JP2000086952A - Luminous ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a luminous ink composition colorless in visible light, capable of emitting light by irradiation with light rays at a specific wavelength by making the composition include a rare-earth complex having a specific structure as a luminous material. SOLUTION: This luminous ink composition contains a rare-earth complex of formula I (M is a rare-earth metal; n1 is 2 or 3; n2 is 2, 3 or 4; Rf1 and Rf2 are each a 1-22C aliphatic group or aromatic group or a heterocyclic group not containing H; X1 and X2 are each an atom of the group IVA or the like; n3 and n4 are each 0 or 1; Y is N, P or the like) or formula II (Rf3 is as shown for Ff1; X3 is as shown for X1). Preferably the composition contains a polar solvent. The content of the rare-earth complex is preferably 0.005-20.0 wt.%. A printed material obtained from the composition is colorless in an ordinary light, has high luminescence by irradiation with light rays at specific wavelength and can be expected to have use for a hidden letter of papers, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a luminescent ink composition which is colorless under visible light and is used for printed matter which emits light when irradiated with light of a specific wavelength.

[0002]

2. Description of the Related Art There are many luminescent organic compounds, which have been used as fluorescent whitening agents or dyes for lasers. In particular,
For various special uses, inks and paints that are difficult to recognize in the visible region but are made visible by special light or readable by a sensor have been developed. Conventionally, for such applications, substances that emit purple light, such as fluorescent whitening agents, have been used. Since the fluorescent brightener is an aqueous dye, there is a disadvantage that the water resistance of the recorded matter is inferior. Further, since the fluorescent whitening agent is widely used for paper, fiber and the like, there is a disadvantage that it is difficult to distinguish the light emission from the light emission. In addition, a fluorescent pigment in which a fluorescent dye is made into particles with a resin is a mixture of a fluorescent dye with a resin or the like, and can be used like a dye by dissolving in an organic solvent, but also has absorption in the visible region. In addition, the display object can be visually confirmed without applying fluorescent light, and could not be used as a material of so-called hidden ink.

As a means for solving the above-mentioned problems, various inks using a complex of a β-diketone type compound such as hexafluoroacetylacetone and a rare earth metal as a light emitting material have recently been developed (JP-A-63-26583, Kaisho 64
-6085). For example, in JP-A-63-26583, a compound in which a quaternary ammonium salt is further added to a rare earth complex of β-diketone having a thienyl group in a side chain has been developed, and in JP-A-64-6085, Compounds obtained by further adding a quaternary ammonium salt to a rare earth complex of β-diketone having a benzene ring in the side chain have been developed, and all have improved the durability of the rare earth complex. However, these β-diketone-type rare earth complexes have not been satisfactory in terms of luminescence intensity or luminescence quantum yield.

[0004]

An object of the present invention is to use a novel and useful luminescent material, which is colorless under visible light.
An object of the present invention is to provide an ink composition that emits light when irradiated with light having a specific wavelength.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, an ink composition containing a rare earth complex having a specific structure as a luminescent material is a novel ink composition. Yes, it has been found that the luminous intensity is higher than that of the conventional luminescent ink, and that the luminescent ink has excellent performance. Furthermore, in the subsequent studies, it has been found that the luminescence intensity can be further enhanced by suspending and dispersing the rare earth complex in a specific solvent, and based on such findings, the present invention has been completed. Was.

That is, the luminescent ink composition of the present invention comprises the following eight items. (A) General formula (1) [Wherein, M represents a rare earth metal, and n1 represents 2 or 3.
n2 represents 2, 3 or 4. Rf ¹ and Rf ² are the same or different and each represent a C ₁ -C ₂₂ aliphatic group containing no hydrogen atom, an aromatic group containing no hydrogen atom, or a heterocyclic group containing no hydrogen atom, and X ₁ and X _{1 2} is the same or different and represents any one of a group IVA atom, a group VA atom excluding nitrogen, and a group VIA atom excluding oxygen; n3 and n4 each represent 0 or 1;
Y is CZ (Z represents a C ₁ -C ₂₂ aliphatic group containing no deuterium atom, halogen atom or hydrogen atom), N,
Indicates P, As, Sb or Bi. However, when X ₁ is a carbon atom n3 is 0, when X ₂ is a carbon atom n4 is 0. When X ₁ and X ₂ are simultaneously carbon atoms, Rf ¹ ,
At least one of Rf ^{2 is} an aromatic group containing no hydrogen atom. ] Or general formula (2) Wherein M, n1 and n2 are as defined above. Rf ³ represents a C _{1 to} C ₂₂ aliphatic group containing no hydrogen atom, an aromatic group containing no hydrogen atom, or a heterocyclic group containing no hydrogen atom, and X ³ represents a group IVA atom and V excluding nitrogen.
Indicates any of Group A atoms and Group VIA atoms excluding oxygen. A luminescent ink composition comprising the rare earth complex represented by the formula:

(B) Item a further comprising a polar solvent in the composition
3. The luminescent ink composition according to item 1.

(C) The rare earth complex is represented by the general formula (3) Wherein M, Rf ¹ , Rf ² , n1 and n2 are as defined above. A or b which is a complex represented by the formula:
3. The luminescent ink composition according to item 1.

(D) the rare earth complex is represented by the general formula (4) Wherein M, Rf ¹ , Rf ² , n1 and n2 are as defined above. A or b which is a complex represented by the formula:
3. The luminescent ink composition according to item 1.

(E) The rare earth complex is represented by the general formula (5) Wherein M, Rf ¹ , Rf ² , n1 and n2 are as defined above. A or b which is a complex represented by the formula:
3. The luminescent ink composition according to item 1.

(F) General formula (6) Wherein M, n1 and n2 are as defined above.
Z ′ represents a hydrogen atom or Z (as described above). Rf ⁴ and Rf ⁵ are the same or different and are each a hydrogen atom-free C
Aliphatic group of ₁ -C _22, showing a heterocyclic group containing no aromatic group or a hydrogen atom do not contain hydrogen atoms. A luminescent ink composition comprising a dispersion or suspension mixture of the rare earth complex represented by the formula (1) and a polar solvent.

[0012] (g) the polar solvent is luminous ink composition according to any one of Items term b~f a _{DMSO-d 6.}

(H) 0.005 to 20.0 rare earth complex
The luminescent ink composition according to any one of items a to g, wherein the light-emitting ink composition contains the composition in an amount of 1% by weight.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the rare earth complex according to the present invention, Rf ¹ , Rf ² , Rf ³ , Rf ⁴ and Rf ⁵ are the same or different and are a C _{1 to} C ₂₂ aliphatic group containing no hydrogen atom, It represents an aromatic group containing no hydrogen atom or a heterocyclic group containing no hydrogen atom.

The C ₁ -C ₂₂ aliphatic group containing no hydrogen atom includes: * a perfluoroalkyl group (C _n F _{2n + 1} ; n = 1
To 22), a perchloroalkyl group (C _n Cl _{2n + 1} ; n)
= 1 to 22) and a linear or branched perhalogenated alkyl group, specifically, trichloromethyl, trifluoromethyl, pentachloroethyl, pentafluoroethyl, heptachloropropyl, heptafluoropropyl, heptachloro Isopropyl, heptafluoroisopropyl, nonachlorobutyl, nonafluorobutyl, nonachloroisobutyl, nonafluoroisobutyl, undecachloropentyl, undecafluoropentyl, undecachloroisopentyl, undecafluoroisopentyl,
Tridecachlorohexyl, Tridecafluorohexyl,
Tridecachloroisohexyl, tridecafluoroisohexyl, pentadecachloroheptyl, pentadecafluoroheptyl, pentadecachloroisoheptyl, pentadecafluoroisoheptyl, heptadecachlorooctyl,
Heptadecafluorooctyl, heptadecachloroisooctyl, heptadecafluoroisooctyl, nonadecachlorononyl, nonadecafluorononyl, nonadecachloroisononyl, nonadecafluoroisononyl, henicosachlorodecyl, henicosafluorodecyl , Henicosachloroisodecyl, henicosafluoroisodecyl, tricosachloroundecyl, tricosafluoroundecyl, tricosachloroisoundecyl, tricosafluoroisoundecyl, pentacosachlorododecyl, pentacosafluorododecyl, Pentacosachloro isododecyl,
Pentacosafluoroisododecyl, heptacosachlorotridecyl, heptacosafluorotridecyl, heptacosachloroisotridecyl, heptacosafluoroisotridecyl, etc .; * perfluoroalkenyl groups (perfluorovinyl, perfluoroallyl, Furuorobuteniru group), straight chain or C ₂ -C ₂₂ perhalogenated alkenyl group having a branch, such as perchlorethylene alkenyl group, preferably, trifluoroacetic ethynyl, trichloroacetic ethynyl, pentafluoro propenyl, pentachlorophenol propenyl, hepta Furuorobuteniru, hepta-chloro butenyl and the like; * perfluoro alkynyl group, C ₂ -C ₂₂ perhalogenated alkynyl groups having a linear or branched, such as perchlorethylene alkynyl group; * perfluorocycloalkyl group (C _n F _n-1;
n = 3 to 22, preferably 3 to 8, more preferably 3 to
6), perchlorethylene cycloalkyl group _{(C n} Cl _{2n -1;}
n = 3 to 22, preferably 3 to 8, more preferably 3 to
6) C ₃ ~C ₂₂ perhalogenated cycloalkyl groups such as, preferably, pentachlorophenol cyclopropyl, pentafluorocyclopropyl, hepta-chloro cyclobutyl,
Heptafluorocyclobutyl, nonachlorocyclopentyl, nonafluorocyclopentyl, undecachlorocyclohexyl, undecafluorocyclohexyl, tridecachlorocycloheptyl, tridecafluorocycloheptyl, pentadecachlorocyclooctyl, pentadecafluorocyclooctyl, etc .; fluoro cycloalkenyl group (perfluoro cyclopentenyl group, a perfluoro-cyclohexenyl group), C ₃ -C such perchlorethylene cycloalkenyl group
₂₂ , preferably C ₃ -C ₈ , more preferably C ₃ -C
₆ , perhalogenated cycloalkenyl groups; and * perhalogenated aralkyl groups such as perfluorobenzyl group and perfluorophenethyl group.

The aromatic group of the "aromatic group containing no hydrogen atom" includes phenyl, naphthyl, anthranyl, phenanthryl, pyrenyl and the like; the heterocyclic group of the "heterocyclic group containing no hydrogen atom" is pyridyl, Thienyl, pyrrolyl, pyrimidinyl, quinolyl, isoquinolyl, benzimidazolyl, benzopyranyl, indolyl, benzofuranyl, imidazolyl, pyrazolyl, biphenyl, etc., and all hydrogen atoms of these aromatic groups and heterocyclic groups are fluorine atoms, chlorine atoms, A halogen atom such as a bromine atom, a nitro group, a C ₁ -C ₄ perhalogenated alkyl group (such as trifluoromethyl), a C ₁ -C ₄ perhalogenated alkoxy group (such as trifluoromethoxy),
₂ -C ₅ perhalogenated alkyl group (trifluoroacetyl, _etc.), C 1 -C ₄ perhalogenated alkylene group (difluoromethylenedioxy, _etc.), perhalogenated alkenyl C 2 -C ₅ (Eg, perhalogenated vinyl), perhalogenated phenoxy group,
It is substituted with substituent groups that do not contain C ₂ -C ₂₂ hydrogen atoms, such as perhalogenated alkylcarbonyloxy.

Specific examples of the aromatic group containing no hydrogen atom include a perfluorophenyl group, a perchlorophenyl group, a perfluoronaphthyl group, a perchloronaphthyl group,
A perfluoroanthranyl group, a perchloroanthranyl group, a perfluorophenanthryl group, and a perchlorophenanthryl group are mentioned, and as the heterocyclic group containing no hydrogen atom, a perhalogenated 2-pyridyl group and the like are mentioned.

One or more of the halogen atoms bonded to the aromatic or hetero ring of the perhalogenated aromatic group, perhalogenated heterocyclic group or perhalogenated aralkyl group may be cyano, nitro, nitroso, C ₁ -C It may be substituted with a substituent containing no hydrogen atom, such as C ₄ perhalogenated alkoxy, C ₂ -C ₅ perhalogenated alkoxycarbonyl, and C ₂ -C ₂₂ perhalogenated alkylcarbonyloxy.

_Further, C 1 _{-C 22} perhalogenated alkyl _group, C 2 _{-C 22} perhalogenated alkenyl groups, _{C 2}
-C ₂₂ C at any position of the perhalogenated alkynyl group
-O-, -COO-, and -CO- are separated by 1 between -C single bonds.
An ether, ester or ketone structure may be formed by interposing one or a plurality of them.

The rare earth elements represented by M include La,
Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
Lanthanum series elements such as y, Ho, Er, Tm, Yb, Lu and the like, preferably Nd, Eu, Tb and Y
b is more preferably Nd, Eu and Tb.

X ¹ and X ² are C, Si, Ge, S
n, any of a group IVA atom such as Pb, a group VA atom excluding nitrogen such as P, As, Sb, and Bi; and a group VIA atom excluding oxygen such as S, Se, Te, and Po; It represents S, P or Se, more preferably C or S.

X ³ is an IV of Si, Ge, Sn, Pb, etc.
VA excluding nitrogen such as group A atoms, P, As, Sb, Bi, etc.
A group atom, or any of group VIA atoms excluding oxygen, such as S, Se, Te, and Po, and preferably S.

Y is CZ (Z is the same as above), N, P,
As, Sb or Bi, preferably CZ (Z is the same as above), N or P.

Z is a deuterium, a halogen atom or a C ₁ -C ₂₂ aliphatic group containing no hydrogen atom, preferably deuterium or a linear or branched C ₁ -C ₂₂ perhalogenated alkyl group. Show.

Z ′ represents a hydrogen atom or Z.

N1 represents 2 or 3, preferably 3.

N2 represents 2 to 4, preferably 2 or 3, especially 3.

N3, n4 and n5 are 0 or 1. In particular, when X ¹ , X ² or X ³ is S, n 3, n 4 or n 5 is preferably ^{1. When} X ¹ or X ² is C, n 3 or n 4 is 0.
It is.

In the complex of the present invention, two, three or four ligands can be coordinated, but a four-coordinated complex is a minor component and has a coordination of two or three molecules. The main component is a complex coordinated with a ligand, particularly a ligand of three molecules.

As shown in the general formula (1), the ligand of the present invention is obtained by removing hydrogen or deuterium at the 2-position of the ligand.
The ligand is usually coordinated to a rare earth ion as a ligand of a valent anion, but it may be coordinated as a neutral diketone ligand from which hydrogen or deuterium at position 2 has not been eliminated. Complexes in which such a neutral diketone ligand is coordinated are also included in the complexes of the present invention.

Among the rare earth complexes represented by the general formula (1), more preferred rare earth complexes include a rare earth complex represented by the general formula (3), a rare earth complex represented by the general formula (4),
The rare earth complex represented by the general formula (5) is exemplified.

Among the rare earth complexes represented by the general formula (6), more preferred rare earth complexes include Rf ⁴ and Rf
⁵ is a linear or branched perhalogenated alkyl group represented by C _n X _{2n + 1} (where X is F, B
a halogen atom such as r or Cl), and Z ′ is X or deuterium (D), and F is particularly recommended as the halogen atom.

The ligand of the complex to be incorporated in the composition of the present invention is a known compound or can be easily synthesized from a known compound. For example, Journal of Chemical and Enzyme
gineering Data, Vol. 16, No. 3, (1971), and The
Journal of Organic Chemistry, Vol. 35, No. 4, (1970)
Can be synthesized according to a method described in a literature such as

The complexes represented by the general formulas (1) to (6) are
A corresponding ligand and at least one rare earth metal compound selected from the group consisting of a rare earth metal oxide, a rare earth metal hydroxide, a rare earth metal alkoxide, a rare earth metal amide, and a rare earth metal salt are mixed, for example, in a solvent. Can be manufactured.

The rare earth complex according to the present invention can be prepared using one or more kinds of ligands, and the rare earth atoms forming the complex are one or more kinds of compounds. You can use it.

The specific method for producing the rare earth complexes represented by the general formulas (1) to (6) is as follows.

That is, the corresponding ligand is dissolved in a solvent, and a rare earth metal compound (regardless of powder or granule) is added thereto.
Stir for about 0 hours. Then, the product is subjected to purification means such as crystallization or liquid-liquid extraction to obtain a rare earth complex. Further, recrystallization may be performed using a solvent such as chloroform or methanol.

Among the rare earth metal compounds, examples of rare earth metal oxides include trivalent M ₂ O ₃ (M represents a rare earth element), and other forms such as MO and M ₄ O ₇ Oxides may be used. Similarly, as the rare earth metal hydroxide, M (OH) n ₁ is exemplified; as the rare earth metal alkoxide, M (OR ¹ ) n ₁ (R ¹ is an alkyl group) is exemplified; As the rare earth metal amide, M (NR
^a R ^b ) ₃ (R ^a and R ^b are the same or different and each is hydrogen, alkyl, phenyl); examples of rare earth metal salts are M ³⁺ (Z) n ₁ (Z is chlorine ion, bromine ion, iodine ion; Monocarboxylic acid ions such as fluorine ion, 1/2 sulfate ion, nitrate ion and acetate ion, 1/2 (dicarboxylate ion such as oxalate ion, succinate ion and malonate ion), 1/3 (citric acid etc. tricarboxylic acid ion), 1/3 anions) are exemplified phosphate ions (n ₁ are as defined above).

The solvent used for producing the complexes represented by the general formulas (1) to (6) is not particularly limited, and any solvent can be used. Specific examples include a protic solvent and an aprotic solvent. Examples of the protic solvent include alcoholic solvents such as water, methanol and ethanol sugar, and examples of the aprotic solvent include ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether and tetrahydrofuran, chloroform, and methylene chloride. A halogenated solvent,
DMSO, DMF and the like. Among them, water is preferred.

The amount of the solvent used is 1 to the total amount of the ligand and the rare earth metal compound (1 part by weight).
About 100 parts by weight, and preferably about 1 to 20 parts by weight.

The complex represented by the general formula (2) is a compound of the above-mentioned rare earth metal
Compound and known substance Rf³-X ³(= O) n5 + 1 (O
H) with an equivalent or excess amount in water
Obtainable. The complex of the general formula (2) is represented by H₂O is distributed
Easy to position, H₂When O is coordinated, its properties as an optical functional material
Loss of quality, so that H is higher than that of the complex of the general formula (1).₂Against O
More unstable.

The amount of the rare earth metal compound used in producing the rare earth complexes represented by the general formulas (1) to (6) is 1 to 10 equivalents to 1 equivalent of the corresponding ligand, and is preferably 1.05 to 3 equivalents. Also, the rare earth complex of the general formula (2) can be produced at the same mixing ratio as described above.

When the rare earth complex represented by any one of the general formulas (1) to (6) contains coordinating water, for example, a sample of the complex is made of Me
Add a deuterated solvent such as OD or D ₂ O and add the sample /
After freezing the deuterated solvent to create a vacuum,
It is allowed to stand for about 4 hours, and then the deuterated solvent is distilled off to convert the coordinated H ₂ O into D ₂ O.

Since the rare-earth complex according to the present invention has a high luminous intensity, luminous properties can be exhibited by using 0.005 to 20% by weight in the ink composition, and more preferably 0.01 to 10% by weight. is there. When the concentration is less than 0.005% by weight, it is difficult to confirm light emission. On the other hand, when the concentration is more than 20% by weight, the emission intensity is higher than a sufficiently identifiable level and is uneconomical.

The ink composition of the present invention has the general formula (1)
Alternatively, a polar solvent can be added in addition to the rare earth complex represented by the general formula (2). By using the rare earth complex represented by the general formula (1) or (2) in combination with the polar solvent, the emission intensity, the quantum yield and the like can be greatly increased.

The method for adding the polar solvent is not particularly limited. As a specific method, a method in which a rare earth complex polar solvent solution, suspension, or dispersion is prepared in advance and mixed with a separately prepared ink composition, rare earth complex, polar solvent, and separately prepared And a method of simultaneously mixing all the components to form an ink composition.

Among them, a solution, suspension or dispersion of a rare earth complex in a polar solvent is prepared in advance (preferably in a state of a solution, dispersion or suspension of a polar solvent in a range of 0.01 to 0.01).
(48 hours, more preferably 0.1 to 6 hours), and a method of mixing this into a separately prepared ink composition is preferable.

The rare earth complex represented by the general formula (6) includes those already used as a luminescent ink composition.
By adding a rare earth complex in a polar solvent suspension or dispersion into the ink composition, that is, preparing a polar solvent solution, suspension or dispersion of the rare earth complex in advance,
Due to the method of mixing this with the ink composition, the emission intensity is significantly increased as compared with the conventional one.

The amount of the polar solvent used is rare earth complex 1
The solvent is exemplified by 0 to 200 parts by weight per part by weight, preferably 0 to 50 parts by weight.

Examples of the polar solvent include aprotic polar solvents having a higher dielectric constant than water, such as DMSO (dimethyl sulfoxide), DMF (dimethylformamide), formamide, acetamide, HMPA (hexamethylphosphoric triamide) and nitromethane. , Preferably DMS
O. Furthermore, the polar solvent is deuterated, for example, _{DMSO-d 6} more preferred.

The printed matter obtained from the luminescent ink composition containing the above rare earth complex is colorless when irradiated with visible light, and emits light when irradiated with a specific wavelength. That is, for example, the Eu complex is red (61
5b), the Tb complex emits green (545 nm) upon irradiation with ultraviolet light, and the Nd complex emits 585
nm wavelength (using germanium light emitting diode etc.)
Has a light emission characteristic of 1060 nm by irradiation.

The ink composition of the present invention can be applied to offset printing ink, gravure printing ink, printing ink such as silk screen, ink for inkjet printing, and ink for writing.

The ink composition of the present invention may contain a solvent, a binder, and various additives. By selecting the type of the solvent, the presence or absence of the binder, the type, the amount, etc., and adjusting the viscosity, surface tension, conductivity, drying property, etc., it can be applied to various printers and various recording media. It becomes possible. When an absorptive recording medium such as paper is used, the ink composition is prepared by dissolving the rare earth complex of the present invention, a solvent, and if necessary, a binder component and an additive.

As the solvent used in the ink composition of the present invention, specifically, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and 4-methoxy-4-methylpentanone, cyclohexane, methylcyclohexane, n-pentane, n Hydrocarbon solvents such as hexane and n-heptane, alcohol solvents such as methanol, ethanol, propanol and isopropanol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, dipropylene glycol, and 1,2-
Polyols such as hexanediol, 2,4,6-hexanetriol, dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ether solvents such as diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethyl acetate, and acetic acid n Ester solvents such as -propyl, halogen solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane and chloroform, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ
-Butyl lactone, toluene, xylene, and high-boiling petroleum solvents (eg, Shellsol, Shell Chemical, Hysol, Nippon Oil and the like). Among them, acetone,
Ketones such as methyl ethyl ketone, alcohol solvents such as N-methylpyrrolidone, methanol, ethanol and isopropanol, ester solvents such as toluene, xylene, ethyl acetate and n-propyl acetate, dimethyl sulfoxide, ethylene glycol and the like are recommended. It is also possible to use a small amount of water in combination with the above solvent. These solvents are used alone or as a mixture in the range of 0 to 95% of the ink composition.

The binder component used in the ink composition of the present invention is for fixing the luminescent material well, has good solubility in the above-mentioned solvent, and can appropriately adjust the viscosity of the ink composition. Examples thereof include the following resins. That is, polyacrylates such as polymethyl acrylate, polyethylene acrylate, polymethyl methacrylate, and polyvinyl acrylate, polyolefins such as polystyrene, polyurethane, acrylic urethane, polyester, vinyl chloride, vinylidene chloride, polyethylene, and polypropylene, polyvinyl formal, and copolymers thereof. Coalescing, amino resin, alkyd resin, epoxy resin, phenol resin, polyester imide resin, polyamide resin, polyamide imide resin, silicone resin, phenol resin, rosin, rosin modified resin (phenol, maleic acid, fumaric resin, etc.), Examples include petroleum resins, cellophane, cellulosic resins such as ethylcellulose and nitrocellulose, and natural resin types (gum arabic, gelatin, etc.). Polymethyl acrylate, polyethylene acrylate, polymethyl methacrylate, polyacrylate such as polyvinyl acrylate, polystyrene, polyvinyl alcohol and their copolymers, rosin, rosin-modified resin (phenol, maleic acid, fumaric acid resin, etc.) are recommended. .

The amount of these binders 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 material cannot be sufficiently fixed to the impermeable recording medium. If 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 material, not only may the light emission of the light emitting material be reduced, but also the generation of light emission caused by the resin may be an obstacle. When a resin is used, stronger water resistance can be obtained in a recorded matter.

On the other hand, as the binder used in the ink composition, inorganic fine particles can be used in addition to the above resin. As specific inorganic fine particles, titanium oxide,
Examples thereof include iron oxide, calcium carbonate, barium sulfate, and silica gel. The particle size is 0.01 μm to 1 μm
m, preferably 0.05 μm to 0.5 μm. These inorganic substances may be subjected to a surface treatment, if necessary, to improve the dispersion stability.

Examples of various additives used in the ink composition of the present invention include a penetrant, an antifoaming agent, a coloring agent, an ultraviolet absorber, and a dispersant.

Examples of the penetrant used in the ink composition of the present invention include glycol ethers such as diethylene glycol monobutyl ether, alkylene glycol, polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate,
Examples thereof include sodium oleate and sodium dioctyl sulfosuccinate. The penetrant is added for the purpose of stopping the penetration of the ink composition into the paper by the printing medium and increasing the apparent dryness. These penetrants are present in the ink composition at 0.1
10 to 10% by weight, preferably 1 to 5% by weight. If the content is more than 10% by weight, bleeding of printing and paper missing (print-through) occur, which is not preferable.

As the defoaming agent used in the ink composition of the present invention, various surfactants (anionic, nonionic,
Cationic and zwitterionic surfactants). The defoamer circulates or moves the ink composition,
It is added for the purpose of preventing the generation of bubbles during the production of the ink composition. These surfactants also have the effect of improving the ejection stability of the ink composition and the recorded image.

Specific anionic activators include fatty acid salts, alkyl sulfate salts, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, Alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid Esters and the like are exemplified.

Specific nonionic activators include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester,
Polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based,
A nonionic activator such as a silicon type is exemplified.

Specific examples of the cationic activator include an alkylamine salt, a quaternary ammonium salt, an alkylpyridinium salt, and an alkylimidazolium salt.

Specific examples of zwitterionic activators include alkyl betaine, alkylamine oxide, phosphadylcholine and the like.

These antifoaming agents are used in the ink composition in an amount of 0.1%.
10 to 10% by weight, preferably 1 to 5% by weight.

As the colorant used in the ink composition of the present invention, general pigments and dyes can be used, and as the dye, oily dyes, metal-containing dyes, disperse dyes and the like are used. Although the recorded matter obtained from the ink composition of the present invention is difficult to visually discriminate, the recorded matter is easily distinguished by using a coloring agent. However, it is necessary to limit the use of the ink composition to 3% or less, and preferably 2% or less, in order to sufficiently exhibit light emission characteristics. These dyes are preferably purified dyes from which inorganic salts have been removed.

As the ultraviolet absorber used in the ink composition of the present invention, o-hydroxybenzophenone, 2-
Hydroxy-4-n-octoxybenzophenone, 2-
Benzophenones such as hydroxy-4-methoxybenzophenone, 2- (2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy- 3'-t-butyl-5'-methylphenyl)-
Benzotriazoles such as 5-chlorobenzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenylacrylate, 5-ethylhexyl-2-cyano-3 Cyanoacrylates such as 1,3-diphenyl acrylate, salicylic acids such as phenylsalicylate and 4-t-butylphenylsalicylate, 2-ethyl-5 '
Examples thereof include anilide oxalates such as -t-butyl-2'-ethoxy-N, N'-diphenyloxalamide, and inorganic oxides such as zinc oxide, titanium oxide and zirconium oxide. The light stability can be improved by adding an ultraviolet absorber.

The dispersants used in the ink composition of the present invention include rosin acid soap, stearic acid soap, oleic acid soap, Na-di-β-naphthylmethane disulfate, Na-lauryl sulfate, and Na-diethylhexyl sulfo. Surfactants such as succinate and Na-dioctylsulfosuccinate are exemplified.

Further, in addition to the above additives, conductivity adjusting agents such as lithium nitrate, ammonium formate, ammonium acetate, lithium halide and sodium thiocyanate, preservatives and the like may be added to the ink composition of the present invention. It is possible. Their use amount in the ink composition is 0.0
Amounts of 1 to 3% by weight are exemplified.

As a method of producing the ink composition, a rare earth complex, a solvent, a binder, an additive, and the like are mixed as needed, dissolved by stirring, diluted if necessary, and mixed with other additives. Obtain an ink composition. Mixing and stirring can be performed by a high-speed disperser, emulsifier, or the like, in addition to stirring by a stirrer using a normal blade. The mixed ink composition is filtered sufficiently before or after dilution with a filter having a pore size of 3 μm or less as necessary. Preferably, it is filtered with a filter of 1.0 μ or less. Prior to filtration of the filter, filtration by centrifugation can also be used,
Clogging during filtration by the filter is reduced, and the usable period of the filter is extended.

The recorded matter obtained from the ink composition of the present invention is colorless under ordinary light, but has a high luminous property when irradiated with light of a specific wavelength, and is used for hidden letters, symbols, cardboard, etc. The present invention can be used in the field of hard-to-recognize recordings such as marking, numbering, and barcodes (for example, for customer barcodes to be printed on mail), and recordings having a security function.

[0072]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Production Example 1 Synthesis of C ₈ F ₁₇ SO ₂ NHSO ₂ C ₈ F ₁₇ (POS) Under a nitrogen atmosphere, 18 mmol of C ₈ F ₁₇ SO ₂ NHN
[(CH ₃ ) ₃ Si] ₂ NH (18 ml, 86.5)
mmol) was added dropwise. Add 2 ml of dioxane and add 12
After refluxing at 0 ° C. for 8 hours, [(CH ₃ ) ₃ Si] ₂
NH was distilled off and vacuum drying was performed for 12 hours. 30 ml of dry acetonitrile and C ₈ F ₁₇ SO ₂ F (21 mmol
1) was added and refluxed at 100 ° C. for 48 hours. Thereafter, acetonitrile was distilled off, protonation was performed using sulfuric acid, and the target product (white solid, yield: 12%) was obtained by ether extraction and sublimation.

IR (cm ^-1 ): 1373 (S = Os
t. ), 1237 (C-Fst.), 1206 (C-Fs.)
t. ), 1151 (S = Ost.) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ;
ppm): -79.51 (3F), -111.59 (2
F), -118.43 (2F), -120.10 (6
F), -121.06 (2F), -124.59 (2
F).

Production Example 2 Synthesis of C ₄ F ₉ SO ₂ NHSO ₂ C ₄ F ₉ (PBS) Instead of C ₆ F ₁₃ SO ₂ NHNa and C ₆ F ₁₃ SO ₂ F, each was C ₄ F ₉ SO ₂ NHNa. And C ₄ F ₉ SO ₂
Except for using F, C ₄ F ₉ SO ₂ N
HSO ₂ C ₄ F ₉ (white solid, yield 26%) was obtained.

IR (cm ^-1 ): 1373 (S = Os
t. ), 1237 (C-Fst.), 1206 (C-Fs.)
t. ), 1151 (S = Ost.) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ;
ppm): -79.31 (6F), -111.47 (4
F), -119.18 (4F), -124.19 (4
F).

Production Example 3 Synthesis of Nd (POS) ₃ Complex C ₈ F ₁₇ SO ₂ NHSO ₂ C ₈ F ₁₇ obtained in Production Example 1
(0.8 g, 0.82 mmol) was dissolved in 30 ml of distilled water, Nd ₂ O ₃ (46 mg, 0.14 mmol) was added, and the mixture was stirred at room temperature for 3 days. The precipitated solid was filtered, washed with water, dissolved in methanol, centrifuged, and filtered to remove unreacted Nd ₂ O ₃ . The target complex (Nd (POS) ₃ ; red-purple solid) was obtained by distilling off methanol.
The obtained complex was confirmed to have no water by differential thermal analysis (DSC).

IR (cm ^-1 ): 3449 (O-Hs)
t. ), 1368 (S = Ost.), 1237 (C-Fs)
t. ), 1150 (S = Ost.) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ;
ppm): -79.33 (3F), -111.24 (2
F), -118.07 (2F), -119.81 (6
F), -120.78 (2F), -124.29 (2
F). By performing the same operation using PBS instead of POS, a red-purple solid of Nd (PBS) ₃ was obtained.

Production Example 4 Synthesis of Eu (POS) ₃ Complex C ₈ F ₁₇ SO ₂ NHSO ₂ C ₈ F ₁₇ obtained in Production Example 1
(0.8 g, 0.82 mmol) was dissolved in 30 ml of distilled water, Eu ₂ O ₃ (50 mg, 0.14 mmol) was added, and the mixture was stirred at room temperature for 3 days. The precipitated solid was filtered, washed with water, dissolved in methanol, centrifuged, and filtered to remove unreacted Eu ₂ O ₃ . The target complex (Eu (POS) ₃ ; white solid) was obtained by distilling off methanol. The obtained complex was confirmed to have no water by differential thermal analysis (DSC).

IR (cm ^-1 ): 1354 (S = Os
t. ), 1237 (C-Fst.), 1209 (S-Fs.)
t. ), 1056 (S = Ost.) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ;
ppm): -79.2 (3F), -111.33 (2
F), -118.15 (2F), -119.87 (4
F), -120.8 (2F), -124.29 (2
F).

Production Example 5 Synthesis of Tb (POS) ₃ Complex As a rare earth metal compound, Tb ₄ O ₇ (60 mg, 0.1 mg) was used.
A target complex (Tb (POS) ₃ ; white crystal) was obtained in the same manner as in Production Example 4 except that 82 mmol) was used.
The obtained complex was confirmed to have no water by differential thermal analysis (DSC).

IR (cm ^-1 ): 1353 (S = Os
t. ), 1243 (C-Fst.), 1208 (C-Fs.)
t. ), 1056 (S = Ost.) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ;
ppm): -79.3 (3F), -111.1 (2
F), -118.0 (2F), -119.9 (4F),
-120.9 (2F), -124.4 (2F).

[0083] Production Example _{6 Nd (O 3 SC 8 F} 17) Nd 2 O 3 of 3 · 6D ₂ O 0.56g penta perfluorooctane sulfonic acid solution 30ml Synthesis 0.34M of (1.72 mmol)
After stirring for 24 hours at room temperature, a purple solid was obtained. This was filtered, washed with water, and recrystallized with a mixed solvent of chloroform and methanol to obtain purple needle crystals. The obtained crystals were dried at 5 mmHg for 2 days. Yield 30%. From the results of TG-DTA measurement, the obtained crystals were confirmed to be hexahydrate.

IR (cm ^-1 ): 3432 (O-Hs)
t. ), 1637 (O-Hδ), 1241 (C-Fs
t. ), 1204 (C-Fst.), 1152 (S-Os
t. ) ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ;
ppm): -79.61 (3F), -112.85 (2
F), -119.16 (2F), -120.30 (6
F), -121.19 (2F), -124.67 (2
F)

[0085] The resulting _{Nd (O 3 SC 8 F 17} ) 3 · 6
H ₂ O (80 mg) was dissolved in CD ₃ OD (2.0 ml), degassed at −78 ° C., and left at room temperature for 24 hours.
Then, CD ₃ OD is distilled off to obtain Nd (O ₃ S
To obtain a _{C 8 F 17) 3 · 6D} 2 O. This compound is converted to H-NM
By measuring with R, it was confirmed that H ₂ O was replaced with D ₂ O.

Production Example 7 Synthesis of Nd (PDDH) ₃ Journal of Chemical and Engineering Data, Vol.
As described in No. 3 (1971), 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9,
10,10,10-pentafluoro-1-pentafluorophenyl-1,3-decanthion (hereinafter abbreviated as “PDDH”) was produced. PDDH
(0.52 g) was dissolved in ether, an aqueous solution of neodymium nitrate hexahydrate (880 mg) was added, and the mixture was vigorously stirred at room temperature for 3 days. The precipitated solid was filtered, washed with water, dissolved in methanol, centrifuged, and filtered to remove unreacted neodymium nitrate. The target complex (Nd (PDDH) ₃ ; red-purple solid) was obtained by distilling off methanol. The obtained complex was confirmed to have no water by differential thermal analysis (DSC).

IR (cm ^-1 ): 3410 (OH), 1
623 (C = O), 1513 (C-H), 1243, 1
211 (CF), 1148 (CO). ¹⁹ F-NMR (acetone-d ₆ , standard substance C ₆ F ₆ ;
ppm): -161 (d, 2F, m-F), -153
(D, 1F, p-F), -140 (d, 2F, o-
F), - 124~-114 ( m, 12F, CF 2), -
_{79.4 (d, 3F, CF 3} ). ¹ H-NMR δ 6.00 ppm (1H, S, C-
H).

Production Example 8 Synthesis of TBSA In a three-necked flask (100 ml) equipped with a cooling tube, 30 ml of THF was added under a nitrogen stream, and then CF ₃ C was added.
ONH ₂ (6.44 g, 57 mmol) (manufactured by Wako Pure Chemical Industries) and triethylamine (11.5 g, 114 mm)
ol) was dissolved and stirred at 65 ° C. for 1 hour. Subsequently, C ₄ F ₉ SO ₂ F (17.2 g, 57 mmol)
(Manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was refluxed under normal pressure for 30 hours. Subsequently, THF was distilled off under reduced pressure, then the residue was dissolved in ether, and the ether layer was washed with ion-exchanged water. Further, after drying the ether over magnesium sulfate, the ether was distilled off under reduced pressure. Subsequently, vacuum distillation (220 ° C., 3 mmHg) by, pale yellow liquid _{[C 4 F 9 SO 2 NCOCF} 3] - Et 3 NH +
(Hereinafter, abbreviated as TBSA) was obtained at a yield of 24.6 g and 87%.

IR (painting): 3110, 2822,
1668, 1326, 1236, 1197, 1141c
m ^-1 . ¹⁹ F-NMR (acetone-d ₆ , standard compound hexafluorobenzene, δ, ppm) -74.20 (3
F), -79.37 (3F), -112.42 (2
F), -119.23 (2F), -124.19 (2
F). ¹ H-NMR (acetone-d ₆ , δ, ppm): 1.4
(3H x 3), 3.5 (2H x 3), 8.0 (NH). ¹³ C-NMR (acetone-d ₆ , δ, ppm): 10
8-124 (C3F8), 141.26 (CF2), 1
37.46 (CF2), 162.78 (CO). Elemental analysis value C ₁₂ H ₁₆ O ₃ N ₂ F ₁₂ S: Theoretical value (%) C: 29.03, H: 3.26, N: 5.
64. Obtained value (%) C: 28.89, H: 3.35, N: 5.
81. UV (λmax): 334 nm (acetone).

Production Example 9 Synthesis of HBSB In a three-necked flask (100 ml) equipped with a cooling tube, THF (30 ml) was added under a nitrogen stream, and then C ₄
F ₉ SO ₂ F (17.2 g, 57 mmol) (manufactured by Tokyo Kasei) and triethylamine (11.5 g, 114 m)
mol) was stirred and stirred at room temperature for 1 hour. Subsequently, C ₃ F ₇ CONH ₂ (11.86 g, 57 mmo
l) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature under normal pressure for 30 hours. Subsequently, THF was distilled off under reduced pressure, then the residue was dissolved in ether, and the ether layer was washed with ion-exchanged water. Further, after drying the ether over magnesium sulfate, the ether was distilled off under reduced pressure. Subsequently, light-colored liquid [C ₄ F ₉ SO ₂ NCOC ₃ F ₇ ] was obtained by distillation under reduced pressure (260 ° C., 3 mmHg).
^- Et ₃ NH ⁺ (hereinafter, abbreviated as HBSB) 22.75
g, 81% yield.

IR (painting): 3102, 2821,
1667, 1325, 1217, 1139 cm ^-1 . ¹⁹ F-NMR (acetone-d ₆ , δ, ppm) -7
9.29 (3F, 3F), -112.50 (2F),-
115.75 (2F), -119.10 (2F), -1
24.15 (2F), -124.73 (2F). ¹ H-NMR (acetone-d ₆ , δ, ppm): 1.4
(3H x 3), 3.4 (2H x 3), 7.8 (NH). UV (λmax): 334 nm (acetone).

Production Example 10 Production of Nd (PMS) ₃ Commercially available CF ₃ SO ₂ NHSO ₂ CF ₃ (g, 1.12 m
mol) (manufactured by Fluka) in 30 ml of distilled water.
₂ O ₃ (46 mg, 0.14 mmol) was added and stirred at room temperature for 3 days. After distilling off water, the precipitated solid was washed with methylene chloride, and the obtained solid was further dissolved in methanol and filtered to remove unreacted Nd ₂ O ₃ . The target Nd (PMS) ₃ · nH ₂ is obtained by distilling off methanol.
O: A red-purple solid was obtained. ¹⁹ F-NMR: -77.53 (m, 6F, CF ₃ ) ¹ H-NMR: none (2.06 ppm as crystallization water) UV (MeOH): 352, 522, 576, 744;
801 and 865 nm

Production Example 11 Eu (PMS) ₃ : a white solid was obtained in the same manner. ¹⁹ F-NMR: -77.51 (m, 6F, CF ₃ ) ¹ H-NMR: none (2.06 ppm as water of crystallization) UV (MeOH): 362, 376, 394, 465;
527 nm

Production Example 12 Synthesis of Nd (HBSB) ₃ The HBSB obtained in Production Example 10 (2.92 g, 4.9 m
mol) with neodymium nitrate hexahydrate (0.80 g, 1.
(8 mmol) in acetone (8 ml) and stirred vigorously at room temperature for 3 days. Subsequently, after the acetone was distilled off under reduced pressure, the residue was dissolved in ether, and the ether layer was washed with ion-exchanged water. After the ether was distilled off under reduced pressure, the residue was added with a chloroform / hexane solution and precipitated to precipitate the desired complex (Nd (HBSB) ₃ : blue-violet solid, 60 mg, 0.04 mmol, yield 2.3%).
I got

[0095]¹⁹F-NMR (acetone-d₆, Δ, p
pm) -79.13 (t, 3F, CF ₃), -79.4
2 (t, 3F, CF₃), -112.88 (br, 2
F, CF ₂), -115.58 (br, 2F, C
F₂), -119.93 (br, 2F, CF₂), -1
24.39 (t, 2F, CF₂), -124.62
(T, 2F, CF₂).

Production Example 13 Synthesis of Eu (TBSA) ₃ TBSA obtained in Production Example 9 (6.9 g, 13.9 mm)
ol) was converted to europium nitrate hexahydrate (2.1 g, 4.g).
(6 mmol) in acetone (10 ml) and stirred vigorously at room temperature for 3 days. Subsequently, after the acetone was distilled off under reduced pressure, the residue was dissolved in ether, and the ether layer was washed with ion-exchanged water. After the ether was distilled off under reduced pressure, the residue was added with a chloroform / hexane solution and precipitated to give the desired complex (Eu (TBSA) ₃ : white solid, 240 mg, 0.18 mmol, yield 10.2).
%).

[0097]¹⁹F-NMR (acetone-d₆, Δ, p
pm): -74.20 (t, 3F, CF₃), -79.
31 (t, 3F, CF₃), -112.21 (t, 2
F, CF ₂), -118.92 (br, 2F, C
F₂), -124.11 (br, 2F, CF₂).

Test Example 1 Eu (POS) ₃ , Nd (PBS) ₃ , Nd (O ₃ SC ₈ F) obtained in Production Examples
_{17) 3, Nd (PMS)} 3, Nd (HBSB) 3, Eu (TBSA) 3, known in the literature Eu (HFA-D) ₃ and Nd (HFA-D) ₃ quantum yield in various solutions, Table 1 shows the emission lifetime. The concentration of the solution is 0.05
Mol / l. The excitation wavelength (nm) and emission wavelength (μm) of each complex were 585 nm and 1.0 nm for the Nd complex, respectively.
6 μm, Eu complex at 394 nm and 0.618 μm. Detection is N
The d complex was performed using a Ge photodiode, and the Eu complex was performed using a photomultiplier.

[0099]

TABLE 1 complex Solvent quantum yield emission lifetime (%) (μs) Eu ( POS) 3 DMSO-d 6 56.8 1500 Nd (PBS) 3 Acetone _{-d 6 2.5 1 Nd (O 3} SC 8 _{F 17) 3 DMSO-d 6} 4.1 - Nd (PMS) 3 DMSO-d 6 3.3 - Nd (HBSB) 3 DMSO-d 6 3.3 - Eu (TBSA) 3 DMSO-d 6 72 - Nd _{(HFA) 3} ^Note acetone _{-d 6 0.4 - Nd (HFA)} 3 DMSO-d 6 1.1 - Eu (HFA-D) 3 ^Note _DMSO-d 6 60 - Note) hexafluoroacetylacetone (hereinafter "HFA" And deuterated ones are hereinafter referred to as [HFA-D]) and neodymium nitrate or europium oxide in the same manner as in Production Example 3 or Production Example 4, respectively.

[0100] Incidentally, DMSO-d ₆ suspension of the rare earth complex was prepared by allowing to stand at room temperature for 2 hours was suspended rare earth complex (1 part) in DMSO-d _{6 (0.5} parts) .

Example 1 5.0 parts Eu (POS) ₃ Varnish for aqueous gravure (styrene acrylic acid type) 50.0 parts 3 mm Φ glass beads 50.0 parts

The above compound was placed in a 225 ml mayonnaise bottle, dispersed with a paint conditioner for 90 minutes, 45.0 parts of an additional varnish was added, and the mixture was further dispersed with a paint conditioner for 10 minutes, and the glass beads were filtered off. Thus, a fluorescent aqueous gravure ink was obtained. The ink was spread on manila board paper with a # 3 bar coater. This coated paper cannot be distinguished from the paper before coating under normal light (fluorescent light),
When illuminated by an ultraviolet lamp, it emitted a bright red emission color. Further, as a result of visually observing the change in the color fading of the fluorescence after exposing the coated paper for 100 hours without water injection using a sunshine weather meter, no decrease in the fluorescence was observed.

Example 2 Tb (POS) ₃ 3.0 parts Acrylic varnish (xylene solution of methyl methacrylate) 72.0 parts Methyl ethyl ketone 25.0 parts

The above compound was dissolved in a stirrer for 20 minutes and then filtered through a 0.45 μm membrane filter to produce an ink composition. The ink was applied on flat glass. This glass plate could not be distinguished from the glass plate before coating under normal light (fluorescent lamp), but when illuminated by an ultraviolet lamp, it emitted a bright green luminescent color.

Example 3 Nd (O ₃ SC ₈ F ₁₇ ) ₃ in DMSO-d ₆ suspension 15.0 parts Rosin phenol resin-based offset varnish 85.0 parts

The above compound was subjected to Hoover-type Mahler
The ink was prepared by kneading at 0 rotation, 1501 bs, and 4 rotations, and the ink was adjusted on an art paper using a small rotary printing press (RI tester). This coated paper cannot be distinguished from the paper before coating under normal light (fluorescent lamp), but emission of a wavelength of 1060 nm was confirmed by the germanium photodiode.

Example 4 Nd (PDDH) ₃ in DMSO-d ₆ suspension 1.0 part Petroleum-based solvent (Shellsol AB manufactured by Shell Chemical) 30.0 parts Dimethyl sulfoxide 15.0 parts N-methyl- 54.0 parts of 2-pyrrolidone

The above compound was dissolved in a stirrer for 20 minutes and then filtered through a 0.45 μm membrane filter to produce an ink composition. This ink was placed in a cartridge of "deskwriter" manufactured by Hewlett-Packard Company and recorded on plain paper. This plain paper cannot be distinguished from the paper before coating under normal light (fluorescent light), but emission of a wavelength of 1060 nm was confirmed by the germanium photodiode. I dripped water on the recording surface and checked for ink bleeding.
The ink did not bleed or flow out and had sufficient water resistance.

Example 5 Nd (PMS) ₃ in DMSO-d ₆ suspension 1.0 part Methyl ethyl ketone 78.0 parts Ethyl acetate 5.0 parts N-methyl-2-pyrrolidone 15.0 parts Sodium thiocyanate 0 copies

The above compound was dissolved in a stirrer for 20 minutes and then filtered through a 0.45 μm membrane filter to produce an ink composition. The ink was put into a Hitachi IJ Printer manufactured by Hitachi, Ltd., and recording was performed on plain paper. This plain paper is indistinguishable from the paper before coating under normal light (fluorescent light).
Emission at a wavelength of 060 nm was confirmed.

Example 6 Nd (PBS) ₃ 1.0 part Vinyl chloride-vinyl acetate copolymer (VYMH manufactured by Union Carbide) 1.0 part Methyl ethyl ketone 80.0 parts Ethyl acetate 11.0 parts N-methyl-2 -Pyrrolidone 2.0 parts Ethyl alcohol 4.0 parts Sodium thiocyanate 1.0 part

The above compound was dissolved in a stirrer for 30 minutes and then filtered through a 0.45 μm membrane filter to produce an ink composition. This ink was put into a Hitachi IJ Printer manufactured by Hitachi, Ltd., and recording was performed on the surface of an aluminum plate. This aluminum plate is normal light (fluorescent light)
Below, although it cannot be distinguished from the plate before application, emission of a wavelength of 1060 nm was confirmed by the germanium photodiode.

Example 7 Nd (HBSB) ₃ 0.5 part Vinyl chloride-vinyl acetate copolymer (VYMH manufactured by Union Carbide) 1.0 part Methyl ethyl ketone 80.0 parts Ethyl acetate 11.0 parts N-methyl-2 -Pyrrolidone 1.0 part Ethyl alcohol 5.5 parts Sodium thiocyanate 1.0 part

The above compound was dissolved in a stirrer for 30 minutes and then filtered through a 0.45 μm membrane filter to produce an ink composition. This ink was put into a Hitachi IJ Printer manufactured by Hitachi, Ltd., and recording was performed on the surface of an aluminum plate. This aluminum plate is normal light (fluorescent light)
Below, although it cannot be distinguished from the plate before application, emission of a wavelength of 1060 nm was confirmed by the germanium photodiode.

Example 8 Eu (TBSA) ₃ in DMSO-d ₆ suspension 0.8 part AT-100 (Acrylic resin solution NV50%, manufactured by Toyo Ink Mfg. Co., Ltd.) 5.0 parts Cyclohexanone 5.0 parts Aluminum Chelating agent (Alkenmer S, manufactured by Kawaken Fine Chemicals) 0.5 part Methyl ethyl ketone 70.0 parts Toluene 5.5 parts Sodium thiocyanate 1.2 parts Ethyl acetate 11.0 parts N-methyl-2-pyrrolidone 1.0 part

To the rare earth complex, the resin solution and the chelating agent, 10 parts of methyl ethyl ketone was added and dissolved well. After dissolution, the mixture was diluted with the remaining solvent, and sodium thiocyanate was added to adjust the ink composition. Thereafter, the mixture was filtered with a 0.8 μm membrane filter, and was then placed in a “Hitachi IJ Printer” manufactured by Hitachi, Ltd. to record on the surface of the steel sheet.
When the recorded matter was irradiated with an ultraviolet lamp, red light emission was confirmed.

[0117] Example 9 Eu _{(HFA-D) 3} of _{DMSO-d 6} suspension 0.8 parts Diethylene glycol monobutyl ether 5.2 parts of dimethyl sulfoxide 15.0 parts N- methyl-2-pyrrolidone 79.0 parts

The above compound was dissolved in a stirrer for 20 minutes and filtered through a 0.45 μm membrane filter to produce an ink composition. This ink was placed in a cartridge of "deskwriter" manufactured by Hewlett-Packard Company, and recording was performed on plain paper. When this recorded matter was irradiated with an ultraviolet lamp, red light emission was confirmed.

Comparative Example 1 Eu (HFA-D) ₃ 0.5 part Diethylene glycol monobutyl ether 5.5 parts Dimethyl sulfoxide 15.0 parts N-methyl-2-pyrrolidone 79.0 parts

Using the above compound, an ink composition was produced in the same manner as in Example 9. This ink was further recorded on plain paper in the same manner as in Example 9, and when checked with a UV lamp, it emitted red light, but its intensity was much weaker than that of Example 9.

Comparison between Example 9 and Comparative Example 1 shows that DMSO-d
The rare earth complex suspended in ₆ compared to rare earth complex which is not suspended in DMSO-d ₆ by using the ink composition it is found that the luminous intensity increases.

[0122]

The luminescent ink composition of the present invention is colorless under normal light, but emits light upon irradiation with light of a specific wavelength, and is therefore a very valuable compound. Printed matter, film, etc. using this ink cannot recognize the color under normal light, so it is possible to perform recording that is difficult to distinguish from the base, and it can be used in a system that reads with a light receiving element as a special luminescent recording material It can be used for printing on hidden characters and security.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H048 AA03 AB92 AB99 VA00 VA11 VA20 VA30 VA40 VA70 VB20 4J039 AD03 AD05 AD08 AD10 AE02 AF01 BA25 BC01 BC05 BC06 BC12 BC16 BC20 BC22 BC32 BC49 BC53 BC54 BC55 BC56 BC59 BC63 BE02 BE12 BE29 EA21 FA02 GA02 GA03 GA04 GA21 GA24 GA26 GA27 GA34

Claims (8)

[Claims] 1. General formula (1) [Wherein, M represents a rare earth metal, and n1 represents 2 or 3.
n2 represents 2, 3 or 4. Rf ¹ and Rf ² are the same or different and each represent a C ₁ -C ₂₂ aliphatic group containing no hydrogen atom, an aromatic group containing no hydrogen atom, or a heterocyclic group containing no hydrogen atom, and X ¹ and X ^{1 2} is the same or different and represents any one of a group IVA atom, a group VA atom excluding nitrogen, and a group VIA atom excluding oxygen; n3 and n4 each represent 0 or 1;
Y is CZ (Z represents a C ₁ -C ₂₂ aliphatic group containing no deuterium atom, halogen atom or hydrogen atom), N,
Indicates P, As, Sb or Bi. However, when X ¹ is a carbon atom n3 is 0, when X ² is a carbon atom n4 is 0. When X ¹ and X ² are simultaneously carbon atoms, Rf ¹ ,
At least one of Rf ^{2 is} an aromatic group containing no hydrogen atom. ] Or general formula (2) Wherein M, n1 and n2 are as defined above. Rf ³ represents a C _{1 to} C ₂₂ aliphatic group containing no hydrogen atom, an aromatic group containing no hydrogen atom, or a heterocyclic group containing no hydrogen atom, and X ³ represents a group IVA atom and V excluding nitrogen.
Indicates any of Group A atoms and Group VIA atoms excluding oxygen. A luminescent ink composition comprising the rare earth complex represented by the formula: 2. The composition according to claim 1, further comprising a polar solvent.
3. The luminescent ink composition according to item 1. 3. The rare earth complex represented by the general formula (3) Wherein M, Rf ¹ , Rf ² , n1 and n2 are as defined above. The luminescent ink composition according to claim 1, wherein the luminescent ink composition is a complex represented by the following formula: 4. The rare earth complex represented by the general formula (4) Wherein M, Rf ¹ , Rf ² , n1 and n2 are as defined above. The luminescent ink composition according to claim 1, wherein the luminescent ink composition is a complex represented by the following formula: 5. The rare earth complex represented by the general formula (5) Wherein M, Rf ¹ , Rf ² , n1 and n2 are as defined above. The luminescent ink composition according to claim 1, wherein the luminescent ink composition is a complex represented by the following formula: 6. The general formula (6) Wherein M, n1 and n2 are as defined above.
Z ′ represents a hydrogen atom or Z (as described above). Rf ⁴ and Rf ⁵ are the same or different and are each a hydrogen atom-free C
Aliphatic group of ₁ -C _22, showing a heterocyclic group containing no aromatic group or a hydrogen atom do not contain hydrogen atoms. A luminescent ink composition comprising a dispersion or suspension mixture of the rare earth complex represented by the formula (1) and a polar solvent. 7. polar solvent luminous ink composition according to any one of claims 2-6 is DMSO-d _6. 8. The luminescent ink composition according to claim 1, comprising 0.005 to 20.0% by weight of a rare earth complex.