JP2002037791A - Red fluorescent material and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a red fluorescent material having improved solubility in solvents each containing water, and to develop an ink composition using the same. SOLUTION: A red fluorescent material represented by general formula (1) (X is an aromatic ring or heterocyclic group which may have one or more substituents; Y is a 1 to 10C fluorohydrocarbon group; R1 to R4 are each independently H, an alkyl or an aralkyl which has at least one hydrophilicity imparting group and may further have one or more substituents, or R1 to R4 may be bound to each other to form one or more rings), and a composition containing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a compound which is colorless under visible light and develops and visualizes under ultraviolet irradiation.
And compositions thereof. More specifically, the present invention relates to a red fluorescent material having excellent solvent solubility, particularly excellent solubility in a solvent containing water, and a composition thereof.

[0002]

2. Description of the Related Art Compounds which are colorless under visible light such as tris (thenoyltrifluoroacetonate) europium complex and tris (benzoyltrifluoroacetonate) europium complex and which develop a red color under ultraviolet irradiation are known. Application to various inks, etc. is planned, but complexes with excellent stability and durability are insufficient in solubility in solvents, especially in solvents containing water, and their applications have been limited. . For example, JP-A-8-253715, JP-A-8-
No. 239609 describes an application to a solvent containing water, but in fact, sufficient solubility has not yet been obtained.

[0003]

SUMMARY OF THE INVENTION The present invention provides a red fluorescent material which emits red light when irradiated with ultraviolet light, has excellent stability, and has improved solubility in solvents and the like, particularly improved solubility in solvents containing water. And a composition containing the same.

[0004]

As a result of the present inventors' intensive efforts to solve the above problems, the europium complex having a quaternary salt having a hydrophilicity-imparting group as a counter ion is excellent in solubility. This led to the completion of the present invention. That is, the present invention provides (1) an anionic europium complex, which is a quaternary salt having a counter ion having at least one hydrophilic group, (2) a red fluorescent material represented by the following general formula (1),

[0005]

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(Wherein X represents an aromatic ring or a heterocyclic group which may have a substituent, Y represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and R 1 to R 4 each independently represent at least 1 One represents an alkyl group, an aralkyl group or a hydrogen atom which has a hydrophilicity-imparting group and may have a substituent, and may be bonded to each other to form a ring.) (3) The hydrophilicity-imparting group is a sulfone Acid group, carboxyl group,
The red fluorescent material according to (2), which is a hydroxyl group or a phosphonic acid group. (4) The red fluorescent material according to (2) or (3), wherein X is an optionally substituted benzene ring group, naphthalene ring group, pyridine ring, thiophene ring group or furan ring group. (5) The red fluorescent material according to (2) to (4), wherein Y is a trifluoromethyl group. (6) A composition comprising the red fluorescent material according to any one of (1) to (5). (7) An ink composition comprising the red fluorescent material according to any one of (1) to (5). (8) The ink composition according to (7), containing water and an organic solvent. (9) For inkjet recording (7) to (8)
The ink composition according to any one of the above. (10) In an ink jet recording method for recording on a recording material by discharging ink droplets according to a recording signal,
(7) An inkjet recording method using the ink composition according to any one of (9) to (9). (11) The ink jet recording method according to (10), wherein the recording material is an information transmission sheet. (12) The ink jet recording method according to (11), wherein the information transmission sheet is a surface-treated sheet. (13) An ink jet printer loaded with a container containing the ink composition according to any one of (7) to (9).

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. The red fluorescent material of the present invention is represented by the general formula (1), and X in the anion portion in the general formula (1) includes an aromatic ring or a hetero ring which may have a substituent. As an aromatic ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, an azulene ring, a phenanthrene ring and the like, and as a heterocyclic ring, for example, a pyridine ring, a thiophene ring,
Examples thereof include a furan ring, a pyrazine ring, a thiazole ring, an oxazole ring, a quinoline ring, and an indole ring. Preferable examples include a benzene ring, a naphthalene ring, a pyridine ring, a thiophene ring, and a furan ring. Examples of the substituent of X include a hydrogen atom, an alkyl group, an alkoxyl group, an aromatic ring group, a heterocyclic group, an amino group, an alkylamino group, a dialkylamino group, a hydroxyl group, an aralkyl group, and a halogen atom. Preferred are a hydrogen atom, a halogen atom, an alkyl group and the like.

Y represents a fluorocarbon group having 1 to 10 carbon atoms, and specific examples thereof include a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a heptadecafluorooctyl group; Or a monofluoromethyl group, a difluoromethyl group, a trifluoroethyl group, a tetrafluoropropyl group, an octafluoropentyl group, or the like. It is preferably a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptadecafluorooctyl group, and more preferably a trifluoromethyl group.

[0009] R1 in the cation moiety in the general formula (1)
~ R4 each independently has at least one hydrophilicity-imparting group, may represent a saturated or unsaturated alkyl group, an aralkyl group or a hydrogen atom which may have a substituent, and are bonded to each other to form a ring. Is also good. Specific examples of the hydrophilicity-imparting group include a hydroxyl group, a carboxyl group, a sulfonic acid group,
Examples include a phosphonic acid group, preferably a hydroxyl group, a carboxylic acid group, and a sulfonic acid group, and more preferably a hydroxyl group and a carboxylic acid group. The carboxyl group, sulfonic acid group and phosphonic acid group may be free or not, and may be a general cation as a counter ion. As a saturated or unsaturated alkyl group which may have a substituent, an alkyl group such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group or an allyl group, or an alkyl halide such as a chloroethyl group. Groups, alkoxyalkyl groups such as methoxyethyl groups, and the like, and aralkyl groups such as benzyl groups and phenethyl groups. Further, they may combine with each other to form a ring such as a pyridine ring, a quinoline ring, a pyrimidine ring, and a piperidine ring. The cation represented by the following formula (2) governs the cation moiety.

[0010]

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As specific examples of the cation (counter ion) of the formula (2), when the hydrophilicity-imparting group is a hydroxyl group, tetramethanol ammonium, tetraethanol ammonium, methyl triethanol ammonium, diethyl diethanol ammonium, p-hydroxybenzyl trimethyl ammonium , N-methanolpyridinium, N-dihydroxybenzylpyridinium and the like. When the hydrophilicity-imparting group is a carboxyl group, tetracarboxymethylammonium, tetracarboxyethylammonium, dimethyldicarboxymethylammonium, trimethylcarboxymethylammonium, dimethylallylcarboxyethylammonium, N-carboxymethylpyridinium, N-
Carboxypropylquinolinol and the like.

When the hydrophilicity-imparting group is a sulfonic acid group, examples thereof include tetrasulfopropylammonium, trisulfomethylethylammonium, benzyltrisulfopropylammonium, trimethylsulfopropylammonium, and N-sulfopropylpyridinium. When the hydrophilicity-imparting group is a phosphonic acid group, examples thereof include tetraphosphopropylammonium, tributylphosphoethylammonium, and N-phosphopropylpyridinium. Specific examples of the compound into which two or more kinds of hydrophilicity-imparting groups are introduced include triethanolcarboxymethylammonium, dimethanolcarboxyethylpropylammonium, and the like.

Preferred examples of the cation of the general formula (2) include those having a hydroxyl group such as tetramethanol ammonium, tetraethanol ammonium and methyltriethanol ammonium, and carboxylic acid groups such as dimethyl dicarboxymethyl ammonium and trimethyl carboxymethyl ammonium. One having a sulfonic acid group such as tetrasulfopropylammonium and N-sulfopropylpyridinium; and one having two or more hydrophilic groups such as triethanolcarboxymethylammonium and dimethanolcarboxyethylpropylammonium. More preferably, those having two or more types of hydrophilic groups such as those having a hydroxyl group such as tetraethanolammonium and methyltriethanolammonium, those having a carboxylic acid group such as trimethylcarboxymethylammonium, and the like are exemplified.

The compound of the above general formula (1) is, for example, as shown in the following formula, for example, in an alcohol or acetone solvent, for example, perfluoroalkyl-1- (2-aryl) -1,3-
By reacting butanedione with, for example, europium perchlorate or europium chloride in the presence of sodium hydroxide, the cation represented by the general formula (2) is allowed to act in the form of, for example, an ammonium salt, without isolation or isolation.
It is easily synthesized. However, depending on the structure of the cation, some unstable complexes may be formed, and some may not be stably isolated, but some may be stably isolated by adjusting the pH or temperature. I do.

[0015]

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Table 1 lists examples of the compounds. In this, the benzene ring is Ph, the naphthalene ring is Np, and the pyridine ring is P
y, thiophene ring is Th, furan ring is Fu, benzyl group is Bz
Respectively.

Compound examples

[0018]

【table 1】

At least one of these compounds represented by the general formula (1) is prepared by adjusting various solvents, water, resin binders and other additives such as dyes, pigments and surfactants as required. A composition of a red fluorescent material is obtained and can be used for various paints, inks and the like. In preparing the ink composition of the present invention, the compound or dye mixture of the present invention used preferably has a low inorganic salt content. When used as a water-based ink composition, those having a low inorganic salt content are particularly preferred. The standard is, for example, the total content of sodium chloride and sodium sulfate in the compound or the dye mixture of the present invention.
% By weight, preferably 0.5% by weight or less.

The content of the inorganic salt is, for example, Cl- and SO ₄
²⁺ is ion chromatography, heavy metals are atomic absorption or ICP (Inductively Coupled Plasma) emission analysis,
For Ca ²⁺ and Mg ²⁺ , ion chromatography,
It is measured by an atomic absorption method or an ICP emission spectrometry.

In order to make the ink composition of the present invention a dye having a lower inorganic salt content, a washing treatment with water or, if necessary, the compound of the present invention with a lower alcohol such as methanol, ethanol or isopropanol is used. It is preferable to process.

The ink composition of the present invention is obtained by dissolving the above-mentioned dye component in water and / or an organic solvent. When this ink composition is used in an ink jet recording printer, it is preferable to use a pigment component having a low content of inorganic salts such as metal cation chlorides and sulfates as described above.

The composition of the present invention varies depending on the field of use.
The content is 1 to 10% by weight, preferably about 0.01 to 3% by weight. The ink composition of the present invention may further contain an organic solvent. The content thereof depends on the content of the ink composition, but is generally about 99 to 0% by weight, preferably about 80 to 10% by weight, and most preferably about 70 to 20% by weight. In particular, an ink composition using a photocurable monomer may not contain an organic solvent.
The organic solvent content of the aqueous ink composition is about 99 to 20% by weight, preferably about 80 to 30% by weight or less, and most preferably about 70 to 40% by weight. The ink composition of the present invention may contain a resin binder in an amount of about 0 to 99% by weight, preferably 20% by weight or less, and an ink preparation in an amount of about 0 to 10% by weight, preferably 5% by weight or less. In the case of an aqueous ink composition, the balance other than the above components includes water.

Examples of the organic solvent include C 1 -C 4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, and tert-butanol; N, N-dimethylformamide or N, N-dimethylacetamide. Lower carboxylic acid '(mono or di) lower alkyl amides; lactams such as ε-caprolactam and N-methylpyrrolidin-2-one, preferably 4- to 8-membered lactams;
Cyclic urea such as urea, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimid-2-one, preferably a 5- to 6-membered cyclic urea; acetone, methyl ethyl ketone, 2- A straight carbon chain such as methyl-2-hydroxypentan-4-one has a carbon number of 4
To 7 ketones or keto alcohols; ethers such as tetrahydrofuran and dioxane, preferably 5 to 6
Membered cyclic ether; ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4
-Butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol,
C2 ~ such as dipropylene glycol, thiodiglycol, polyethylene glycol and polypropylene glycol
Mono-, oligo- or polyalkylene glycols or thioglycols having C6 alkylene units; polyols such as glycerin, hexane-1.2.6-triol (preferably triols having 3 to 6 carbon atoms in the carbon chain); ethylene glycol monomethyl- C1 -C4 alkyl ethers of polyhydric alcohols (preferably ethylene glycol or polyethylene glycol) such as ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; γ-butyrolactone or dimethyl sulfoxide,
Examples thereof include ester solvents such as ethyl acetate and butyl acetate, aromatic solvents such as toluene and xylene, halogen solvents such as chloroform, and cellosolve solvents such as methyl cellosolve and butyl cellosolve.

These organic solvents may be used in combination of two or more. Among these, particularly preferred organic solvents as the aqueous ink composition include, for example, methanol, ethanol,
C1 ~ such as propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, etc.
C4 alkanol, N-methylpyrrolidin-2-one,
Mono, di, tri or polyalkylene glycols having C2 -C6 alkylene units (preferably mono, di or triethylene glycol, dipropylene glycol,
Polyethylene glycol having a molecular weight of about 200 to 600), dimethyl sulfoxide, and the like, and particularly, methanol, ethanol, propanol, isopropanol, N-methylpyrrolidin-2-one, diethylene glycol, and dimethyl sulfoxide are preferably used.

Examples of the ink preparation agent for preparing the ink composition include all the components other than the above-mentioned water, pigment component, organic solvent, and water-soluble polymer compound. Rust inhibitors, ultraviolet absorbers, surfactants, and the like. Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol and the like. pH
As the adjusting agent, any substance can be used as long as it can control the pH of the ink within the range of 6 to 10 without adversely affecting the ink to be prepared. Examples thereof include alkanolamines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, and lithium carbonate, sodium carbonate, and potassium carbonate. Examples thereof include carbonates of alkali metals. Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like.

The resin binders that can be used in the present invention include, for example, polyacrylate, polymethacrylate,
Acrylic resin such as polymethyl methacrylate, polyvinyl pyrrolidone, polyvinyl alcohol, polybutyl butyral, polyvinyl acetate, polycarbonate, epoxy resin, urethane resin, nylon resin, for example, celluloses such as methyl cellulose, ethyl cellulose, acetyl cellulose, nitrocellulose, polyolefins And the like. Examples of the varnish for ink include a varnish for polyamide-based oil-based ink, a varnish for cellulose-based ink, and a varnish for acrylic-based ink. A water-soluble polymer compound, particularly when used as an aqueous ink composition,
Binders include, for example, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, anion-modified or anion-modified polyvinyl alcohol, polyethyleneimine, polyvinylpyrrolidone, polyvinylpyrrolidone / vinyl acetate copolymer, methyl vinyl ether / maleic anhydride copolymer, base-containing Polyacrylate, polymethacrylate, acrylic resin such as polymethyl methacrylate, base-containing polyacrylamide,
Examples thereof include those conventionally used in inks for jet printing, such as acrylamide / base-containing ethyl acrylate copolymer, styrene / base-containing maleic acid resin, and urethane resin.

When the resin is contained, for example, a resin such as polystyrene and the red material of the present invention are mixed and melted by heating to form a resin plate by an injection molding machine. For example, a methacrylate monomer and a polymerization initiator are mixed with the red material of the present invention. A resin film or the like can be obtained by mixing the fluorescent material and irradiating it with an ultraviolet lamp to polymerize, mixing polyvinyl pyrrolidone dissolved in a solvent with the red fluorescent material of the present invention, and spin coating. When applied to various ink varnishes, for example, a composition is prepared by dissolving the red light-emitting material of the present invention in a xylene solution of methyl acrylate polymer and methyl ethyl ketone,
It can be obtained by applying it to art paper or the like. In particular, the red fluorescent material of the present invention has high solubility in a solvent containing water, and can be used in combination with a water-soluble solvent to produce an ink that is environmentally friendly, such as reducing the odor and flammability of the solvent.

Specific examples of the recording material used in the ink jet recording method of the present invention include, for example, an information transmission sheet such as paper and film. As the information transmission sheet, those subjected to a surface treatment, specifically, those provided with an ink receiving layer on these substrates are preferable. In the ink receiving layer, for example, by impregnating or coating the above-described base material with a cationic polymer, inorganic fine particles capable of absorbing the dye in the ink such as porous silica, alumina sol, and special ceramics are coated with polyvinyl alcohol or polyvinyl pyrrolidone. It is provided by coating on the surface of the base material together with a hydrophilic polymer such as Further, a fluorescent dye may be applied to improve whiteness. Of course, it can be used for plain paper. Usually, the image is clearer when used for the information transmission sheet provided with the ink receiving layer,
And it is known that water resistance is strong.

In order to record on a recording material by the ink jet recording method of the present invention, for example, a container containing the above-described aqueous ink composition is set in an ink jet printer, and the recording material as described above is used in a usual manner. Just record it.
Examples of the inkjet printer include a piezo-type printer using mechanical vibration and a bubble-jet (registered trademark) type printer using bubbles generated by heating.

[0031]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. In the examples, parts are by weight unless otherwise specified.

Example 1 (Synthesis of Compound (3)) 70 parts of ethanol, 4,4,4-trifluoroalkyl-1-
(2-thienyl) -1,3-butanedione 11 parts, 10%
19 parts of caustic soda were mixed at room temperature, and an aqueous solution in which 4.4 parts of europium chloride hexahydrate was dissolved in 10 parts of water was added dropwise to the solution, and the mixture was stirred for 1 hour. Further, 5.2 parts of an 80% aqueous solution of triethanol methyl ammonium iodide was added.
Stirring was continued for 2 hours. After the reaction, 1000 g of the reaction solution
Was added dropwise, and the precipitated white solid was filtered and dried to obtain 11 parts of a compound (3) represented by the following formula. Absorption spectrum (methanol) Maximum absorption wavelength 340 nm Fluorescence spectrum (methanol) Maximum excitation wavelength 340 nm:
Fluorescence maximum wavelength 614nm Melting point 110 ° C: Decomposition point 256 ° C (using TG-DTA)

[0033]

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Example 2 (Synthesis of Compound (4)) 70 parts of ethanol, 4,4,4-trifluoroalkyl-1-
(2-thienyl) -1,3-butanedione 11 parts, 10%
19 parts of caustic soda were mixed at room temperature, and an aqueous solution in which 4.4 parts of europium chloride hexahydrate was dissolved in 10 parts of water was added dropwise to the solution, and the mixture was stirred for 1 hour. Further, 1.7 parts of betaine was added and stirring was continued for 2 hours. After completion of the reaction,
The solution was dropped into 00 g of ice water, and the precipitated white solid was filtered and dried to obtain 9.6 parts of a compound (3) represented by the following formula. Absorption spectrum (methanol) Maximum absorption wavelength 341 nm Fluorescence spectrum (methanol) Maximum excitation wavelength 340 nm:
Fluorescence maximum wavelength 614nm Melting point around 80 ° C: decomposition point around 263 ° C (using TG-DTA)

[0035]

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Example 3 2 parts of the compound (4) was dissolved in 70 parts of ethanol, 28 parts of water was added and mixed and dissolved, and the solution was filtrated to obtain an ink composition of the present invention. The ink composition of the present invention did not cause precipitation and separation during storage, and did not change in physical properties even after long-term storage. The composition was recorded using an ink jet printer, and it was confirmed that the composition developed well when irradiated with ultraviolet rays.

Example 4 One part of the compound (4) was dissolved in 25 parts of ethanol, and 74 parts of an NC varnish for gravure ink was added and dissolved by stirring to obtain a composition for gravure ink. The ink composition of the present invention did not cause precipitation and separation during storage, and did not change in physical properties even after long-term storage. This composition was spread on art paper with a bar coater. Irradiation with ultraviolet light confirmed that red light emission was excellent.

Example 5 1 part of the compound (4) was dissolved in 80 parts of methyl ethyl ketone, and then 10 parts of ethyl acetate, 6 parts of ethanol, 2 parts of N-methyl-2-pyrrolidone and 1 part of sodium thiocyanate were dissolved.
And 1 part of a vinyl chloride-vinyl acetate copolymer were added, mixed and dissolved, and the solution was subjected to liquid filtration to obtain an ink composition of the present invention. The ink composition of the present invention did not cause precipitation and separation during storage, and did not change in physical properties even after long-term storage. This composition is recorded using an inkjet printer,
Irradiation with ultraviolet light confirmed good color development.

Example 6 0.3 parts of the compound (4) was dissolved in 60 parts of ethanol, 34.7 parts of water and 5 parts of diethylene glycol were mixed and dissolved, and the solution was further passed through a 0.45 micron membrane filter. After fine filtration, the ink composition of the present invention was obtained. This ink composition did not undergo precipitation and separation during storage, and did not change in physical properties even after long-term storage. This composition was applied to an inkjet printer (product name: PI manufactured by NEC).
(CTY100L), inkjet printing of a solid pattern and a bar code was performed on plain paper (Canon Printer Paper A4 (TLB5A4S)). Although the recorded mark could not be recognized under normal light, it was confirmed that the mark was satisfactorily colored red when irradiated with ultraviolet light. Also, cut off the printed barcode, immerse it in water for 2 minutes,
Irradiation of ultraviolet rays to the air-dried product confirmed that there was no bleeding of the bar and that the bar developed well.

Example 7 0.3 parts of the compound (5) was dissolved in 60 parts of ethanol, 34.7 parts of water and 5 parts of diethylene glycol were mixed and dissolved, and the solution was further passed through a 0.45 micron membrane filter. After fine filtration, the ink composition of the present invention was obtained. This ink composition did not undergo precipitation and separation during storage, and did not change in physical properties even after long-term storage. This composition was applied to an inkjet printer (product name: PI manufactured by NEC).
(CTY100L), inkjet printing of a solid pattern and a bar code was performed on plain paper (Canon Printer Paper A4 (TLB5A4S)). Although the recorded mark could not be recognized under normal light, it was confirmed that the mark was satisfactorily colored red when irradiated with ultraviolet light. Also, cut off the printed barcode, immerse it in water for 2 minutes,
Irradiation of ultraviolet light on the air-dried product confirmed that there was no bleeding of the bar and that the bar developed well.

Example 8 0.3 parts of the compound (4) was dissolved in 50 parts of ethanol, and then 44.7 parts of water and polyvinylpyrrolidone (molecular weight: 38) were dissolved.
000) (Product name PVP manufactured by ASP Japan)
K-30) (5.0 parts) was mixed and dissolved, and the solution was subjected to microfiltration with a 0.45 micron membrane filter to obtain an ink composition of the present invention. This ink composition did not undergo precipitation and separation during storage, and did not change in physical properties even after long-term storage. Using an ink-jet printer (PICTY100L, manufactured by NEC), this composition was applied to plain paper (Canon Printer Paper A4 (TL)
B5A4S)), and ink jet recording of a solid pattern and a bar code was performed on three types of paper and film such as an OHP film. Although the recorded mark could not be recognized under normal light, it was confirmed that the mark was satisfactorily colored red when irradiated with ultraviolet light. Further, when the bar code portion was rubbed with a finger immediately after printing, the mark was well colored without being rubbed. Further, the bar code was cut off, immersed in water for 2 minutes, and air-dried, and irradiated with ultraviolet rays. As a result, it was confirmed that the bar did not bleed and that the color developed well.

Example 9 0.3 part of compound (5), 50 parts of ethanol and 44.7 of water
Part, polyvinylpyrrolidone (molecular weight 38,000) (PVP K-30, manufactured by ASP Japan)
5.0 parts were mixed and dissolved, and this solution was subjected to microfiltration with a 0.45 micron membrane filter to obtain an ink composition of the present invention. This ink composition did not undergo precipitation and separation during storage, and did not change in physical properties even after long-term storage. This composition was applied to an ink jet printer (NE
Using plain paper (Canon Printer Paper A4 (TLB5A4
S)), solid pattern and barcode ink jet recording were performed on three types of paper and film of OHP film. Although the recorded mark could not be recognized under normal light, it was confirmed that the mark was satisfactorily colored red when irradiated with ultraviolet light. Further, when the bar code portion was rubbed with a finger immediately after printing, the mark was well colored without being rubbed. In addition, cut off the bar code, immerse in water for 2 minutes,
Irradiation of ultraviolet light on the air-dried product confirmed that there was no bleeding of the bar and that the bar developed well.

[0043]

The red fluorescent material of the present invention and the composition containing the same are substantially invisible in the visible light region and emit red light when irradiated with ultraviolet light. Since the printed marks cannot be recognized under normal light, the sensor can be used with a good sensitivity without affecting the appearance and without affecting the background, even for media containing fluorescent dyes to increase the whiteness. It is possible to detect. Therefore, the composition of the present invention can be used for a printed matter relating to hidden characters and security, which has a sensor reading function. Furthermore, the red fluorescent material of the present invention and the composition containing them are excellent in stability, and have improved solvent solubility, especially solubility in a solvent containing water, as compared with conventional ones. , And compositions containing it. By using this red fluorescent material, it is possible to handle non-dangerous substances from the viewpoint of safety because the solubility is high and the stability of the composition is improved and the applicable range is expanded. High utility value.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 213/26 C07D 307/42 4H006 307/42 333/16 4H048 333/16 C09D 11/00 4J039 C09D 11 / 00 C09K 11/06 660 C09K 11/06 660 C07C 49/92 // C07C 49/92 215/08 215/08 229/12 229/12 B41J 3/04 101Y F-term (reference) 2C056 FC01 2H086 BA01 BA15 BA33 BA35 BA53 BA56 4C023 BA04 4C037 HA04 4C055 AA01 BA01 CA02 CA16 CB13 DA01 GA02 4H006 AA01 AB92 BN10 BS10 BU30 BU50 4H048 AA01 AB92 VA70 VB10 4J039 BC05 BC07 BC19 BC31 BC33 BC54 BC55 BC56 BC59 BC24 EA15 EA28

Claims (13)

[Claims] 1. An anionic europium complex wherein the counter ion is a quaternary salt having at least one hydrophilicity-imparting group. 2. A red fluorescent material represented by the following general formula (1). Embedded image (Wherein X represents an aromatic ring or a heterocyclic group which may have a substituent, Y represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms, and R 1 to R 4 each independently represent at least one hydrophilic group. An alkyl group, an aralkyl group, or a hydrogen atom, which has a property-imparting group and may have a substituent, and may be bonded to each other to form a ring.) 3. The red fluorescent material according to claim 2, wherein the hydrophilicity-imparting group is a sulfonic acid group, a carboxyl group, a hydroxyl group, or a phosphonic acid group. 4. A benzene ring group wherein X may have a substituent,
4. The red fluorescent material according to claim 2, which is a naphthalene ring group, a pyridine ring group, a thiophene ring group or a furan ring group. 5. The red fluorescent material according to claim 2, wherein Y is a trifluoromethyl group. 6. A composition comprising the red fluorescent material according to any one of claims 1 to 5. 7. An ink composition comprising the red fluorescent material according to any one of claims 1 to 5. 8. The ink composition according to claim 7, comprising water and an organic solvent. 9. The ink composition according to claim 7, which is for inkjet recording. 10. An ink jet recording method in which ink droplets are ejected in accordance with a recording signal to perform recording on a recording material, wherein the ink composition according to claim 7 is used. Inkjet recording method. 11. The ink jet recording method according to claim 10, wherein the recording material is an information transmission sheet. 12. The ink jet recording method according to claim 11, wherein the information transmission sheet is a surface-treated sheet. 13. An ink jet printer loaded with a container containing the ink composition according to any one of claims 7 to 9.