JP2002188026A - Aqueous fluorescent ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous fluorescent ink composition friendly to the global environment and realizing excellent fixity onto impermeable printing media such as plastic films without using such a device as an ultraviolet irradiator or a heater and suitable for ink-jet printers applied to commodity distribution system using bar code management. SOLUTION: This aqueous fluorescent ink composition comprises a fluorescent coloring matter, a resin and a solvent composed of 30-95 wt.% water and 70-5 wt.% water-miscible solvent and also contains a fixing agent. This ink composition has <4 sec fixing time when printed to coat on a plastic film with 300-980 μm printed dot diameter at 20-25 deg.C and 40-60% relative humidity using an ink-jet printer having 70 μm nozzle diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based fluorescent ink composition having an excellent fixing speed and being environmentally friendly, and particularly to an ink jet printing method which can withstand high-speed printing applied to a system for printing barcodes and distributing articles by code management. It relates to the above composition for a printer.

[0002]

2. Description of the Related Art In recent years, various kinds of cards such as security utilizing the properties of fluorescent materials, factory automation, and various 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-A-8-239607 and JP-A-9-18883
5, JP-A-11-279474, JP-T-11-51
No. 0213 and other publications. These fluorescent complexes are uniformly dissolved as a dye in a liquid such as a solvent or dispersed uniformly as a pigment to form an ink.

However, since these inks use an organic solvent as a solvent, they have problems such as pollution such as air pollution, occupational safety and health such as organic solvent poisoning, and the danger of fire and explosion. As one means for solving these problems, an aqueous fluorescent ink composition using water and a highly safe water-soluble solvent as a solvent has been proposed (Japanese Patent Publication No. Sho 5).
4-22336). However, since water is contained in the ink composition, there is a drawback that drying properties are inferior to conventional organic solvent-based inks.

In order to avoid this drawback, a proposal has been made to improve the apparent dryness by adding a penetrating agent to the ink to increase the permeation rate of the ink into the printing object (Japanese Patent Laid-Open No. 8-239609). JP-A-8-2537
No. 15, etc.). However, the effect is small when the printed material is highly permeable such as paper, but less effective when the material is non-permeable such as a plastic film. For this reason, it has been proposed to improve the drying property of a non-permeable printing material such as a plastic film by using ultraviolet curing or heat curing (Japanese Patent Application Laid-Open No. 10-7956). However, in this case, devices such as an ultraviolet irradiation device and a heating device are required.

[0006] Without using such an apparatus, if a water-based fluorescent ink composition is bar-coded on a mail or the like based on a non-permeable plastic film and applied to a system for distributing the bar-coded ink, it may cause a problem during transportation. The printed barcode may be peeled off or rubbed. As a result, there has been a problem that the bar code cannot be recognized by the reader, and the mail cannot be sorted. For these reasons, it has heretofore been considered difficult to utilize the aqueous fluorescent ink composition in a system for distributing articles under barcode management.

[0007]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a non-permeable printing object such as a plastic film without using an apparatus such as an ultraviolet irradiation apparatus or a heating apparatus. To provide a water-based fluorescent ink composition exhibiting excellent fixability and which is friendly to the global environment, and in particular, to provide a water-based fluorescent ink composition for an inkjet printer having excellent fixability which is applied to an article distribution system by barcode management. It is in.

[0008]

In order to solve the above-mentioned problem, the present inventors have developed an article distribution system using barcode management by shortening the fixing time of ink without printing the ink and completely drying the ink. Based on this idea, based on this idea, a suitable fixing agent is added to the aqueous fluorescent ink composition which is kind to the global environment, and the plastic film is formed under the environment of temperature of 20 to 25 ° C. and humidity of 40 to 60%. Fixing time when coated on top with a film thickness of 1 to 5 μm is 1 to
When it is configured to be 15 seconds, excellent fixability is obtained for a non-permeable printed material such as a plastic film, and a barcode printed during transport in an article distribution system by barcode management is obtained. It was found that the barcode could be sufficiently recognized by the reader without peeling or rubbing, and that the mail could be sorted well.

The aqueous fluorescent ink composition thus constituted is printed and coated on a plastic film using an ink jet printer having a nozzle hole diameter X [μm] under an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60%. The fixing time T [seconds] satisfying the relationship of Expression (1): T ≦ (X / 12) is satisfied, and good fixing properties can be obtained with an ink jet printer. In this case, the recording dot diameter Y
[Μm] satisfies the relationship of Expression (2): Y ≦ (X × 14), and it is also possible to avoid the problem that bar-to-bar overlaps during barcode printing, making it difficult to read barcodes. Fixing time is less than 4 seconds when printing and coating on plastic film with a recording dot diameter of 300 to 980 μm using an inkjet printer with a nozzle hole diameter of 70 μm, and the bar code printed during transport is peeled off or rubbed, making it impossible to read It was found that the method can be applied very well to an article distribution system based on barcode management without causing any problem.

The present invention has been completed based on the above findings. That is, the present invention contains a fluorescent dye, a resin and a solvent consisting of 30 to 95% by weight of water and 70 to 5% by weight of a water-soluble solvent, and further contains a fixation-imparting agent at a temperature of 20 to 25 ° C. A water-based fluorescent ink composition wherein the fixing time when coated on a plastic film in a film thickness of 1 to 5 μm in an environment of a humidity of 40 to 60% is 1 to 15 seconds. It is related to.

Further, the present invention comprises a fluorescent dye, a resin and a solvent consisting of 30 to 95% by weight of water and 70 to 5% by weight of a water-soluble solvent, further containing a fixing agent.
Fixing time T when printing and coating on a plastic film using an inkjet printer having a nozzle hole diameter X [μm] under an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60%.
[Second] relates to an aqueous fluorescent ink composition characterized by satisfying the relationship of Formula (1): T ≦ (X / 12). Furthermore, in the present invention, the recording dot diameter Y [μm] when printed and applied on a plastic film using an ink jet printer having a nozzle hole diameter X [μm] under an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60%. Formula (2): The present invention relates to the aqueous fluorescent ink composition having the above structure, which satisfies the relationship of Y ≦ (X × 14).

In particular, the present invention relates to fixing when printing and coating with a recording dot diameter of 300 to 980 μm on a plastic film using an ink jet printer having a nozzle hole diameter of 70 μm under an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60%. The present invention relates to the aqueous fluorescent ink composition having the above-mentioned constitution, wherein the time is within 4 seconds.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous fluorescent ink composition of the present invention contains a fluorescent dye, a resin and a solvent composed of 30 to 95% by weight of water and 70 to 5% by weight of a water-soluble solvent. 20-25 ° C, humidity 4
In an environment of 0 to 60%, the fixing time when coated on a plastic film in a thickness of 1 to 5 μm is 1 to 1
It is 5 seconds, particularly preferably 3 to 10 seconds. If the fixing time is faster than 1 second, the nozzles of the ink jet printer will be clogged.

The aqueous fluorescent ink composition of the present invention is printed on a plastic film using an ink jet printer having a nozzle hole diameter X [μm] in an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60%. The fixing time T [sec] at the time of application satisfies the relationship of the formula (1): T ≦ (X / 12), and the recording dot diameter Y [μm] is the formula (2): Y ≦ (X × 14). In particular, the aqueous fluorescent ink composition having the above configuration was printed and applied on a plastic film at a recording dot diameter of 300 to 980 μm using an inkjet printer having a nozzle hole diameter of 70 μm under an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60%. The fixing time at that time is within 4 seconds, preferably within 3 seconds, more preferably within 2 seconds.

When the relationship of the above formula (1) is not satisfied, the fixing property becomes insufficient, and when the bar code is printed, the bar code is peeled off or rubbed, and cannot be read. If the relationship of the above equation (2) is not satisfied, the bars overlap each other when the barcode is printed, and the barcode cannot be read.

On the other hand, if the recording dot diameter is smaller than 300 μm, it is difficult to recognize the dot as a bar when a barcode is printed because the dot is too small, and the fixing time is slow. If it is larger than 980 μm, when dots are too large and bar codes are printed, the bars are connected and cannot be read. When the fixing time exceeds 4 seconds when printing and applying at the recording dot diameter, the fixing time is too slow, and the barcode is peeled off or rubbed by contact with a transport roll or the like,
Cannot read.

In the present invention, the fixing agent having the above-mentioned constitution preferably has a melting point of 20 to 250 ° C. Further, those having a lower solubility in water than a solubility in a water-soluble solvent are preferable. Usually, the solubility in water is 0.1 to 60% by weight, and the solubility in a water-soluble solvent is 0.5 to 80% by weight.

Such a fixing agent greatly increases the fixing speed due to the difference in solubility between water and a water-soluble solvent. That is, the above fixing agent weakens the interaction between water and a water-soluble solvent, and makes it easier for a fluorescent dye or the like to be present on the water-soluble solvent side, while the fluorescent dye has a higher solubility in water than a water-soluble solvent. Because of its small size, when the water-soluble solvent partially evaporates, it cannot be completely dissolved in the solvent and precipitates or separates. As a result, it is considered that a fluorescent dye or the like is instantaneously fixed to the print-receiving material, and apparently the drying property is dramatically improved.

Such a fixing agent is used in a proportion of 0.5 to 10% by weight, preferably 1 to 8% by weight in the ink composition. If the amount is less than 0.5% by weight, the above effects cannot be sufficiently exerted. If the amount is more than 10% by weight, the above effects are saturated, and ink characteristics such as viscosity may be largely changed. All of these are undesirable.

The above-mentioned fixing agent used in the present invention comprises:
Cyclic compounds having at least one element of nitrogen, oxygen or sulfur and a water-soluble functional group in the molecule are preferred. For example, bemeglide, benzalphthalide, 1,2,4-benzenetricarboxylic anhydride, benzyl, benzimidazole, 2-benzimidazole propionic acid, 2-benzimidazolylacetonitrile, benzo [C] cinnoline, benzo -12-crown-4, benzo-15-crown-5, benzo-18-crown-6, 1,4-benzodioxane-6-carboxaldehyde, 3H-1,
2-benzodithiol-3-one, 2-benzofurancarboxylic acid, benzofuroxan, 2,1,
3-benzothiadiazole, 2H-1,4-benzothiazin-3 (4H) -one, 1,2,3-benzotriazin-4 (3H) -one, benzotriazole, benzotriazole-5-carboxylic acid, 1H- Benzotriazole-1-methanol, 1-benzotriazolyl-9-fluorenylmethyl carbonate, N
-(1H-benzotriazol-1-ylmethyl) formamide, 2H-1,4-benzoxazine-3 (4
H) -one, benzoxazole, 2-benzoxazolinone, 2-benzoylthiophene, 2-benzylamino-4-methylpyridine, 4-benzylamino-7-nitro-2,1,3-benzoxadiazole, 6-benzylaminopurine, 2-benzylaminopyridine,
(-)-2,3, -o-benzylidene-L-threitol, 1-benzylimidazole, N-benzylmaleimide, (S)-(-)-4-benzyl-1-oxazolidinone, N- ( Benzyloxycarbonyloxy)
Succinimide, 4-benzyloxy-2- (1H)-
Pyridone, 4-benzyloxy-3-pyrrolin-2-one, 5-benzyl-1H-pyrrolo [2,3-c] pyridine-3-carboxaldehyde, N-benzylphthalimide, 3,4-bis (acetoxymethyl) Furan, bis [(benzo-15-crown-5) -15-ylmethyl] pimelate, 1,4-bis (5-phenyloxazol-2-yl) benzene, 1,2-bis (4-pyridyl) ethane, 1, , 2-bis (2-pyridyl) ethylene,
1,3-bis (3-pyridylmethyl) -2-thiourea, 2,3-bis (2-pyridyl) pyrazine, N- (2
-Bromobenzyloxycarbonyloxy) succinimide, butadiene sulfone, 3-carboxy-1,4-
Dimethyl-2-pyrroleacetic acid, 2-coumalanone, coumarin, coumarin-3-carboxylic acid, 18-crown-6, dihydroascorbic acid, 3,4-dihydro-DL-proline, 3,5-diacetyl- 1,4-dihydro-2,6-
Dimethylpyridine, 3,5-diacetyl-2,6-dimethylpyridine, 1,3-diacetyl-2-imidazolidinone, 2,6-diacetylpyridine, (+)-diacetyl-L-tartaric anhydride, 3 , 5-Diacetyltetrahydropyran-2,4,6-trione, dibenzo-18-crown-6, dibenzo-24-crown-8, dibenzo-30-crown-10, dibenzofuran, dibenzothiophene, dibenzothiophene sulfone, 5, 8-difluoro-1,4-benzodioxane,
Diglycolic anhydride, dihydro-4,4-dimethyl-2,3-furandione, 5,6-dihydro-5
-Methyl-4H-1,3,5-dithiazine, 2,5-dimercapto-1,3,4-thiadiazole, 4,4'-
Dimethyl-2,2'-dipyridyl, dimethyl-3,4-
Furancarboxylate 2,3-dimethylmaleic anhydride, ethylenediaminetetraacetic dianhydride, furfuryl sulfide, furyl,
Homophthalic anhydride, 4-hydroxy-1,
3-benzodioxol-2-one, 2-hydroxybenzothiazole, 6-hydroxy-1,3-benzoxathiol-2-one, N- (2-hydroxyethyl) phthalimide, N-hydroxysuccinimidylacetate Acetate, N-methylsuccinimide, N-phenylmaleimide, phthalazine, 1 (2H) -phthaladione, phthalide, piperonal, piperonyl alcohol, poperonylic acid, 1-piperonylpiperazine, sesamol, 2-thiophene Acetic acid, 3-thiophene maleic acid, and the like. Among them, compounds containing a functional group and an aromatic ring in a molecule, such as 2-mercaptobenzoxazole, benzotriazole, 2-benzoxazolinone, and phthalimide, are preferably used. In particular, oxazole or triazole compounds are preferably used.

As the fixing agent, in addition to the above compounds, any compound that can utilize the difference in solubility between water and a water-soluble solvent can be used widely. For example, a compound having high water absorption may be used to improve the fixing property. The compound having high water absorption absorbs water, and makes the fluorescent dye easily exist on the water-soluble solvent side. When a part of the water-soluble solvent evaporates, the fluorescent dye becomes insoluble and precipitates, thereby improving fixability. Such compounds include starch, gelatin, cellulose acacia, casein, carrageenan, feserelan, alginate, propylene glycol alginate,
Guar gum, gum arabic, pectin, pullulan cyclodextrins, chitin, chitosan, sucrose, gluctose, fructose, xylose and the like.

In the present invention, 30 to 95% by weight of water is used in the solvent in order to obtain sufficient drying properties while reducing the risk.
And 70 to 5% by weight of a water-soluble solvent, particularly preferably 35 to 80% by weight of water and 65 to 20% of a water-soluble solvent.
% By weight. If the amount of water in the solvent is less than 30% by weight, the flash point of the ink composition is lowered and the danger is increased, while if it exceeds 95% by weight, the proportion of water becomes too high, The drying property is slow, and the fixing property is impaired.

As the water-soluble solvent, methyl alcohol,
Alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol and pentyl alcohol; amides such as dimethylformaldehyde and dimethylacetamide; acetone;
Ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as tetrahydrofuran, 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,
Polyhydric alcohols such as triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, diethylene glycol, polyethylene glycol, polypropylene glycol, glycerin; N-methyl-pyrrolidone, 1,3-dimethyl-2-imidazolidinone And the like, and one or more of these are used.

Among such various water-soluble solvents, it is particularly preferable to use at least one of alcohols, ketones and ethers. In consideration of the fixing property, those having a boiling point of 100 ° C. or less are preferable. Further, in consideration of safety, alcohols having 3 or less carbon atoms, such as ethyl alcohol and propyl alcohol, are particularly preferably used.

In the present invention, the fluorescent dye is preferably a fluorescent dye containing a rare earth element, that is, a fluorescent dye comprising a rare earth element and a ligand. As the rare earth element which is the emission center of the fluorescent dye, at least one of europium, dysprosium, terbium, neodymium, pseodymium, samarium, saddle, holmium, erbium and thulium is used. According to these elements, a fluorescent complex can be formed stably, and a sufficient emission intensity can be obtained.

Considering applications to security, FA, various cards, bar code systems, etc., it is desirable to use europium among the above rare earth elements. When europium is used as the emission center, the emission is red at 615 ± 20 nm. For this reason, the printed mark emits the visible light on the long wavelength side when excited by ultraviolet light, so that the printed mark is hardly affected by the color of the base and can be detected with high sensitivity by a silicon photodiode or the like.

When a blue or green luminescent dye is used, the detectability may be poor. For example, 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 photodiode that 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. For relatively short wavelength visible light of blue or green, 60
The sensitivity is less than half that of visible light on the long wavelength side near 0 nm, and it may be difficult to obtain sufficient detection sensitivity.

As the ligand of the fluorescent dye, tenoyl trifluoroacetone, naphthoyl trifluoroacetone,
Benzoyltrifluoroacetone, methylbenzoyltrifluoroacetone, furoyltrifluoroacetone,
Pivaloyltrifluoroacetone, hexafluoroacetylacetone, trifluoroacetylacetone, fluoroacetylacetone, heptafluorobutanoylpivaloylmethane, 8-hydroquinoline, 8-mercaptoquinoline, tri-n-butyl phosphate, tri-n-butylphosphine Oxides, tri-n-octylphosphine oxide, di-n-butylsulfoxide, pyridine, α-picoline, β-picoline, γ-picoline, piperidine, quinoline and the like are used.

Further, as other ligands, dendritic compounds such as dendrimers and calix arrays and clathrates, which can form a more stable complex by incorporating a rare earth element into the molecule, may be used. I don't care. The compound is not particularly limited as long as it is a compound containing a coordination site such as nitrogen, oxygen, sulfur, and phosphorus in the molecule. A polymer ligand containing the above element may be used. Among these various ligands,
Tenoyl trifluoroacetone and naphthoyl trifluoroacetone are most preferred.

In the present invention, the above-mentioned fluorescent dye can be easily synthesized according to a conventionally known method. For example, it is easily synthesized by reacting a ligand such as tenoyltrifluoroacetone, naphthoyltrifluoroacetone, or hexafluoroacetylacetone with a rare earth metal halide such as europium chloride under appropriate conditions. be able to.

In the present invention, various known resins such as a vinyl resin, an acrylic resin, an amino resin, a polyester resin, an alkyd resin, a phenol resin, a cellulose resin, and a copolymer thereof are used as the resin. Among them, at least one of polyvinylpyrrolidone, polyvinyl alcohol, polyurethane, polyacrylic acid, polyether or a copolymer thereof is used to increase the intensity of fluorescent light emission or improve fixability.
Particularly preferably used.

In the present invention, the content of the above-mentioned fluorescent dye is usually 0.1 to 8% by weight in the ink composition,
Preferably, it is 0.5 to 5% by weight. When the amount is less than 0.1% by weight, the luminous intensity decreases. When the amount exceeds 8% by weight, the luminous intensity also decreases due to concentration quenching. The content of the above resin is preferably 1 to 8% by weight, more preferably 2 to 7% by weight in the ink composition. When the amount is less than 1% by weight, the fixability to a print object becomes unsatisfactory.

The aqueous fluorescent ink composition of the present invention contains, in addition to the above-described fluorescent dye, resin, solvent (water and water-soluble solvent), and a fixing agent, a non-absorbing ink which does not absorb ink such as a polystyrene film as a material to be printed. When printing on a sexual article, it is desirable to include at least one of a silicon-based or fluorine-based surface treatment agent. The aqueous fluorescent ink composition has a low surface tension, and the non-absorbent articles as described above have good wettability of the ink, so that bleeding is likely to occur.However, by including the surface treatment agent, the wettability of the ink can be reduced. Lowering and bleeding can be suppressed.

As the silicon-based surface treating agent, "BYK" manufactured by BYK-Chemie and various silicon compounds manufactured by Shin-Etsu Chemical Co., Toray Silicone Co., Chisso Co., and Toshiba Silicone Co., Ltd. are used. As a fluorine-based surface treatment agent, "Surflon" manufactured by Asahi Glass Co., Ltd., 3M
Various fluorine compounds such as "Florald" manufactured by Daikin Incorporated, "Megafac" manufactured by Dainippon Ink and Daikin Co., Ltd. are used. In particular, silicon-based surface treatment agents
Compared with a fluorine-based surface treatment agent, it is preferable because it is inexpensive, has excellent safety, has high solubility, and has little foaming. If the amount of the surface treating agent is too large, the ink properties such as viscosity may be affected, and the amount is preferably 0.01 to 2% by weight in the ink composition.

The aqueous fluorescent ink composition of the present invention may further include a charge-imparting agent, a pH adjuster, a fluorescent sensitizer, a surfactant, a leveling agent, an ink defoaming agent, and a germicidal agent, which are contained in ordinary ink compositions. Various additives such as an agent and an antioxidant may be included.

For example, as a charge control agent, LiNO
_And lithium salts such as ₃ , potassium salts such as KCN and KSCN, and cationic compounds such as tetraphenylphosphonium bromide. As a pH adjuster,
In addition to amine compounds such as diethanolamine, triethanolamine, and triethylenetetramine, amide compounds, hydroxides and carbonates such as lithium hydroxide, sodium hydroxide, and potassium hydroxide are exemplified. Examples of the fluorescent sensitizer include phosphine oxide compounds, phosphine sulfide compounds, phosphorus-based organic compounds such as phosphine compounds, and nitrogen-based organic compounds such as benzotriazole.

The aqueous fluorescent ink composition of the present invention is obtained by mixing the above-mentioned components with a container driving medium mill such as a ball mill, a centrifugal mill and a planetary ball mill, and a high-speed rotating mill such as a sand mill.
It can be prepared by mixing and dispersing using a medium stirring mill such as a stirring tank type mill, or using a simple disperser such as a disper.

The aqueous fluorescent ink composition of the present invention contains components other than the solvent (water and water-soluble solvent) in the ink composition.
It is preferably from 10 to 10% by weight. If the content is less than 5% by weight, it is difficult to obtain sufficient light emission intensity and fixability. It is preferable that the viscosity is 1 to 8 cp and the flash point is 20 ° C. or higher. If the viscosity is out of the above range, printing cannot be performed stably, and if the flash point is lower than 20 ° C., the flammability increases.

The printed matter using the aqueous fluorescent ink composition of the present invention is completely or substantially invisible to the naked eye and cannot be confirmed. A printed material using europium as a rare earth element at the emission center emits red light in a visible light region when irradiated with ultraviolet light, so that printing can be confirmed. Further, a printed material using neodymium as a rare earth element at the emission center is excited by infrared light and emits light in the infrared light region, and can be detected only by a dedicated detector.
Both these visible light and infrared light printed matter,
Since it is normally invisible, it can be applied to various uses such as security, FA, and various cards.

In particular, when a barcode is printed using the aqueous fluorescent ink composition of the present invention, it can be used as an improvement of a black-and-white barcode. Conventional black-and-white barcodes have drawbacks such as impairing the appearance of articles, but they can be avoided. Further, since the aqueous fluorescent ink composition of the present invention has a high fixing speed, as described above, an inkjet printer capable of withstanding high-speed printing applied to a system for performing barcode printing and article distribution by code management. It is most preferable to use it. In particular, it can be used for mail or the like.

The aqueous fluorescent ink composition of the present invention can be printed by any printing method such as ink jet printing, offset printing, gravure printing, and thermal transfer printing. Among these printing methods, ink jet printing is particularly preferable. In particular, as described above, a printing method using a continuous-type inkjet printer that can withstand high-speed printing is preferable. In this case, there is no risk of causing nozzle clogging of the inkjet printer, and stable ejection and printing can be performed.

[0042]

The present invention will now be described more specifically with reference to examples. In the following, “parts” means “parts by weight”.

Example 1 Tenoyl trifluoroacetone 12.6 parts Ethanol 274.0 parts Europium (III) chloride hexahydrate 3.0 parts Ion-exchanged water 274.0 parts The above components were stirred with a magnetic stirrer. While adding 6.9 parts of dimethylethanolamine dropwise, pH
Adjusted to 6.8. Then, resin: "Polyvinylpyrrolidone K3" manufactured by Wako Pure Chemical Industries, Ltd.
0 "was added, and the mixture was stirred at 60 ° C. for 3 hours and then filtered to obtain a phosphor solution A. Further, to this phosphor solution A, 0.2 part of a surface treatment agent: "BYK-348" manufactured by BYK-Chemie, a fixing agent: 17.0 parts of 1,2,3-benzotriazole was added, and the mixture was stirred at 25 ° C. for 1 hour. Thereafter, the mixture was filtered to obtain an aqueous fluorescent ink composition A.

Example 2 An aqueous fluorescent ink composition B was obtained in the same manner as in Example 1, except that the same amount of benzoxazole was used instead of 1,2,3-benzotriazole.

Example 3 An aqueous fluorescent ink composition C was obtained in the same manner as in Example 1 except that the same amount of 2-benzoxazolinone was used instead of 1,2,3-benzotriazole.

Example 4 An aqueous fluorescent ink composition D was obtained in the same manner as in Example 1 except that the same amount of 2-mercaptobenzoxazole was used instead of 1,2,3-benzotriazole.

Example 5 An aqueous fluorescent ink composition E was prepared in the same manner as in Example 1 except that the use of the surface treatment agent “BYK-348” was omitted.
I got

Example 6 An aqueous fluorescent ink composition F was obtained in the same manner as in Example 1 except that the same amount of neodymium chloride hexahydrate was used instead of europium chloride hexahydrate.

Example 7 Fluorescent dye (“Lumix CD332” manufactured by Rieder de Haan) 5.2 parts Ethanol 301.0 parts Ion-exchanged water 247.0 parts Resin: “Polyvinylpyrrolidone K30” 22 manufactured by Wako Pure Chemical Industries, Ltd. 3.3 parts Lithium nitrate 1.8 parts Surface treatment agent: BYK-348 (manufactured by BYK Chemie) 0.2 part Fixing agent: 1,7.0 parts 1,2,3-benzotriazole 17.0 parts of the above components were mixed, After stirring at 25 ° C. for 1 hour, the mixture was filtered to obtain an aqueous fluorescent ink composition G.

Comparative Example 1 An aqueous fluorescent ink composition H was obtained in the same manner as in Example 1, except that 1,2,3-benzotriazole as a fixing agent was omitted.

Comparative Example 2 Ink composition I was prepared in the same manner as in Example 1 except that the use of 274.0 parts of ion-exchanged water was omitted and the number of used ethanol was changed from 274.0 parts to 548.0 parts. I got

The ink compositions A to I of Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to an ink fixing test and a code control test by the following methods. These test results were as shown in Table 1.

<Ink fixability test> The ink composition was treated with N
o. Using a 4-wire bar (manufactured by Toyo Seiki Co., Ltd.), temperature 2
In an environment of 5 ° C. and 50% humidity, it is applied on a polyethylene terephthalate film (hereinafter referred to as a PET film) so that the film thickness after drying becomes a predetermined thickness (3 μm or 3.5 μm) and printed. Was rubbed at intervals of 3 seconds with a PET film on which a weight was placed, and the time (second) until the printed matter did not peel off was measured.

<Code management test>"Inkjet printer CB3" manufactured by Domino (head nozzle hole diameter:
40 μm), printing was performed on the cell window of an envelope with cell windows (the cell window was made of polystyrene). After 0.7 seconds, the printed matter was rubbed with a brush for oil-based paint, and code management was confirmed. evaluated. Environment is temperature 25 ℃, humidity 50%
Met. ：: The printed matter can be read without rubbing, and the code can be managed. ×: The printed matter cannot be rubbed and the code cannot be managed.

[0055]

As is clear from the above results, according to the aqueous fluorescent ink compositions A to G of Examples 1 to 7 of the present invention,
It can be seen that articles can be sufficiently separated in a system for distributing articles by barcode management, which was not possible with the aqueous fluorescent ink composition H of the comparative example 1 of the related art, and can be applied to the above system.

Next, the ink compositions A to E of Examples 1 to 5 and the ink compositions H and I of Comparative Examples 1 and 2 were subjected to a luminescence test by the following method to evaluate the ink and printed matter. The emission intensity was measured. The results were as shown in Table 2.

<Emission intensity of ink and printed matter> 365
The excitation peak light of 615 nm is irradiated, and the emission peak intensity of 615 nm is measured with a fluorescence spectrophotometer (manufactured by JASCO Corporation: “FP750”).
The ink composition I of Comparative Example 2 (an ethanol solvent containing no water) was evaluated as a relative value with respect to 100. The luminescence intensity of the printed matter was determined by using Dom
Plain paper (XEROX) using “Inkjet Printer CB3” (head nozzle hole diameter: 40 μm) manufactured by Ino
Was printed and evaluated.

[0059]

As is clear from the above results, according to the aqueous fluorescent ink compositions A to E of Examples 1 to 5 of the present invention,
The luminous intensity of the ink and the printed matter was almost equal to or higher than that of the fluorescent ink composition I of the ethanol solvent-based comparative example 2, indicating that a sufficiently satisfactory luminous intensity was obtained.

In addition, according to another luminescence test, Examples 1 to 5
The aqueous fluorescent ink composition G of Example 7 using a fluorescent dye different from the aqueous fluorescent ink compositions A to E of
The same good emission intensity as described above was obtained. further,
The aqueous fluorescent ink composition F of Example 6 using neodymium as the rare earth element of the fluorescent dye was irradiated with excitation light of 810 nm, and the emission peak intensity at 1,065 nm was measured in the same manner as described above. It was found that an emission intensity that could be obtained was obtained.

Next, for the ink compositions A to I of Examples 1 to 7 and Comparative Examples 1 and 2, the fixing time and dot diameter of the printed matter by an ink jet printer were measured by the following methods. The results were as shown in Table 3.

<Fixing Time and Dot Diameter of Printed Material> An envelope with a cell window (the cell window was made of polystyrene) was obtained by using an ink jet printer 170i (head nozzle hole diameter: 70 μm) manufactured by Marconi Data System Japan Co., Ltd. ) Is printed on the cell window, and after a predetermined time,
The printed matter was rubbed with a paint brush, and the time during which the printed matter was not rubbed was measured. The dot diameter of the printed matter was also measured. The environment was a temperature of 25 ° C. and a humidity of 50%.

[0064]

As is apparent from the above results, the aqueous fluorescent ink compositions A to G of Examples 1 to 7 of the present invention have excellent fixability as compared with the conventional aqueous fluorescent ink composition H of Comparative Example 1. This is a result comparable to that of the fluorescent ink composition I of the ethanol solvent-based comparative example 2, which is safe with less problems such as pollution such as air pollution, occupational health and safety such as organic solvent poisoning, and danger of flammable explosion. It can be seen that the characteristics are fully utilized as an environmentally friendly aqueous fluorescent ink composition.

Examples 1 to 3 in which a surface treating agent was added
The aqueous fluorescent ink compositions A to D, F, and G of 4, 6, and 7 are:
It was also confirmed that the dot diameter was small and the bleeding was small as compared with the aqueous fluorescent ink composition E of Example 5 to which no surface treatment agent was added.

[0067]

As described above, according to the present invention, a fluorescent dye, a resin, 30 to 95% by weight of water and 70%
-5% by weight of a solvent, further containing a fixing agent, at a temperature of 20 to 25 ° C and a humidity of 40 to 60%.
% On a plastic film in an environment of 1% to 5μ
Fixing time when applied within the range of m is 1 to 15 seconds, without using equipment such as an ultraviolet irradiation device or a heating device, it can be applied to non-permeable printing materials such as plastic films. On the other hand, it is possible to provide a water-based fluorescent ink composition that exhibits excellent fixability and is environmentally friendly.

The fixing time T when the composition having the above-mentioned composition was printed and applied on a plastic film using an ink jet printer having a nozzle diameter X [μm].
[Second] satisfies the relationship of Expression (1): T ≦ X / 12, and the recording dot diameter Y [μm] is expressed by Expression (2): Y ≦ (X × 1
By satisfying the relationship of 4), in particular, the fixing time when printing and applying a recording dot diameter of 300 to 980 μm on a plastic film using an ink jet printer having a nozzle hole diameter of 70 μm is set to be within 4 seconds, so that bar code management is achieved. The present invention can provide an aqueous fluorescent ink composition for an inkjet printer having excellent fixability, which is applied to an article distribution system according to the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 EA19 FC01 2H086 BA53 BA55 BA59 BA60 BA61 BA62 4J039 AD04 AD06 AD09 AD23 AE04 AE06 AE11 BA39 BC07 BC12 BC16 BC31 BC50 BC52 BC54 BC59 BE12 CA03 CA06 EA28 EA43 EA48 FA02 GA24

Claims (17)

[Claims] 1. A fluorescent dye, a resin and a solvent consisting of 30 to 95% by weight of water and 70 to 5% by weight of a water-soluble solvent, further containing a fixing agent, and having a temperature of 20 to 2%.
Aqueous fluorescent ink characterized in that the fixing time when coated on a plastic film in a film thickness of 1 to 5 μm in an environment of 5 ° C. and a humidity of 40 to 60% is 1 to 15 seconds. Composition. 2. A fluorescent dye, a resin and a solvent consisting of 30 to 95% by weight of water and 70 to 5% by weight of a water-soluble solvent.
Under an environment of 5 ° C. and a humidity of 40 to 60%, the nozzle hole diameter X [μ
m], wherein the fixing time T [seconds] when printing and coating on a plastic film using the ink jet printer satisfies the relationship of formula (1): T ≦ (X / 12). Ink composition. 3. A recording dot diameter Y [μm] when printing and coating on a plastic film using an ink jet printer having a nozzle hole diameter X [μm] in an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60% is expressed by the following formula. (2): Y ≦ (X × 1
The aqueous fluorescent ink composition according to claim 2, which satisfies the relationship of 4). 4. A recording dot diameter of 30 μm on a plastic film in an environment of a temperature of 20 to 25 ° C. and a humidity of 40 to 60% using an ink jet printer having a nozzle hole diameter of 70 μm.
4. The aqueous fluorescent ink composition according to claim 2, wherein the fixing time when printing and coating at 0 to 980 [mu] m is within 4 seconds. 5. The aqueous fluorescent ink composition according to claim 1, wherein the fixing agent has a melting point of 20 to 250 ° C. 6. The aqueous fluorescent ink composition according to claim 1, wherein the solubility-imparting agent has lower solubility in water than solubility in a water-soluble solvent. 7. The fixing agent has a solubility in water of 0.1.
1 to 60% by weight, solubility in water-soluble solvent is 0.5 to
The aqueous fluorescent ink composition according to claim 6, which is 80% by weight. 8. The ink composition according to claim 8, wherein the fixing agent comprises
The aqueous fluorescent ink composition according to any one of claims 1 to 7, wherein the amount is 10 to 10% by weight. 9. The aqueous fluorescent ink composition according to claim 1, wherein the fluorescent dye is a fluorescent dye containing a rare earth element. 10. The aqueous fluorescent ink composition according to claim 1, wherein the resin is at least one of polyvinylpyrrolidone, polyvinyl alcohol, polyurethane, polyacrylic acid, polyether and a copolymer thereof. object. 11. The aqueous fluorescent ink composition according to claim 1, wherein the water-soluble solvent is at least one of alcohols, ketones, and ethers. 12. The aqueous fluorescent ink composition according to claim 1, wherein the water-soluble solvent has a boiling point of 100 ° C. or lower. 13. The aqueous fluorescent ink composition according to claim 1, wherein the water-soluble solvent is an alcohol having 3 or less carbon atoms. 14. An ink composition comprising components other than a solvent,
The aqueous fluorescent ink composition according to any one of claims 1 to 13, which is 5 to 10% by weight. 15. The aqueous fluorescent ink composition according to claim 1, which has a viscosity of 1 to 8 cp and a flash point of 20 ° C. or higher. 16. The aqueous fluorescent ink composition according to claim 1, which comprises at least one of a silicon-based or fluorine-based surface treatment agent. 17. The aqueous fluorescent ink composition according to claim 1, which is used for an ink jet printer capable of withstanding high-speed printing applied to a system for performing barcode printing and distributing articles by code management.