JP2002173622A - Ultraviolet excitation-type ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet excitation-type ink composition exhibiting sufficient emission intensity under ultraviolet irradiation. SOLUTION: This ultraviolet excitation-type ink composition contains an europium complex of the formula ( wherein, A is a 2-naphthyl group optionally having substituent (s) selected from alkyl, alkoxy and halogen atom; and R is a 1-3C fluoroalkyl or methyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-excitation ink composition containing a europium complex having an absorption wavelength in an ultraviolet region and a fluorescent color region in a red region.

[0002]

2. Description of the Related Art In recent years, the term "functional organic material" has been used, and research on using organic materials for electronic and optical devices has been actively conducted. Among them, a luminescent compound (self-luminous compound) having a photoluminescence (PL) phenomenon is known.

[0003] One example of the use of the luminescent compound is a security ink. The security ink is an ink in which handwriting is invisible under visible light, but the handwriting emits light when irradiated with ultraviolet light, for example, a black light lamp, so that recorded information can be read.

[0004] Security inks are used to prevent counterfeiting or copying and to record confidential information for the purpose of maintaining confidentiality. For example, if a product's lot number, code, etc. are recorded with security ink, it is easy to track the distribution route of the product and prevent counterfeit products, and since it is not visible under visible light, there is less fear of tampering and damage. .

[0005] JP-A-2000-144029 discloses that
It contains a dye containing europium (Eu), which is substantially invisible in the visible light region and has an emission center wavelength of 610 ± 20 μm when excited by ultraviolet light, and a polyvinyl resin, and also contains a phosphine oxide compound and a phosphine sulfide. There has been proposed an ink composition containing at least one phosphoric acid compound selected from a compound and a phosphine compound, and containing 94% by weight or more of water or / and ethanol in a solvent.

[0006] Further, the present invention relates to an ink composition using a light-emitting compound of a europium-based complex, which is an aqueous ink for jet printing which can be visually recognized by ultraviolet irradiation (Japanese Patent Publication No. 54-22336).
Ink composition containing a fluorescent europium complex for thermal transfer (Japanese Patent Publication No. 6-15269) and a luminescent compound (for example, a tetra (benzoyltrifluoroacetonato) europium complex having an ammonium salt as a counter ion) Nos. 64-6085 and 64-26583
), A luminescent ink composition containing a europium complex coordinated with a bidentate ligand, for example, a bipyridine derivative or a phenanthroline derivative (JP-A-3-50291).
4,4,4-trifluoro-1- (2-thienyl) -1,3
-An ink composition for ink-jet printing containing a butanedionate-europium chelate compound and an alcohol-based solvent (JP-A-2000-160083) is known.

[0007] Japanese Patent Publication No. 6-15269 discloses a europium complex shown below (same as Comparative Example Compound 1 described later).
Are described. That is, the compound 6 in the publication is obtained by dissolving a tris (thenoyltrifluoroacetonate) europium (III) complex (1 mmol) in ethanol (10 ml) and, for example, using 2,2-bipyridine (1 mmol) as a bidentate ligand. ) Was added with stirring, and after 15 minutes, 20 ml of water was added, and the resulting precipitate was obtained by filtration and drying.

(Comparative Example Compound 1)

[0009]

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The synthesis of the following tris (benzoyltrifluoroacetonate) europium complex (same as Comparative Example Compound 2 described below) is described in, for example, JP-A-3-50291 (Example 2). ing.

(Comparative Example Compound 2)

[0012]

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For practical use as a security ink, handwriting of the ink needs to emit light to such an extent that it can be clearly recognized when irradiated with a black light lamp, particularly 360 nm light. However, these conventional luminescent compounds and ink compositions still have insufficient luminous intensity.

[0014] Therefore, there is a need for the development of an ultraviolet-excited ink composition which can clearly recognize handwriting under ultraviolet irradiation and has excellent emission intensity.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, and an object of the present invention is to provide an ultraviolet-excitation ink composition which exhibits a sufficient luminous intensity under irradiation of ultraviolet rays. It is in.

[0016]

The present invention is substantially colorless under visible light, but has absorption at an ultraviolet wavelength,
An object of the present invention is to provide an ultraviolet-excitation ink composition containing a europium complex which emits strong light at a wavelength near red when excited by ultraviolet light.

The present invention provides an ultraviolet-excitable ink composition containing any of the europium complexes represented by the following formulas (I) to (IV). These europium complexes are known per se. Its synthesis method and characteristics are described in, for example, The Chemical Society of Japan, 1981, No. 1, pages 66-73, and
Bull. Chem. Soc. Jpn., 71, 225-2258 (1998).

[0018]

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[0019]

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[0020]

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[0021]

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In the formulas (I) to (IV), A is a 2-naphthyl group which may have a substituent, R is a fluorinated alkyl group having 1 to 3 carbon atoms or a methyl group, R ¹ ,
R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group or an aryl group.

Heretofore, europium-based β-diketone complexes have been known as red light-emitting compounds for ink compositions. As the europium complex having a monodentate or bidentate ligand, those of thenoyl trifluoroacetone type or benzoyl trifluoroacetone type have been proposed. An ink composition containing a fluoroacetone-based europium complex has not been known.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The luminescent compound represented by the formula (I), (II), (III) or (IV) contained in the ink composition of the present invention contains trivalent europium, A specific β-diketone derivative to which a naphthyl group is bonded, 2,2′-bipyridine (derivative) as a bidentate ligand, 1,1
It is a europium (III) complex having a structure composed of 0-phenanthroline (derivative), 2,2′-biquinoline (derivative) or an ethylenediamine derivative.

In the formulas (I), (II), (III) and (IV), the substituent of the 2-naphthyl group A may be an alkyl group, an alkoxy group or a halogen. More specifically, the substituent of the 2-naphthyl group A is selected from the group consisting of an alkyl group having up to 4 carbon atoms, an alkoxy group having up to 4 carbon atoms, and a halogen atom.

Specific examples of the 2-naphthyl group A include 2-
Naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 5-
1 to 4 carbon atoms such as methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl, 8-methyl-2-naphthyl, 4-ethyl-2-naphthyl Alkyl-substituted 2-naphthyl group; 1-methoxy-2-naphthyl group, 3-methoxy-2-naphthyl group,
4-methoxy-2-naphthyl group, 5-methoxy-2-naphthyl group, 6-methoxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group,
1 to 4 carbon atoms such as 6-ethoxy-2-naphthyl group
Alkoxy-substituted 2-naphthyl group; or halogen-substituted 2-naphthyl group.

Formula (I), Formula (II), Formula (III) or Formula
In (IV), R is CF_ThreeGroup, CF _TwoH group, CFH
_TwoGroup, C_TwoF_FiveGroup, CH (CF_Three)_TwoGroup, CF_TwoCF_TwoCF_ThreeBase
C1-C3 fluorinated alkyl group or methyl group
And generally CF_ThreeIt is preferably a group.

Specific examples of R ¹ , R ² , R ³ and R ⁴ in the ethylenediamine derivative which is a bidentate ligand of the formula (IV) include a hydrogen atom, a methyl group, an ethyl group, a propyl group and a butyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as a group, a phenyl group, and a substituted phenyl group.

The bidentate ligand of the formula (I), (II) or (III) (2,2'-bipyridine (derivative), 1,1
0-phenanthroline (derivative) or 2,2′-biquinoline (derivative)) may have a substituent. As the substituent, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group,
Isoamyl group, hexyl group, cyclohexyl group), alkoxy group having 1 to 3 carbon atoms (eg, methoxy group, ethoxy group, isopropoxy group), aryl group (eg, phenyl group, tolyl group), aralkyl group (eg, benzyl group) Group, phenethyl group), and as the halogen group, Cl, F,
Br, I and the like.

Further, the bidentate ligand may have a carboxyl group, a hydroxyl group, an acyl group, an alkoxycarbonyl group or the like as a substituent.

The following compounds can be exemplified as the above-mentioned bidentate ligand. Of course, the methyl group as the substituent may be any other substituent exemplified above.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The europium complex used in the present invention is β-
For example, 4,4,4-trifluoro-1- (2-naphthyl) -1,3-butanedione (3 mol) as a diketone derivative and trivalent europium chloride (1mo)
l) and 2,2′-bipyridine (derivative), 1,10-phenanthroline (derivative), 2,2′-biquinoline (derivative), or ethylenediamine derivative (1 mol) and 1N as the bidentate ligand -NaOH,
It is obtained by heating and mixing in an organic solvent (for example, ethanol).

Specifically, 4,4,4-trifluoro-
1- (2-naphthyl) -1,3-butanedione (3 mm
ol) and europium (III) chloride hexahydrate (1 mm
ol) and, for example, 1,10-phenanthroline (derivative) (1 mmol) as a bidentate ligand and 1N—N
It can be synthesized by mixing aOH with ethanol and heating.

The obtained europium complex is used as a coloring agent or a fluorescent coloring agent in the ink composition of the present invention. That is, the europium complex is dissolved in a solvent and mixed with components normally contained in the ink composition such as a binder resin and various surfactants to obtain the ink composition of the present invention.

The amount of the europium complex is such that the concentration of the europium complex in the ink composition is 0.01 to 5% by weight,
Preferably, the amount is 0.1 to 3% by weight. When the concentration of the europium complex in the ink composition is less than 0.01% by weight, the amount of light emission is reduced, and it becomes difficult to read the light emission. When the concentration exceeds 5% by weight, self-absorption occurs, and the light emission intensity decreases.

Examples of the solvent used in the ink composition of the present invention include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-methoxy-4-methylpentanone, cyclohexane, methylcyclohexane, and the like. hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; alcohol solvents such as methanol, ethanol, propanol and isopropanol; glycol solvents such as ethylene glycol, diethylene glycol and propylene glycol; and 1,2-hexanediol , 2,4,6-Hexanetriol and other polyols, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and other ether solvents Ethyl acetate, ester solvents such as acetic acid n- propyl, 1,2-dichloroethane, 1,
Examples thereof include halogenated hydrocarbon solvents such as 1,2-trichloroethane and chloroform, dimethyl sulfoxide, n-methyl-2-pyrrolidone, γ-butyl lactone, toluene, xylene, and high boiling petroleum solvents. These solvents are used alone or in combination of two or more.

Preferred solvents are alcohol-based solvents, ketone-based solvents, ester-based solvents, or mixtures thereof, which can dissolve the luminescent compound contained in the ink composition of the present invention.

The binder resin used in the ink composition of the present invention is for fixing the luminescent compound satisfactorily, has good solubility in the above-mentioned solvents, and can appropriately adjust the viscosity of the ink composition. And the following resins. That is, polymethyl acrylate, polyethylene acrylate, polymethyl methacrylate, polyacrylates such as polyvinyl methacrylate, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl resins such as vinyl pyrrolidone-vinyl acetate copolymer, polystyrene,
Polyolefins such as polyurethane, acrylic urethane, polyester, vinyl chloride, vinylidene chloride, polyethylene and polypropylene, polyvinyl formal and their copolymers, amino resins, alkyd resins, epoxy resins, phenol resins, polyester imide resins, polyamide resins, polyamide imides Resin, silicone resin,
Phenolic resin, rosin, rosin modified resin (phenol, maleic acid, fumaric acid resin, etc.), petroleum resin, cellulose resin such as ethyl cellulose, nitrocellulose,
Examples include natural resins (gum arabic, gelatin, etc.).

Preferred binder resins are polyamide resins, polyvinyl resins and polyacrylate resins.

The ink composition of the present invention includes a varnish for polyamide ink (polyamide resin, ethyl alcohol, isopropyl alcohol, ethyl acetate, n-heptane, etc.) and a varnish for acrylic ink (acrylic resin, isopropyl resin). Oil-based varnishes such as varnishes for dye-type inks (alcohol, tannic acid or phenol resin, etc.), varnishes for fluorescent inks (ethylhydroxyethyl cellulose, pentaerythrol ester of rosin, mineral spirits, etc.) Can also be suitably used.

The amount of the binder resin to be used is, for example, 0.5 to 30% by weight, preferably 1 to 10% by weight in the ink composition. If the amount is less than 0.5% by weight, the luminescent compound cannot be sufficiently fixed to the impermeable recording medium. On the other hand, when the content is more than 30% by weight, the ejection stability of the ink composition may be reduced. In addition, since the binder layer thickly covers the periphery of the light emitting compound, the light emission of the light emitting compound may not only be reduced, but also the generation of light emission caused by the resin may be an obstacle.

The ink composition of the present invention may contain various surfactants (eg, anionic, nonionic, cationic, and zwitterionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ethers, and alkylamine salts). Agents), dispersants (eg, rosin acid soap, stearic acid soap, oleic acid soap, Na-di-β-naphthyl methane disulfate, Na-lauryl sulfate, Na-diethylhexyl sulfosuccinate), or cyclodextrin (CD ) (Eg, β-CD, dimethyl-β
-CD, methyl-β-CD, hydroxyethyl-β-C
D, hydroxypropyl-β-CD, etc.), an antifoaming agent (for example, various surfactants) and the like can be added. These additives can be used in an amount of about 0.5 to 10% by weight, preferably about 1 to 5% by weight, based on the ink composition.

The luminescent compound contained in the ink composition of the present invention generally shows solubility or good dispersibility in the above-mentioned various solvents and / or resins, and when it is excited by ultraviolet light, it emits light in the red region (610 to 630 nm). Fig. 4 shows a color-developed light (see Examples). For example, ultraviolet light (about 360 nm) is irradiated to an organic solvent solution (for example, ethanol solution) of the europium complex of the present invention by an ultraviolet lamp such as a black light lamp to excite the europium complex and emit light in a red region. it can. Therefore, the ink composition of the present invention does not emit light under visible light but emits red light under ultraviolet light, and is useful as a security ink.

[0055]

According to the present invention, since it is practically invisible under visible light and shows a strong luminescent color in a red region under ultraviolet light, it can be used for office documents, marking of various containers, blind printing of bar codes, etc., and security functions. The present invention can provide an ink composition useful in the field of printed matter.

[0056]

EXAMPLES The present invention will now be described specifically with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. In the following, “parts” means “parts by weight”.

Synthesis Example 1 4,4,4-trifluoro-1- (2-naphthyl)-
1,3-butanedione [7.98 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry Co., Ltd.)], 2,2′-bipyridine [1.56
g, 0.01 mol (manufactured by Wako Pure Chemical Industries)], europium (III) chloride hexahydrate [3.66 g, 0.01 mol
(Manufactured by Wako Pure Chemical Industries)], and 1N sodium hydroxide 30
was mixed with 100 ml of ethanol, and heated and stirred (about 40 ° C. for about 1 hour) to obtain the desired product 1 having the following structure
0 g (luminescent compound 1) was obtained.

[0058]

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Synthesis Example 2 4,4,4-Trifluoro-1- (2-naphthyl)-
1,3-butanedione [7.98 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry)], 1,10-phenanthroline [1.98 g, 0.01 mol (manufactured by Tokyo Chemical Industry)], europium (III) chloride hexahydrate [3.66 g, 0.0
1 mol (manufactured by Wako Pure Chemical Industries, Ltd.)] and 30 ml of 1N sodium hydroxide in 100 ml of ethanol, and heated and stirred (about 40 ° C. for about 2 hours) to obtain 10 g of the target compound having the following structure (light-emitting compound 2). I got

[0060]

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Synthesis Example 3 4,4,4-trifluoro-1- (2-naphthyl)-
1,3-butanedione [7.98 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry Co., Ltd.)], 2,2′-biquinoline [2.56
g, 0.01 mol (manufactured by Tokyo Chemical Industry Co., Ltd.)], europium (III) chloride hexahydrate [3.66 g, 0.01 mol]
(Manufactured by Wako Pure Chemical Industries)], and 1N sodium hydroxide 30
was mixed with 100 ml of ethanol, and heated and stirred (about 40 ° C. for about 1 hour) to obtain the desired product 1 having the following structure.
1 g (luminescent compound 3) was obtained.

[0062]

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Synthesis Example 4 4,4,4-Trifluoro-1- (2-naphthyl)-
1,3-butanedione [7.98 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry Co., Ltd.)], N, N, N ', N'-tetramethylethylenediamine [1.16 g, 0.01 mol (manufactured by Tokyo Chemical Industry Co., Ltd.)], europium (III) chloride hexahydrate [3.66 g] , 0.01 mol (manufactured by Wako Pure Chemical Industries)], and 30 ml of 1N sodium hydroxide in ethanol 10
The mixture was mixed in 0 ml, and heated and stirred (about 40 ° C. for about 2 hours) to obtain 9 g of the target compound having the following structure (luminescent compound 4).

[0064]

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Synthesis Example 5 4,4,4-Trifluoro-1- (2-naphthyl)-
1,3-butanedione [7.98 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry)], 4,4'-dimethyl-2,2'-
Bipyridine [1.84 g, 0.01 mol (manufactured by Wako Pure Chemical Industries)], Europium (III) chloride hexahydrate [3.66]
g, 0.01 mol (manufactured by Wako Pure Chemical Industries, Ltd.)] and 30 ml of 1N sodium hydroxide in 100 ml of ethanol, and heated and stirred (about 40 ° C. for about 2 hours) to obtain 10 g of the target substance having the following structure ( Light-emitting compound 5) was obtained.

[0066]

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Synthesis Example 6 4,4,4-trifluoro-1- (2-naphthyl)-
1,3-butanedione [7.98 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry)], 4,7-diphenyl-1,10-
Phenanthroline [3.32 g, 0.01 mol (manufactured by Tokyo Chemical Industry)], Europium (III) chloride hexahydrate [3.66 g, 0.01 mol (manufactured by Wako Pure Chemical Industries)], and 30 ml of 1N sodium hydroxide With ethanol 10
The mixture was mixed in 0 ml, and heated and stirred (about 40 ° C. for about 2 hours) to obtain 11 g of the desired product (light-emitting compound 6) having the following structure.

[0068]

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Synthesis Example 7 4,4,4-Trifluoro-1- (2-naphthyl)-
1,3-butanedione [7.98 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry Co., Ltd.)], 4,4′-dimethyl-2,2′-biquinoline [2.84 g, 0.01 mol (manufactured by Tokyo Chemical Industry Co., Ltd.)], europium (III) chloride hexahydrate [3.66]
g, 0.01 mol (manufactured by Wako Pure Chemical Industries, Ltd.)] and 30 ml of 1N sodium hydroxide in 100 ml of ethanol, followed by heating and stirring (about 40 ° C. for about 2 hours) to obtain 11 g of the target substance having the following structure ( Light-emitting compound 7) was obtained.

[0070]

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Synthesis of Comparative Example Compound 1 4,4,4-trifluoro-1- (2-thienyl)-
1,3-butanedione [6.66 g, 0.03 mol
(Manufactured by Tokyo Chemical Industry Co., Ltd.)], 2,2′-bipyridine [1.56
g, 0.01 mol (manufactured by Wako Pure Chemical Industries)], europium (III) chloride hexahydrate [3.66 g, 0.01 mol
(Manufactured by Wako Pure Chemical Industries)], and 1N sodium hydroxide 30
The mixture was mixed with 100 ml of ethanol, and heated and stirred (about 50 ° C. for about 1 hour) to obtain 8 g of Comparative Example Compound 1 having the following structure.

[0072]

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Synthesis of Comparative Example Compound 2 4,4,4-trifluoro-1-phenyl-1,3-butanedione [0.03 mol (manufactured by Tokyo Kasei)], 1,
10-phenanthroline [0.01 mol (manufactured by Tokyo Chemical Industry)], europium (III) chloride hexahydrate [0.01
mol (manufactured by Wako Pure Chemical Industries, Ltd.)] and 30 ml of 1N sodium hydroxide in 100 ml of ethanol, and heated and stirred (about 50 ° C. for about 1 hour) to obtain 10 g of Comparative Example Compound 2 having the following structure. Was.

[0074]

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Synthesis of Comparative Example Compound 3, 4,4,4-trifluoro-1- (2-thienyl)-
1,3-butanedione [0.03 mol (manufactured by Tokyo Chemical Industry)], 2,2′-biquinoline [0.01 mol (manufactured by Tokyo Chemical Industry)], europium (III) chloride hexahydrate [0.01 mol (sum) 8 g by mixing 30 ml of 1N sodium hydroxide in 100 ml of ethanol, and heating and stirring (at 50 ° C. for about 1 hour).
Of Comparative Example 3 having the following structure:

[0076]

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Synthesis of Comparative Example Compound 4 4,4,4-trifluoro-1- (2-thienyl)-
1,3-butanedione [e 0.03 mol (manufactured by Tokyo Kasei)], N, N, N ', N'-tetramethylethylenediamine [0.01 mol (manufactured by Tokyo Kasei)], europium (III) chloride hexahydrate A product [0.01 mol (manufactured by Wako Pure Chemical Industries)] and 30 ml of 1N sodium hydroxide are mixed in 100 ml of ethanol, and heated and stirred (about 50 ° C. for about 1 hour) to obtain 7 g of a comparative example having the following structure. Compound 4 was obtained.

[0078]

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Example 1 In this example, the luminescent compounds 1 to 4 of the present invention and the comparative compounds 1 to 4 obtained in the above Synthesis Examples were evaluated. As an evaluation method, 20 mg of each luminescent compound was dissolved in 100 ml of ethanol, and the fluorescence intensity (photoluminescence intensity) was measured using a fluorescence spectrophotometer (RF-5300PC manufactured by Shimadzu Corporation). Table 1 shows the relative fluorescence intensity when the fluorescence intensity of Comparative Example Compound 1 was 1.00.

The solubility of each compound (luminescent compound) was compared. The solubility was measured in 100 ml of ethanol or methyl isobutyl ketone (M1BK).
Each light-emitting compound was dissolved by heating, left at room temperature for 24 hours, and insoluble components were removed by filtration to calculate the solubility. Table 1 shows the results.

[0081]

[Table 1]

FIG. 1 shows the emission spectra of Light-Emitting Compounds 1 to 4 and Comparative Example Compound 1.

Example 2 60 g of polyamide varnish [Polyamide resin (10
Part), ethyl alcohol (25 parts) and isopropyl alcohol (25 parts)] and 40 g of methyl ethyl ketone, to dissolve the light emitting compound example 1 (1 g) to prepare an ink composition (A). A bar code was printed on an aluminum-evaporated polyester film using an ink jet recording apparatus [HG5130 manufactured by Epson Corporation], and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, a bright red light was emitted.

Example 3 An ink composition (B) was prepared in the same manner as in Example 2 except that the luminescent compound 1 used in Example 2 was changed to the luminescent compound 5. Ink jet recording device [HG51 manufactured by Epson Corporation]
30], a bar code was printed on an aluminum-evaporated polyester film, and this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, and emitted a clear red light.

Comparative Example 1 An ink composition (a) was prepared in the same manner as in Example 2 except that the light emitting compound 1 used in Example 2 was replaced with the compound 1 in Comparative Example. Using this ink, a bar code was printed on an aluminum-evaporated polyester film in the same manner as in Example 2, and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, red light was emitted. In the visual evaluation,
The emission intensity was smaller than that of Examples 2 and 3.

Example 4 To 50 g of methyl isobutyl ketone was added luminescent compound 2 (1
g) was dissolved and diluted with 40 g of ethanol. To this was added 10 g of a polybutyral resin [ELEX MB-S (trade name) manufactured by Sekisui Chemical Co., Ltd.] to prepare an ink composition (C). Barcode printing was performed on plain paper using an inkjet recording device [HG5130 manufactured by Epson Corporation], and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, a bright red light was emitted.

Example 5 An ink composition (D) was prepared in the same manner as in Example 4 except that the luminescent compound 2 used in Example 4 was changed to the luminescent compound 6. Ink jet recording device [HG51 manufactured by Epson Corporation]
30], a bar code was printed on plain paper, and this was irradiated with ultraviolet light (about 360 nm) by a black light lamp. As a result, a clear red light was emitted.

Comparative Example 2 An ink composition (b) was prepared in the same manner as in Example 4 except that the luminescent compound 2 used in Example 4 was replaced with the compound 2 in Comparative Example. Using this ink composition, bar code printing was performed in the same manner as in Example 4, and when this was irradiated with ultraviolet light (about 360 nm) from a black light lamp, red light was emitted. In the visual evaluation, the emission intensity was smaller than those in Examples 4 and 5.

Example 6 To 50 g of methyl isobutyl ketone was added luminescent compound 3 (1
g) was dissolved and diluted with 40 g of ethanol. To this, 10 g of polypinyl alcohol was added to prepare an ink composition (E). A bar code was printed on plain paper using an ink jet recording device [HG5130 manufactured by Epson Corporation], and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, it emitted red light.

Example 7 An ink composition (F) was prepared in the same manner as in Example 6, except that the luminescent compound 3 used in Example 6 was changed to the luminescent compound 7. Ink jet recording device [HG51 manufactured by Epson Corporation]
30], a bar code was printed on plain paper, and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, it emitted red light.

Comparative Example 3 An ink composition (c) was prepared in the same manner as in Example 6, except that the light emitting compound 3 used in Example 6 was replaced with the compound 3 in Comparative Example. Using this ink composition, bar code printing was performed in the same manner as in Example 6, and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, red light was emitted. In the visual evaluation, the emission intensity was smaller than those in Examples 6 and 7.

Example 8 A luminescent compound 4 (1 g) was dissolved in 90 g of ethanol, and 10 g of polypinyl alcohol was added thereto to prepare an ink composition (G). Barcode printing was performed on plain paper using an ink jet recording device [HG5130 manufactured by Epson Corporation], and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, it emitted red light.

Comparative Example 4 An ink composition (d) was prepared in the same manner as in Example 8, except that the luminescent compound 4 used in Example 8 was replaced with the compound 4 in Comparative Example. Using this ink composition, bar code printing was performed in the same manner as in Example 8, and when this was irradiated with ultraviolet light (about 360 nm) by a black light lamp, red light was emitted. In the visual evaluation, the emission intensity was smaller than that of Example 8.

Example 9 In order to examine the luminescence intensity of each of the above ink compositions,
Ultraviolet light was irradiated in the state of the ink, and the fluorescence output was measured.
Fluorescence output, put each ink composition in a transparent glass bottle, irradiate using a black light lamp with an excitation center wavelength of 360 nm, receive fluorescence emission from the ink with an objective lens,
After spectroscopy with a spectroscope, measurement was performed with a photomultiplier tube. In Table 2 below, the fluorescent output of each ink composition is shown as a relative value when the initial fluorescent output of the comparative ink composition a is 100%.

[0095]

[Table 2]

[Brief description of the drawings]

FIG. 1 is an emission spectrum of Light-Emitting Compounds 1 to 4 obtained in Synthesis Examples and Comparative Example Compound 1.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H086 BA54 BA55 BA59 4J039 AB02 AB11 AD01 AD03 AD05 AD06 AD10 AD18 AD22 AE02 AE03 AE04 AE05 AE06 AE08 AE09 AE11 BA39 BC01 BC02 BC03 BC04 BC05 BC07 BC08 BC09 BC10 BC11 BC13 BC18 BC22 BC49 BC54 BE02 BE12 BE16 BE22 EA29 GA13 GA21 GA22

Claims (8)

[Claims] (1) Formula (1) [Wherein, A is a 2-naphthyl group which may have a substituent selected from the group consisting of an alkyl group, an alkoxy group, and a halogen, and R is a fluorine-containing alkyl group having 1 to 3 carbon atoms. Or a methyl group. ] The ultraviolet excitation type ink composition containing the europium complex represented by these. 2. The formula: [Wherein, A is a 2-naphthyl group which may have a substituent selected from the group consisting of an alkyl group, an alkoxy group, and a halogen, and R is a fluorine-containing alkyl group having 1 to 3 carbon atoms. Or a methyl group. ] The ultraviolet excitation type ink composition containing the europium complex represented by these. 3. The formula: [Wherein, A is a 2-naphthyl group which may have a substituent selected from the group consisting of an alkyl group, an alkoxy group, and a halogen, and R is a fluorine-containing alkyl group having 1 to 3 carbon atoms. Or a methyl group. ] The ultraviolet excitation type ink composition containing the europium complex represented by these. 4. The formula: [Wherein, A is a 2-naphthyl group which may have a substituent selected from the group consisting of an alkyl group, an alkoxy group, and a halogen, and R is a fluorine-containing alkyl group having 1 to 3 carbon atoms. Or a methyl group, R ¹ , R ² , R ³ and R ⁴
Are each independently a hydrogen atom, an alkyl group or an aryl group. ] The ultraviolet excitation type ink composition containing the europium complex represented by these. 5. The method according to claim 1, wherein said R is a CF ₃ group.
The ultraviolet-excited ink composition according to any one of the above. 6. The ultraviolet excitation according to claim 1, wherein the 2,2′-bipyridine of the formula (I) has a substituent selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aralkyl group and a halogen. Mold ink composition. 7. The ultraviolet-excited type according to claim 1, wherein the 1,10-phenanthroline of the formula (II) has a substituent selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aralkyl group and a halogen. Ink composition. 8. The ultraviolet excitation according to claim 1, wherein the 2,2′-biquinoline of the formula (III) has a substituent selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aralkyl group and a halogen. Mold ink composition.