JP2002038066A - Fluorescent complex and ink composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent complex which is usable for ink compositions, especially for a water-based ink composition, and which is excellent in the storage stability and water resistance. SOLUTION: The fluorescent complex comprises a rare earth element and a macromolecular copolymer having a pyrrolidone part and a hydrophobic part.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fluorescent complex comprising a rare earth element and a polymer copolymer. More specifically, the present invention relates to a water-based ink composition, and as a use, relates to a paint, a plastic, an ink, or the like.

[0002]

2. Description of the Related Art In recent years, various kinds of cards, such as security cards utilizing the properties of fluorescent materials, factory automation, and various kinds of cards used for managing substances, have been actively developed. There is also an example in which a barcode is printed with ink using a fluorescent material, and a system for distributing articles by code management is used for mail or the like.

[0003] As a luminescent material to be used for these, a fluorescent complex in which a low molecular ligand is coordinated to a rare earth element as a luminescent center has been used and has been made into an ink. For example, JP-B-54-22336, JP-A-9-188835, JP-T-11-11102
13 and so on. These fluorescent complexes are uniformly dissolved as a dye in a liquid such as water or a solvent, or are uniformly dispersed as a pigment to form an ink. In particular, an ink using polyvinylpyrrolidone as a binder resin has high emission intensity and good characteristics. Further, it has a feature that a higher emission intensity can be obtained as compared with an inorganic phosphor.

Further, among the fluorescent complexes, a fluorescent complex using a polymer compound as a ligand has been proposed. For example, Journal of Polymer Science, Vol. 20, 1271-1278 (19
82). If these are applied to the ink composition,
It is considered that an ink composition that does not require a binder resin or a dispersant is possible.

[0005]

However, since the above-mentioned fluorescent complex and the fluorescent complex usually use a highly hydrophobic organic substance as a ligand, they are insoluble in a highly polar solvent such as water, and are limited in kind. Only soluble in solvents. In addition, since the affinity for other substances such as water and an organic solvent is weaker than the cohesive force between particles, under normal mixing and dispersion conditions,
It is extremely difficult to mix and disperse uniformly. Also,
Inks using polyvinylpyrrolidone as the binder resin have sufficient solubility in water and the like. However, since the resin itself has high hydrophilicity, the storage stability of the ink and the water resistance of the printed matter are deteriorated in an environment of high temperature and high humidity.

When the above-mentioned fluorescent complex and the fluorescent complex are to be used for an ink composition of, for example, an ink jet printer, a method of dissolving a specific organic solvent as a main solvent is usually employed. However, there is a problem that the vapor of the organic solvent is harmful to the human body and is severely restricted in the use environment. It is also conceivable to disperse the fluorescent complex and the fluorescent complex as a pigment in an aqueous solvent,
In that case, as described above, the dispersion stability of the fluorescent complex is poor, so that nozzle clogging and the like are caused, which is not suitable as an inkjet ink composition.

[0007] In view of the above circumstances, an object of the present invention is to provide a fluorescent complex having excellent storage stability and water resistance which can be used for an ink composition, particularly, an aqueous ink composition.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found a fluorescent complex comprising a high-molecular copolymer comprising a rare earth element and a pyrrolidone moiety and a hydrophobic moiety. Was completed.

The high molecular weight copolymer of the fluorescent complex of the present invention has a pyrrolidone moiety and a hydrophobic moiety. The pyrrolidone moiety can form a stable complex because the nitrogen or oxygen element coordinates with the rare earth element, and can obtain high emission intensity. Furthermore, the pyrrolidone moiety has a high affinity for water because of its hydrophilicity, whereby the fluorescent complex composed of the high molecular weight copolymer is dissolved in the aqueous solvent or is stable in the aqueous solvent due to the steric repulsion by the pyrrolidone moiety. Can be dispersed. However, the use of the pyrrolidone moiety alone does not yet provide sufficient ink storage stability and water resistance of printed matter.

Therefore, in the fluorescent complex of the present invention, the polymer copolymer in the fluorescent complex has a hydrophobic portion in the molecule. By the hydrophobic part, the coordination of the water molecule to the rare earth element can be suppressed, and the stability in water is improved. In addition, high emission intensity can be obtained. Further, the water resistance of the printed matter can be significantly improved.

The hydrophobic portion in the polymer compound includes, for example, acrylic ester, methacrylic ester, vinyl ester, styrene derivative, etc. Among them, acrylic ester, methacrylic ester and alkyl ester are preferable. . Examples of the acrylate and methacrylate include alkyl acrylate, alkyl methacrylate, fluorocarbon acrylate, fluoromethacrylic acid, silicon acrylate compound, and silicon methacrylate compound. When higher water resistance is required, fluorinated carbon acrylate, fluorinated methacrylic acid, a silicon acrylate compound, and a silicon methacrylate compound are preferable, and fluorinated acrylic acid and fluorocarbon methacrylate are more preferable. Fluorocarbon acrylate and fluorocarbon methacrylate have good light resistance and can form a stable fluorescent complex in water, so that high emission intensity can be obtained. The proportion of the hydrophobic part in the polymer copolymer is preferably 3% by weight or more and 70% by weight or less, more preferably 5% by weight or more and 50% by weight or less. If it is less than 3% by weight, the effect of hydrophobicity is not sufficiently exhibited, and the stability in water and the water resistance of the printed matter are insufficient. If it is more than 50 wt%, the hydrophobicity becomes too high and the solubility of the fluorescent complex in the aqueous solvent is lost, which is not preferable.

The molecular weight of the high molecular weight copolymer is preferably from 300 to less than 5,000, more preferably from 1,000 to less than 4,000. Since the rare earth element serving as the emission center is protected by the high molecular weight copolymer, the weather resistance is better than that of a normal fluorescent complex using only a low molecular weight ligand. This is because the high molecular copolymer in the structure blocks oxygen and prevents autoxidation, which is a cause of photodeterioration. If it is less than 300, oxygen cannot be blocked in this way, and weather resistance is insufficient, which is not preferable. On the other hand, if it is more than 5000, the viscosity of the ink becomes too high, and when printing with an ink jet printer or the like, head clogging tends to occur, which is not preferable.

Since the fluorescent complex of the present invention contains a high molecular weight copolymer in its structure, when used in an ink composition, a resin such as a binder is added again in order to improve fixability and weather resistance. You don't have to. Also, when the pigment is dispersed in an aqueous solvent, the resin and the surfactant need not be added again as a dispersant because the pigment is stably dispersed by the steric repulsion by the pyrrolidone portion in the structure.

It is considered that the polymer copolymer of the present invention is coordinated to the rare earth element which is the luminescent center via the nitrogen or oxygen element of the pyrrolidone moiety. The polymer copolymer may be one having a polydentate coordination such as a chelating agent or one having a coordination as a neutral ligand. Further, a high molecular compound having another ligand may form a mixed complex, or the weather resistance does not deteriorate even if a mixed complex is formed with a low molecular weight ligand which is usually used.

The type of the above-mentioned high molecular weight copolymer is not particularly limited, and examples thereof include acrylic, vinyl, urethane, polyester, and polyamide copolymers.

The pyrrolidone moiety is preferably represented by the chemical formula shown below.

[0017]

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The hydrophobic portion in the polymerized copolymer includes, for example, acrylic esters, methacrylic esters, vinyl esters, styrene, and general vinyl compounds having a vinyl group. Further, maleic acid ester, fumaric acid ester, urethane and the like may be used.
Acrylic esters, methacrylic esters, vinyl esters and styrene monomers are preferred, especially
More preferably, it is composed of at least one selected from acrylates, methacrylates, and vinyl esters represented by the chemical formula represented by Chemical Formula 2.

[0019]

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R in the chemical formula is preferably a hydrocarbon group having 2 or more carbon atoms, a fluorocarbon group or a group containing silicon, and a hydrocarbon group having 4 or more carbon atoms, a fluorocarbon group or a group containing silicon. Is more preferable. If the number of carbon atoms is 2 or less, sufficient hydrophobicity cannot be emitted, which is not preferable.

The acrylate and methacrylate monomers include ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, benzyl acrylate, and methacrylic acid. Ethyl, isopropyl methacrylate, n-propyl methacrylate, methacrylic acid
n-butyl, isobutyl methacrylate, methacrylic acid-
t-butyl, tridecyl methacrylate, benzyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, acrylic acid Stearyl, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, phenoxyethyl acrylate, isobonyl acrylate, 2-methacryloyloxyethyl succinic acid, 2- Methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropylphthalic acid, β-methacryloyloxyethyl hydrogen Succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, neopentyl glycol acrylate benzoate, 2-acryloyloxyethylhexyl hydrophthalic acid, 2-acryloyloxyethyl -2-hydroxypropylphthalic acid, acrylic acid 2-
Hydroxy-3-phenoxypropyl, acrylic acid-2
-Hydroxy-3-phenoxypropyl, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, trifluoroethyl methacrylate, pentafluoropropyl methacrylate, meta 2- (perfluorobutyl) ethyl acrylate, 2- (pafluorohexyl) ethyl methacrylate, methacrylic acid 3
-Pafluorohexyl-2-hydroxypropyl, 2- (pafluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate,
2- (Perfluoro-3-methylbutyl) methacrylate
Ethyl, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, methacrylic acid 2
-(Perfluoro-5-methylhexyl) ethyl, 3- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (pafluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 2-methacrylate
(Perfluoro-9-methyldecyl) ethyl, 1H, 1H3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate,
1H, 1H, 9H-hexadecafluorononyl methacrylate, 1H, -trifluoro-1-trifluoromethylethyl methacrylate, 1H, 1H, 3H-methacrylate
Hexafluorobutyl, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 3-perfluoroacrylate Butyl-2-hydroxypropyl, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohexyl acrylate 2-hydroxypropyl, 2- (perfluorooctyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl acrylate) ) Ethyl, 3- (perfluoro-3-methylbutyl) -2-acrylate Kishipuropiru, acrylic acid 2-
(Perfluoro-5-methylhexyl) ethyl, 3- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-9-methyloctyl) ethyl acrylate, 3- (perfluoro-7-methyloctyl) acrylate -2-hydroxypropyl, 2- (perfluoro-9-methyldecyl) ethyl acrylate, 2, acrylate
2,3,3-tetrafluoropropyl, acrylic acid 1H,
1H, 5H-octafluoropentyl, acrylic acid 1H,
1H, 7H-dodecafluoroheptyl, acrylic acid 1H,
1H, 9H-hexadecafluorononyl, acrylic acid 2,
2,2-Trifluoro-1-trifluoromethyl, 2,2,3,4,4,4-hexafluorobutyl acrylate, trimethylsiloxyethyl methacrylate, and (meth) acryl-modified polysiloxane X-manufactured by Shin-Etsu Chemical 22-24
04, X22-174DX and AK- manufactured by Toagosei
5, AK-30, and AK32.

Examples of vinyl ester monomers include vinyl benzoate, vinyl caprate, vinyl caproate, vinyl carlylate, vinyl cinnamate, vinyl crotate, vinyl decanoate, vinyl hexanoate, vinyl laurate,
Vinyl octanoate, vinyl palmitate, vinyl pivalate, vinyl propionate, vinyl stearate, vinyl trimethyl acetate, vinyl 4-tert-butylbenzene,
And vinyl crotonate and vinyl 2-ethylhexanoate.

Other monomers include vinyl anthracene, 4-vinyl benzoic acid, 4-vinyl biphenyl, vinyl caprolactam, 9-vinyl carbazole, vinyl cyclohexane, 4-vinyl-1-cyclohexene, 4-vinyl-1-cyclohexene , Vinylcycloheptane, vinylenetrithiocarbonate, vinylferrocene, 4,4'-vinylidenebis (N, N-dimethylaniline), 1-
Vinylimidazole, 2-vinylnaphthalene, 5-vinyl-2
-Norbonene, N-vinylnaphthalimide, 2-vinylpyridine, vinyltrimethoxysilane, (perfluorobutyl) ethylene, (perfluorohexyl) ethylene, (perfluorooctyl) ethylene, (perfluorodecyl) ethylene, styrene, α -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p
Polymerizable monomers such as -tert-butylstyrene.

The polymerization methods include bulk polymerization, solution polymerization,
Known general methods such as suspension polymerization, emulsion polymerization, and redox polymerization are mentioned, and among them, solution polymerization is preferred because the reaction method is simple. The reaction conditions vary depending on the polymerization initiator and the solvent, but the reaction temperature is 180 ° C. or less,
Preferably, the reaction time is 30 to 150 ° C and the reaction time is 30 to 40 minutes.
Time, preferably 2 hours to 30 hours.

The method for producing the high molecular weight copolymer is not particularly limited. For example, N-vinyl-2-pyrrolidone and an acrylic monomer having a hydrophobic group are mixed in a non-reactive solvent.
Examples include those obtained by reacting in the presence or absence of a catalyst.

Examples of the catalyst include peroxides such as t-butylperoxybenzoate, di-t-butyl peroxide, cumene peroxide, acetyl peroxide, benzoyl peroxide and lauroyl peroxide; azobisisobutylnitrile , Azobis-2,4-
Known polymerization initiators such as azo compounds such as dimethylvaleronitrile and azobiscyclohexanecarbonitrile can be used.

As the non-reactive solvent, water or a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-propyl alcohol, and isopropyl alcohol; amides such as dimethylformaldehyde and dimethylacetamide; Ketones such as acetone and methyl ethyl ketone; tetrahydrofuran,
Ethers such as dioxane, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, and triethylene ethylene glycol monoethyl ether; ethylene glycol, propylene glycol, butylene glycol, and triethylene glycol ,
1,2,6-hexanetriol, thiodiglycol,
Polyhydric alcohols such as diethylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; N-methyl-pyrrolidone, 1,3-dimethyl-2-
And imidazolidinone. Further, these solvents may be used in combination.

In the polymer complex of the present invention, a general low-molecular ligand may be used in combination as the ligand in addition to the above-mentioned polymer. The combined use of low molecular weight ligands is preferred because higher fluorescence emission intensity can be obtained. As low molecular ligands,
Generally, nitrogen-containing, oxygen, sulfur and phosphorus compounds are often used. For example, thenoyltrifluoroacetone, naphthoyltrifluoroacetone, benzoyltrifluoroacetone, methylbenzoyltrifluoroacetone, furoyltrifluoroacetone, pivaloyltrifluoroacetone, hexafluoroacetylacetone, trifluoroacetylacetone, fluoroacetylacetone, heptafluorobutanoyl Pivaloylmethane, 8-hydroquinoline, 8-mercaptoquinoline, tri-n-butyl phosphate, tri-n-butylphosphine oxide, tri-n-octylphosphine oxide, di-n-butylsulfoxide, pyridine, α -Picolin, β-picoline, γ-picoline, piperidine, quinoline and the like.

Of these, tenoyl trifluoroacetone and naphthoyl trifluoroacetone are particularly preferred. The amount of the low molecular weight ligand is preferably 3 to 8 times, and more preferably 4 to 6 times, the mole of the rare earth element. If it is less than three times, a sufficient fluorescence intensity cannot be obtained. If it is more than 8 times, the density will be erased. The low molecular ligand may or may not be coordinated with the rare earth element, but it is preferable that a low molecular ligand not coordinated exists. The storage stability is further improved by the presence of a non-coordinated low molecular weight ligand.

The rare earth element which is the emission center of the fluorescent complex of the present invention is europium, dysprosium, terbium,
Neodymium, Pseodymium, Samarium, Sadmium,
It is preferably made of at least one of holmium, erbium and thulium. These elements can stably form the fluorescent complex of the present invention and can obtain a sufficient emission intensity. In addition, when considering the application of the fluorescent complex of the present invention to security, FA, various cards, barcode systems, etc., europium is the most preferable among the above rare earths. When europium is used as the emission center, the emission is red at 615 ± 20 nm. Therefore, the printed mark emits the visible light on the longer wavelength side when excited by ultraviolet light, so that it is less affected by the color of the base, and can be detected with high sensitivity by a silicon photodiode or the like. . Blue or green emission may be poor in detectability.

When a mark that emits blue light is formed on white paper impregnated with a fluorescent whitening agent, the base also emits light, so that the difference in the amount of emitted light is substantially small, and detection may not be possible. In addition, when detecting visible light to be emitted, if a silicon photo diode, which is generally inexpensive and easily available, is used as a photoelectric conversion element, the light receiving sensitivity of visible light is lower on the short wavelength side than on the long wavelength side, Visible light of a relatively short wavelength of blue or green is less than half the sensitivity of visible light on the long wavelength side near 600 nm, and it may be difficult to obtain sufficient detection sensitivity.

The fluorescent complex of the present invention can be prepared by an appropriate method known to those skilled in the art. Only the ligand is replaced by a high molecular compound from a normal low molecular compound. Therefore, J. Am. Chem. Soc. Volume 186, Section 5117, 1
It can be synthesized by the method described in 964 or JP-B-6-15269. For example, the above-described polymer compound is synthesized, and the polymer compound and a ligand such as acetylacetone are reacted with a rare-earth metal halide such as europium chloride under appropriate conditions to generate the fluorescent complex of the present invention.

Further, the use of the fluorescent complex of the present invention includes:
Examples include inks, paints, plastics, and toner writing instruments. When a rare-earth element such as europium that emits light in the visible region is used as a light-emitting center, it can be dispersed in resin, and vivid colors of light emission can be used for toys, stage equipment, interior decoration, show windows, and the like. On the other hand, from the viewpoint of security and the like, it is preferable to apply the ink composition as an ink composition, and among them, an inkjet ink composition capable of inkjet printing is most preferred.

Various solvents such as ethanol, methanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetate can be used as the solvent for the ink composition containing the fluorescent complex of the present invention.

The ink composition preferably contains 15 to 99 parts by weight of water based on the ink composition. This is because the fluorescent complex of the present invention exhibits hydrophilicity because a water-soluble polymer is used for the ligand, and can be more dissolved or stably dispersed in an aqueous solvent. Further, it is possible to provide a water-based ink composition that is harmless to the human body, and it is possible to avoid the use environment from being restricted by using an organic solvent, such as making it difficult to use it in an office. A preferred range for the water content in the ink composition is 30 to 90 parts by weight.

For the production of the ink composition, a container driving medium mill such as a ball mill, a centrifugal mill, and a planetary ball mill, a high-speed rotation mill such as a sand mill, a medium stirring mill such as a stirring tank type mill, or a simple method such as a disperser. It can also be manufactured using a disperser.

The above-mentioned ink composition is usually composed of a binder, a charge imparting agent, a pH adjuster, a fluorescent sensitizer, a surfactant, a leveling agent, an ink defoaming agent, a bactericide, an antioxidant, etc., which are usually contained in the ink composition. And various additives. As the binder, for example, polyvinyl alcohol,
Vinyl resins such as polyvinyl butyral and polyvinyl acetate, urethane resins, phenol resins, polyester resins, acrylic resins, cellulose resins, polyamides, maleic resins, and copolymers thereof. Is mentioned. As the charge control agent, for example, Li such as LiNO 3
Salts, K salts such as KCN and KSCN, and cationic compounds such as tetraphenylphosphonium bromide. Examples of the pH adjuster include amine compounds such as diethanolamine, triethanolamine and triethylenetetramine, as well as amide compounds, hydroxides and carbonates such as Li hydroxide, sodium hydroxide, and potassium hydroxide. . Examples of the fluorescent sensitizer include phosphorus-based organic compounds such as phosphine oxide compounds, phosphine sulfide compounds and phosphine compounds, and nitrogen-based organic compounds such as benzotriazole.

In the above ink composition, the content of the fluorescent complex of the present invention is preferably from 0.1 to 10% by weight, and more preferably from 0.5 to 5% by weight. When the content is 0.1% by weight or more, the emission intensity can be maintained without reduction. When the content is 10% by weight or less, concentration erasure can be prevented and the emission intensity can be prevented from decreasing again.

In the case where the fluorescent complex of the present invention is used, since the high molecular weight copolymer of the ligand also functions as a binder as described above, the ligand may not be contained at all.
The content of other additives is 10% by weight or less, preferably 5% by weight or less, and the remainder is a solvent.

The printed matter of the above ink composition is completely or substantially invisible to the naked eye and cannot be confirmed.
Printed material using rare earth europium etc. as the luminescent center,
When irradiated with ultraviolet light, it is possible to confirm printing only after emitting red light in the visible light region. When neodymium is used as the rare earth element at the emission center, it is excited by infrared light and emits light in the infrared light region, and can be detected only by a dedicated detector. These printed matter of the present invention, which emit visible light and infrared light, are usually invisible.
A, can be applied to various things such as various cards.

When a bar code is printed using the above ink composition, it can be used as an improvement in a black and white bar code.
Conventional black-and-white barcodes have drawbacks such as impairing the appearance of articles, but they can be avoided. Barcode printing using the above ink composition can also be used for mail or the like to which a system for distributing articles by code management is applied.

The printing method of the printed matter may be any ordinary printing method. For example, inkjet printing, offset printing, gravure printing, thermal transfer printing, and the like. In particular, the ink composition of the present invention is suitable for inkjet printing. Since the ink composition of the present invention is dissolved or stably dispersed in an aqueous solvent, it can be stably ejected without causing nozzle clogging of an ink jet printer.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES Examples of the present invention will be described below in more detail. In the following, “parts” means “parts by weight”.

Synthesis Example 1 N-vinyl-2-pyrrolidone 80.0 parts Ethyl methacrylate 20.0 parts 2,2′-azobis (isobutylnitrile) 1.8 parts 2-propanol 100.0 parts Mix to prepare a solution.

Next, a reaction vessel equipped with a nitrogen introduction pipe was placed in a reaction vessel.
100 parts of 2-propanol was measured, and the temperature was raised to 70 ° C. while sealing with nitrogen. The above solution was added dropwise over 2 hours, and reacted for 14 hours while maintaining the same temperature after completion of the addition,
The solvent after the reaction was distilled off with an evaporator to obtain a polymer copolymer A.

(Synthesis Example 2) N-vinyl-2-pyrrolidone 80.0 parts Ethyl methacrylate 20.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl alcohol 100.0 parts These components are mixed. Then, a solution was prepared. Next, a polymer copolymer B was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 3) N-vinyl-2-pyrrolidone 50.0 parts Ethyl methacrylate 50.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl alcohol 100.0 parts These components are mixed. Then, a solution was prepared. Next, a polymer copolymer C was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 4) N-vinyl-2-pyrrolidone 80.0 parts Butyl methacrylate 20.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl alcohol 100.0 parts These components are mixed. Then, a solution was prepared. Next, a polymer copolymer D was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 5) N-vinyl-2-pyrrolidone 80.0 parts n-lauryl methacrylate 20.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts isopropyl alcohol 100.0 parts Were mixed to prepare a solution. Next, a polymer copolymer E was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 6) N-vinyl-2-pyrrolidone 80.0 parts Benzyl methacrylate 20.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl alcohol 100.0 parts Mix to prepare a solution. Next, a polymer copolymer F was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 7) N-vinyl-2-pyrrolidone 80.0 parts 2-acryloyloxyethyl phthalic acid 20.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts isopropyl alcohol 100.0 Part These components were mixed to prepare a solution. Next, a polymer copolymer G was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 8) N-vinyl-2-pyrrolidone 80.0 parts Styrene 20.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl alcohol 100.0 parts These components were mixed. A solution was prepared. Next, a polymer copolymer H was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 9) N-vinyl-2-pyrrolidone 85.0 parts Trifluoroethyl methacrylate 15.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl alcohol 100.0 parts Were mixed to prepare a solution. Next, a polymer copolymer I was obtained in the same manner as in Example 1.

Synthesis Example 10 N-vinyl-2-pyrrolidone 85.5 parts Perfluorooctylethyl methacrylate 15.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl alcohol 100.0 parts The components were mixed to prepare a solution. Next, a polymer copolymer J was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 11) N-vinyl-2-pyrrolidone 80.0 parts Methacryl-modified polysiloxane monomer X22-174DX manufactured by Shin-Etsu Chemical 20.0 parts 2,2′-azobis (isobutylnitrile) 3.6 parts Isopropyl Alcohol 100.0 parts These components were mixed to prepare a solution. Next, a polymer copolymer K was obtained in the same manner as in Synthesis Example 1.

Table 1 shows the measurement results of the weight average molecular weight of the synthesized high molecular weight copolymer (all values are in terms of polyethylene glycol). The measurement was performed by gel permission chromatography (1050, manufactured by HP).

[0057]

[Table 1]

(Example 1) (Preparation of ink composition) Tenoyl trifluoroacetone 10.6 parts Ethanol 320.0 parts Europium (III) chloride hexahydrate 3.0 parts Ion-exchanged water 227.0 parts While stirring with a magnetic stirrer. 0 parts were added dropwise to adjust the pH to 6. Thereafter, 18.6 parts of the polymer copolymer A was added, and the mixture was stirred at 60 ° C. for 3 hours and filtered to obtain a polymer phosphor solution A.

Further, 0.2 part of a surface conditioner (BYK-348, manufactured by BYK-Chemie) and 17.0 parts of a sensitizer (1,3-Dimethyl-2-imidazolidinone) were added to the obtained polymer phosphor solution A. After stirring at 25 ° C. for 1 hour, the mixture was filtered to obtain ink composition A.

Example 2 An ink composition B was obtained in the same manner as in Example 1 except that “polymer copolymer A” was changed to “polymer copolymer B”.

Example 3 An ink composition C was obtained in the same manner as in Example 1 except that “polymer copolymer A” was changed to “polymer copolymer C”.

Example 4 An ink composition D was obtained in the same manner as in Example 1 except that “polymer copolymer A” was changed to “polymer copolymer D”.

Example 5 An ink composition E was obtained in the same manner as in Example 1 except that the “high molecular weight copolymer A” was changed to the “high molecular weight copolymer E”.

Example 6 An ink composition F was obtained in the same manner as in Example 1 except that the “polymer copolymer A” was changed to the “polymer copolymer F”.

Example 7 An ink composition G was obtained in the same manner as in Example 1 except that “polymer copolymer A” was changed to “polymer copolymer G”.

Example 8 An ink composition H was obtained in the same manner as in Example 1 except that the “polymer copolymer A” was changed to the “polymer copolymer H”.

Example 9 An ink composition I was obtained in the same manner as in Example 1 except that “polymer copolymer A” was changed to “polymer copolymer I”.

Example 10 An ink composition J was obtained in the same manner as in Example 1 except that “polymer copolymer A” was changed to “polymer copolymer J”.

Example 11 An ink composition K was obtained in the same manner as in Example 1 except that “polymer copolymer A” was changed to “polymer copolymer K”.

Example 12 An ink composition L was obtained in the same manner as in Example 1 except that “europium chloride hexahydrate” was changed to “neodymium chloride hexahydrate”.

(Comparative Example 1) (Preparation of ink composition) Tenoyl trifluoroacetone 10.6 parts Ethanol 320.0 parts NaOH aqueous solution (1N) 40. 0 parts are added dropwise to adjust the pH to 6. Thereafter, 3.0 parts of europium (III) chloride hexahydrate and 227.0 parts of ion-exchanged water were added, and the mixture was stirred at 60 ° C. for 3 hours, and filtered to obtain a phosphor liquid M.

Further, 0.2 part of a surface conditioner (BYK-348, manufactured by BYK-Chemie) and 17.0 parts of a sensitizer (1,3-Dimethyl-2-imidazolidinone) were added to the obtained polymer phosphor solution M. After stirring at 25 ° C. for 1 hour, the mixture was filtered to obtain an ink composition M.

(Comparative Example 2) (Preparation of Ink Composition) 12.6 parts of Lumix CD331 manufactured by Rieder DeHaan 320.0 parts of ethanol 227.0 parts of ion-exchanged water The above substances were adjusted while mixing with a disper. After filtration, a phosphor liquid N was obtained.

Further, 0.2 part of a surface conditioner (BYK-348, manufactured by BYK-Chemie) and 17.0 parts of a sensitizer (1,3-Dimethyl-2-imidazolidinone) were added to the obtained phosphor solution N, After stirring at 1 ° C. for 1 hour, the mixture was filtered to obtain an ink composition N.

Comparative Example 3 (Preparation of Ink Composition) Tenoyltrifluoroacetone 10.6 parts Ethanol 320.0 parts Europium (III) chloride hexahydrate 3.0 parts Ion-exchanged water 227.0 parts While stirring with a magnetic stirrer. 0 parts were added dropwise to adjust the pH to 6. Thereafter, 37.2 parts of polyvinylpyrrolidone K25 (average molecular weight: 25,000) manufactured by Wako Pure Chemical Industries, Ltd. was added, and the mixture was further stirred for 1 hour to obtain a polymeric fluorescent substance liquid O.

Further, 0.2 part of a surface conditioner (BYK-348, manufactured by BYK-Chemie) and 17.0 parts of a sensitizer (1,3-Dimethyl-2-imidazolidinone) were added to the obtained polymer phosphor solution O. After stirring at 25 ° C. for 1 hour, the mixture was filtered to obtain an ink composition O.

(Examples 1 to 12, Comparative Examples 1 to 3) The viscosity, solubility and dispersion stability of the ink compositions prepared in the present invention were evaluated by the following methods. Table 2 shows the evaluation results. Further, the fluorescence intensity of the ink and the printed matter was evaluated. Table 3 shows the evaluation results.

(Viscosity of ink composition) E manufactured by Toki Sangyo Co., Ltd.
The viscosity at 25 ° C. was measured using a type viscometer (R100 type).

(Ink Solubility or Dispersion Stability) The ink solubility was evaluated by the presence or absence of sediment after storage at 60 ° C. for one week. Those with sediment were evaluated as x, and those without sediment were evaluated as ○.

(Emission Intensity of Ink and Printed Material) The emission intensity of the ink and the printed material was measured by a fluorescence spectrophotometer (FP750, manufactured by JASCO Corporation). The ink emission intensity was measured before and after storage at 60 ° C. for one week. Printed matter emission intensity is 6
The ink compositions before and after storage at 0 ° C. for one week were printed on plain paper (XEROX) using an inkjet printer (manufactured by EPSON: J-510C) and evaluated. The light resistance of the printed matter was evaluated after a sample printed with the ink before storage in the same manner was subjected to a light resistance test (Shimadzu XF-180CPS, manufactured by Shimadzu Corporation) for 3 hours. The luminescence intensity was measured using a commercially available dye (Lumidel CD331, manufactured by Rieder de Haan) as a reference.
An ink composition in which 2.6 parts was dissolved in 568 parts of ethanol was prepared, and the luminescence intensity was set to 100 to make a relative comparison.
Except for the printed matter with the ink composition L, the ink composition L was irradiated with excitation light of 365 nm, and the emission peak intensity at 615 nm was increased.
The printed matter was irradiated with excitation light at 810 nm, and the emission peak intensity at 1065 nm was used for comparison.

[0081]

[Table 2]

[0082]

[Table 3]

From the above results, it was found that the ink compositions A to L using the fluorescent complex of the present invention were soluble or stable in an aqueous solvent. In addition, the luminescence intensity of the ink composition and printed matter using the fluorescent complex of the present invention has a luminescence intensity equal to or higher than that of an ethanol-based ink using a commercially available dye, and also has better storage stability and weather resistance. It was confirmed that it showed.

[0084]

The fluorescent complex of the present invention comprising a high molecular weight copolymer having a rare earth element as a luminescent center and a pyrrolidone-non-hydrophobic portion has been found to be soluble in an aqueous solvent and to be stable. . Therefore, even when used in a jet printer ink composition, good printing is possible without causing ejection failure such as clogging. The aqueous ink composition is
Since no organic solvent is used, it is safe for the human body and there is no problem of restricting the use environment. Further, the luminescence intensity of the printed matter is equal to or higher than that of the solvent-based ink, and can be applied to various things such as security, FA, various cards, and barcode systems.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 11/06 C09K 11/06 (72) Inventor Takayuki Takao 1-88 Ushitora 1-chome Ushitora, Ibaraki-shi, Osaka, Hitachi F-term in Maxell, Inc. (reference) 4J039 AD03 AD08 AD10 AD23 BA39 CA03 CA06 EA28 EA34 EA41 EA44 GA02 GA03 GA06 GA13 GA24 4J100 AA15Q AA20Q AB00Q AB02Q AB03Q AB04Q AB07Q AC21Q AG02Q AG05Q AG08Q AL03Q AL04Q AP05 A08QAP03 AQ26Q AS15Q BA03Q BA11Q BA15Q BA16Q BA29Q BA77Q BB18Q BC04Q BC08Q BC43Q BC65Q BC66Q BC73Q BC83Q BD07Q CA04 JA07

Claims (8)

[Claims] 1. A fluorescent complex comprising a high molecular weight copolymer having a rare earth element, a pyrrolidone moiety and a hydrophobic moiety. 2. The method according to claim 1, wherein the pyrrolidone moiety is represented by (Chemical Formula 1) and the hydrophobic moiety is represented by (Chemical Formula 2), which is composed of at least one of acrylate, methacrylate and vinyl ester. The fluorescent complex according to claim 1, wherein Embedded image Embedded image 3. The fluorescent complex according to claim 1, wherein the hydrophobic part is a styrene derivative. 4. The high molecular weight copolymer has a weight average molecular weight of 30.
The fluorescent complex according to claim 1, wherein the number is 0 or more and less than 5000. 5. The fluorescent complex according to claim 1, wherein the molar ratio of the dye composed of the β-diketone compound and the high molecular weight copolymer having a pyrrolidone moiety and a hydrophobic moiety to the rare earth element is 3 to 8. 6. The fluorescent complex according to claim 1, wherein the rare earth element is at least one of europium, dysprosium, terbium, neodymium, pseodymium, samarium, saddle, holmium, erbium and thulium. 7. The ink composition according to claim 1, further comprising a fluorescent complex. 8. The ink composition according to claim 7, wherein water is contained in the ink composition, and the content of water in the ink composition is 30 to 90% by weight.