred to the filter paper, and a marking agent is dropped onto the transfer portion. Irradiate the transfer area with black light, and examine the presence of blood stains by the emission of organic EL dyes.

  Here, when the organic EL dye having a sulfonyl group binds to hemoglobin in blood stains that are proteins, the emission wavelength shifts to a shorter wavelength than in the free state, so the blood stain portion and other portions are distinguished. Is possible. The inventor has described in detail in Japanese Patent Application No. 2005-053798 about the wavelength shift due to the binding with protein.

Use 5.
The marking agent of the present invention can also be used for inspection of fraudulent playing card cards.
In the casino amusement hall, the business operator monitors to prevent fraud in the card game. For example, WO2002 / 064225 proposes a method in which an identification code such as a bar code is printed on a playing card with ultraviolet coloring ink, and a stack of playing cards is continuously inspected by an inspection device.

  As the playing card, plastic cards such as polyvinyl chloride, polycarbonate, and polyethylene terephthalate are used. The marking agent of the present invention is highly permeable to these impermeable substrates and binds strongly to these plastic cards. Therefore, the identification code formed using the marking agent of the present invention is not peeled off even by friction, and has high emission intensity. Therefore, the identification code formed using the marking agent of the present invention can exhibit discrimination power over a long period of time.

Hereinafter, the present invention will be described in more detail with reference to examples.
Synthesis Example 1 Synthetic active ester third active ester 3 was synthesized according to Scheme 2 below.

1 with 50 mL three-necked flask oxadiazolopyridine carboxylic acid 1.0 g (0.0026 moL) and N- hydroxysuccinimide 2 0.30 g of (0.0026 Mol) were dissolved in DMF 20 mL. N, N'-dicyclohexylcarbodiimide 0.54 g (0.0026 moL) was added dropwise thereto over 30 minutes. After dropping, the mixture was stirred at room temperature for 30 hours. DMF was distilled off under reduced pressure. The residue was isolated and purified by silica gel column chromatography (chloroform) to obtain 0.76 g of oxadiazolopyridine active ester 3 in a yield of 62%.

Scheme 3 Synthesis Example 2 Synthesis of sulfonyl 4
In a 50 mL three-necked flask, 3 0.5 g (0.0011 mol) of oxadiazolopyridinecarboxylic acid succinimidyl ester and 0.14 g (0.0011 mol) of taurine were dissolved in 20 mL of DMF. This was stirred at room temperature for 5 hours. DMF was distilled off under reduced pressure. The residue was isolated and purified by silica gel column chromatography (chloroform-methanol) to obtain 0.41 g of sulfonyl compound 4 in a yield of 82%.

Scheme 3

Scheme 4 Synthesis Example 3 Synthesis of ethyl ester 8

Scheme 4

(1) Synthesis of diketone derivative 6
In a 500 mL three-necked flask, 37.5 g (0.28 mol) of 4-methylacetophenone 5 and 0.15 g of sodium nitrite were dissolved in 100 mL of acetic acid. In a water bath, 100 mL of HNO ₃ dissolved in 100 mL of acetic acid was added dropwise over 2 hours. Thereafter, the mixture was stirred at room temperature for 2 days. The reaction mixture was slowly poured into 500 mL of water to produce a precipitate. The precipitate was filtered and dissolved in chloroform. The chloroform phase was washed with a saturated aqueous sodium bicarbonate solution and twice with a 10% NaCl aqueous solution. After dehydration with MgSO ₄ , chloroform was distilled off under reduced pressure to obtain 34.3 g (yield 76%) of oxadiazole-N-oxide 6 .

(2) Synthesis of diketone derivative 7
10 g (0.03 mol) of oxadiazole-N-oxide 6 was dissolved in 400 mL of acetonitrile in a 500 mL three-necked flask. Zn 12.0 g, AcOH 7 mL, and Ac ₂ O 20 mL were added thereto. The reaction was terminated by stirring for 6 hours. The reaction mixture was filtered to remove insolubles. Acetonitrile was distilled off under reduced pressure to obtain a residue. The residue was recrystallized from chloroform to obtain 6.75 g (yield 71%) of oxadiazole-N-oxide 7 .

(3) Synthesis of oxadiazolopyridine ethyl ester 8
Oxadiazole-N-oxide 7 was dissolved in 5.0 g (0.016 mol) and butanol 300 mL in a 500 mL three-necked flask. Thereto was added 32.0 g (0.23 mol) of glycine ethyl ester hydrochloride. Reflux was performed for 12 hours, and the reaction was terminated. Butanol was distilled off under reduced pressure to obtain a residue. The residue was dissolved in 200 mL chloroform and washed with 10% HCl, saturated NaHCO ₃ , 10% NaCl. It was dried over MgSO ₄ and the solvent was distilled off. The resulting residue was purified by column chromatography to obtain oxadiazolopyridine ethyl ester 8 in 4.1 g (yield 65%).

Example 1.
A marking agent in which the active ester 3 was dissolved in methanol was sprayed on the fingers of the hand and dried. FIG. 1 shows a photograph of the finger irradiated with black light after spray drying and rubbed with methanol as a solvent. A yellow luminescence was clearly observed.

Example 2
A marking agent was sprayed on the finger in the same manner as in Example 1 except that the sulfonyl compound 4 was used as the marking substance. Luminescence could be clearly observed when the finger was irradiated with black light after being spray dried and rubbed with a solvent.

Example 3
The marking agent was sprayed on the finger in the same manner as in Example 1 except that ethyl ester 8 was used as the marking agent. Luminescence could be clearly observed when the finger was irradiated with black light after being spray dried and rubbed with a solvent.

Comparative Example 1
A marking agent was sprayed on the finger in the same manner as in Example 1 except that rhodamine 6G was used as the marking substance. However, when the finger was irradiated with black light after being spray dried and rubbed with a solvent, only very weak luminescence was observed.

Example 4
(experimental method)
A glass plate with a finger pressed lightly was used as a specimen. The specimen was sprayed with a sulfonyl compound 4 dissolved in an aqueous solution, and then naturally dried. A photograph of the specimen when irradiated with black light is shown in FIG. The fingerprint ridge was clearly confirmed.

Comparative Example 2
The same method as in Example 4 was performed except that rhodamine 6G was used as the marking substance.
Even when the specimen was irradiated with black light, the fingerprint ridges could not be confirmed.

It is a photograph which shows the result of Example 1 of this invention. It is a photograph which shows the result of Example 4 of this invention.

Claims (4)

A marking agent comprising one or more fluorescent dyes and a solvent,
The fluorescent dye comprises an organic EL dye,
The organic EL dye is an azole derivative represented by any one of the following general formulas (1), (2) or (3), or the following general formulas (4), (5), (6), ( 7) or an imidazole derivative represented by any one of (8),
The organic EL dye has a reactive group that reacts with a marking object, and the reactive group is selected from the group consisting of a carboxyl group, a sulfonyl group, a sulfate group, a phosphate group, and combinations thereof A marking agent which is an anionic group, or one kind of covalently bonded group selected from the group consisting of an isocyanate group, an epoxy group, a halogenated alkyl group, a triazine group, a carbodiimide group, and an active esterified carbonyl group .

(In the formula, R ₂ , R ₃ and R ₄ are each independently an aromatic hydrocarbon group or a carbon atom which may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, or a sulfonyl group. An aromatic group containing a hydrogen group, a heterocyclic group or a hetero atom in the ring, R ₁ is bonded to the reactive group directly or through a linkage, and X has a substituent. Represents a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, or a boron atom, and R ′ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group such as an alkyl group or an alkenyl group that may contain an aromatic ring, An ⁻ Represents Cl ⁻ , Br ⁻ , I ⁻ , CF ₃ SO ₃ ⁻ , BF ₄ ⁻ or PF ₆ ⁻ . )

( Wherein R ₂ , R ₃ , R ₄ and R ₅ are each an aromatic hydrocarbon group which may have a substituent such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group or a sulfonyl group, or A hydrocarbon group, a heterocyclic group or an aromatic group containing a hetero atom in the ring, R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and R ₁ is directly bonded to the reactive group Alternatively, R ′ and R ″ may be bonded to a reactive group via a linking portion, and an aliphatic hydrocarbon group or an aromatic hydrocarbon group such as an alkyl group or an alkenyl group that may contain an aromatic ring, An ⁻ is Cl ^{-, Br -, I -,} CF 3 SO 3 -, BF 4 -, PF 6 - shows a). A method for detecting a marking agent attached to a marking object,
Markings by irradiating excitation light to a marking agent according to claim 1, wherein attached to the object to emit fluorescent dyes, detection methods of marking agent detected by the naked eye or detector light emission from the fluorescent dye. The detection method according to claim 2 , wherein the marking agent contains two or more fluorescent dyes having different emission colors, and detects two or more emission colors and / or a mixed color thereof by irradiation with excitation light. A spray device in which a spray solution is accommodated in a container equipped with a spray means,
The spray apparatus which uses the marking agent of Claim 1 for this spray solution.

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