JP2001329258A - Fluorescent composition, ink composition and printed matter - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To print on a product without impairing the appearance of the product, to be able to detect printed matter with high sensitivity for a long period of time, to be safe for the human body, and to be used in an environment of use. Provided is an ultraviolet excitation type ink composition which is not subject to any restrictions. An organic fluorescent dye which is substantially invisible or difficult to recognize in a visible light region and emits in a visible light region when excited by ultraviolet light, has a boiling point of 200.
Present as a particulate having a particle size of 10 to 2,000 nm in a solvent at a temperature of not lower than 10 ° C. or as a particulate having a particle size of 10 to 800 nm in a solvent containing 94% by weight or more of water and / or ethanol. An ink composition comprising:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic fluorescent dye having an emission center in the visible light region when excited by ultraviolet light, and in particular, a fluorescent composition containing an organic fluorescent dye which is substantially invisible or difficult to recognize in the visible light region. And an ultraviolet excitation type ink composition containing the above-mentioned organic fluorescent dye used for printing or other printing by a marker pen, a dot impact type printer, an ink jet printer, etc., and prepared using this ink composition. Printed matter.

[0002]

2. Description of the Related Art In recent years, information such as a manufacturer and a product name of an article is displayed in a bar code, a certain character, a numerical value, or the like, and an optical detection method such as a bar code reader or OCR is used. It is often used to read and aggregate the sales of commodities and analyze distribution. Recently, not only products using such barcodes and OCR systems have been found, but there are also systems that apply this system to file management, etc. For example, goods are distributed by code management. There is also an example of a system that applies to mail items. Furthermore, in banks and the like, a system is also introduced in which information such as characters and numerical values is printed on forms and the information is used for sorting and management.

The bar code printing method includes a contact printing method and a non-contact printing method. Among them, the contact printing method includes a method using a marker pen and a bar code dryer, and the non-contact printing method includes an ink jet printing method. Among these printing methods, the ink jet printing method is to perform printing by injecting an ink composition onto a surface to be printed through a nozzle, and is a non-contact printing method, so that a non-uniform shape surface, for example,
Suitable for printing on plastic sheets, bags, bottles and cardboard surfaces.

The ink composition used in the ink jet printing method is as follows: (1) stable without causing phase separation or precipitation even when stored for a long period of time; (2) passing without clogging the nozzle; Good adhesion between the composition and the printing surface; (4) the ink composition dries quickly on the printing surface,
Moreover, (5) the printed matter after drying must have excellent adhesion to the printing surface and (6) have high weather resistance and durability. Further, the ink composition for ink jet includes (7)
In order for the ink jet printer to be able to control printing, the ink jet ink composition must have a unique property that other ink compositions do not need to be charge-controlled.

[0005] By the way, the bar code printing including the ink jet printing method includes (a) a method of printing a bar code such as black on a white background, and (b) 300 to 400.
A method of printing an ink composition that emits blue, green, or red visible light when excited by ultraviolet light of nm is used or proposed.

The method of printing a bar code such as black on a white background (a) has the advantage of being very inexpensive and is widely used. Since the reading is performed by utilizing the difference, there is a drawback that if the article becomes dirty, the reading becomes extremely difficult. In addition, since reflected light in the visible light region is used, there is a disadvantage that the appearance of the article is necessarily impaired. Furthermore, OC
In a reading system using R, character information is sometimes printed in blue or black, so that the appearance of the article is inevitably deteriorated.

[0007] As an improvement of such a bar code such as black and white, a method of using an ink using an organic fluorescent dye which emits visible light when excited by ultraviolet rays as a bar code (b). Has been proposed. Printed matter using an ink using such an organic fluorescent dye is substantially invisible or difficult to recognize in the visible light region, and thus has the advantage of being able to print without impairing the appearance of the article, and is readable by a machine. At the same time, since the light-emitting region is in the visible light region, there is an advantage that the presence of a printing type or the like can be visually recognized, and it is attracting attention as an alternative to a barcode such as black and white.

[0008]

However, in the method using the above-mentioned conventional ink, the organic fluorescent dye to be used is inherently easily decomposed, and is inferior in light resistance and weather resistance. There is a problem that the light emission intensity in the state decreases with time. That is, even when the above-mentioned conventional ink shows high luminescence intensity at the beginning of preparation, the luminescence intensity tends to be remarkably reduced under storage at high temperature and high humidity. Therefore, in order to solve such a problem, by adding various additives to the ink or by adsorbing the organic fluorescent dye dissolved on the surface of inorganic particles such as silica or organic fine particles such as acrylic,
There have been proposals for improving light fastness and weather fastness.

[0009] However, even though the above-mentioned method using additives and particles is effective in improving the storage stability in the ink state, printing or other printing is performed on articles using this ink to obtain a printed material. In this case, it was found that the luminescence intensity was reduced only by leaving the printed matter at room temperature. That is,
Immediately after printing, even printed matter that shows high luminescence intensity, after storage for a long period of time, it became clear that luminescence could not be confirmed even if irradiated with excitation light, or luminescence intensity was insufficient, making it impossible to read by machine did. For this reason, the method using the above-mentioned organic fluorescent dye has a problem that the conditions of use are significantly limited.

In preparing the ink, a ketone-based organic solvent such as methyl ethyl ketone or methyl isobutyl ketone is usually used to dissolve the organic fluorescent dye in this solvent. When such an ink is used in a printer or a stamp-type printer, there is a problem that the solvent invades the urethane resin or the polyamide resin of the ink occlusion body that absorbs the ink, and the durability of the ink occlusion body is significantly reduced. Further, when printing with an ink jet printer, a dot impact printer, a stamp type printer, or the like, since the vapor of the solvent is harmful to the human body, use in an office becomes difficult, and the use environment is significantly restricted. There was a problem.

According to the present invention, in view of such circumstances, even when printed on an article, the appearance of the article is not impaired, and the printed printed matter can be detected with high sensitivity for a long period of time.
In addition, an ultraviolet-excited ink composition that does not attack the ink occlusion body, is safe for the human body and is not subject to any restrictions on the use environment, a fluorescent composition used for the ink composition, It is an object of the present invention to provide a printed matter printed in a dot shape, a thin film shape, or a thick film shape with the ink composition.

[0012]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object. As a result, the present inventors have found that (1) a base material and a particulate organic fluorescent dye which emits visible light when excited by ultraviolet rays. According to the ink composition obtained by dispersing the fluorescent composition in a solvent having a boiling point of 200 ° C. or higher, water or / and ethanol, it is possible to emit light with high sensitivity over a long period of time and to use an ink occlusion body. It does not invade, is safe to the human body, is not subject to any restrictions on the use environment, and (2) The printed matter printed in the form of a dot, a thin film or a thick film with the above ink composition is Of the present invention can be detected with high sensitivity even when stored for a long period of time, and completed the present invention.

That is, the present invention provides a fluorescent composition comprising a base material and an organic fluorescent dye which emits light in the visible light region when excited by ultraviolet light, wherein the organic fluorescent dye is a granular material. According to the present invention. Further, the present invention provides an ink composition comprising a resin, a solvent, and an organic fluorescent dye, wherein the organic fluorescent dye is composed of a granular material having a particle size of 10 to 2,000 nm, In a printed material having a print layer containing an organic fluorescent dye which is excited by ultraviolet light and emits light in a visible light region, the organic fluorescent dye has a particle diameter of 10 to 2.0.
And printed matter characterized by being made of 00 nm granular material.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The organic fluorescent dye used in the present invention is:
It is a dye that is excited by ultraviolet rays (wavelength less than 400 nm) and has an emission center in a visible light region (wavelength 400 to 700 nm), and particularly a dye that is substantially invisible or difficult to recognize in the visible light region. Although the emission color is not limited, red (wavelength around 600 nm, more preferably 615 ± 20 n
Those emitting m) visible light are particularly preferred because of their excellent detectability.

This is because, when a low-cost and easily obtainable silicon photodiode is used as a photoelectric conversion element for detecting the emitted visible light, the light receiving sensitivity of visible light is higher on the long wavelength side than on the short wavelength side. This is because sufficient detection sensitivity can be easily obtained with a dye that emits red visible light. In addition, generally used white paper contains a fluorescent whitening agent, and may emit blue light when irradiated with ultraviolet light. When printed on white paper to which this optical brightener has been added,
In the case of using an organic fluorescent dye that emits red light, even if the fluorescent whitening agent added to the white paper emits light, its wavelength is far from the emission wavelength of the organic fluorescent dye. Can be detected.

As described above, as the organic fluorescent dye of the present invention, a red-emitting organic fluorescent dye which has no absorption in the visible light region and is excited by ultraviolet light and has a light emission center wavelength in a long wavelength region around 600 nm is preferably used. As a typical example, a metal complex having a rare earth element such as europium or samarium as a light emission center and a ligand having a large number of π electrons as a counter ion is exemplified.

Among these, a europium compound having a large light emission amount is most preferable. Specifically, 400 to 70
It contains europium, which has no absorption in the visible light region of 0 nm and is therefore substantially invisible in the visible light region, and which has an emission center wavelength at 615 ± 20 nm when excited by ultraviolet light, including tenoyl trifluoromethane. acetone,
Naphthoyltrifluoroacetone, benzoyltrifluoroacetone, methylbenzoyltrifluoroacetone, furoyltrifluoroacetone, pivaloyltrifluoroacetone, hexafluoroacetylacetone, trifluoroacetylacetone, fluoroacetylacetone, heptafluorobutanoylpivaloylmethane, etc. And metal complexes as ligands. Among them, a europium compound having a ligand of tenoyltrifluoroacetone, naphthoyltrifluoroacetone, or methylbenzoyltrifluoroacetone having a large light emission amount is preferable.

Such organic fluorescent dyes are described in J. Am. Am. C
hem. Soc. 186, 5117, 1964
For example, it can be synthesized by the method described in Japanese Patent Application Publication No. 6-15269. Examples of commercially available organic fluorescent dyes include "Rumil-Tux CD 335", "L-Mir-Tux CD 331", and "L-Mir-Tux CD 332" manufactured by Rieder DeHaan, and "ER-12" manufactured by Mitsui Chemicals, Inc.
0 "," ER-122 "and the like.

As described above, such organic fluorescent dyes are inferior in storage stability such as light resistance and weather resistance, and the luminescence intensity in the state of the fluorescent composition or ink composition or the state of the printed matter with the passage of time. It tends to decrease, and the storage stability in the state of a fluorescent composition or printed matter is particularly poor. That is, in the ink state, the ink solvent is interposed between the dye and the outside air, thereby preventing direct contact between the dye and the outside air.However, in the state of the fluorescent composition or printed matter, there is an intervening substance such as the ink solvent. Instead, the degradability of the dye directly affects the stability of the printed matter. This phenomenon is the same even when a dye is adsorbed on the surface of inorganic or organic particles, and the dye is present on the particle surface in a molecular state similar to the dissolved state in the ink solvent. However, even when a printed material is used, the dye is in direct contact with the outside air, and the deterioration due to decomposition cannot be suppressed. Further, when the above ink is printed on paper, cloth, or the like, which is a printing material, a certain printing material has various functional groups on the surface, and this functional group promotes the decomposition of the printed organic fluorescent dye. Thus, even when left at room temperature, the light emission output tends to be significantly reduced.

Therefore, the present inventors have reduced the influence of the organic fluorescent dye from the outside air and, when a printed material is obtained, reduced the effect of the functional group of the printed material to suppress the decomposability of the organic fluorescent dye. Various methods were studied. As a result, it was found that by setting the organic fluorescent dye in a bulk state (granular state), not only in an ink state but also in a printed matter, excellent long-term storage stability and high emission output can be maintained. . That is, in the present invention, in using the above organic fluorescent dye, in combination with a base material,
By preferably forming the particles having a particle size of 10 to 2,000 nm, not only in the ink state using a solvent, but also in the case of a fluorescent composition or a printed matter without a solvent, excellent storage stability can be obtained. That is what I found.

The reason why such storage stability is obtained by the present invention is considered as follows. When the organic fluorescent dye is a granular material in a bulk state having a particle diameter of 10 to 2,000 nm, when the fluorescent dye is used as a fluorescent composition or a printed material, even when the dye comes into contact with the outside air or a functional group of a printed material, It is considered that only the surface of the granular material is deteriorated, and an active dye is present inside, so that a decrease in luminescence output is suppressed even after long-term storage. In addition, by adopting the shape of the granular material, compared to the case of using a dissolved organic fluorescent dye as in the past, paper or a material that easily absorbs ink, even when printing or other printing is performed on a printing material such as cloth. It is considered that the ink does not penetrate into the print material and exists in a form that conceals the surface of the print material, and as a result, excellent light output can be obtained even in the initial stage. The reason why the particle size in the above range is good is that, when the particle size is less than 10 nm, the effect of improving the storage stability such as light resistance and weather resistance of the printing material is insufficient, and the dye easily penetrates into the printing material. is there. Also, 2,000
If the thickness is more than 0 nm, problems such as dropping of the dye from the printed matter, and depending on the viewing angle, the organic fluorescent dye may be visible. In addition, as a base material that carries a dye, there are an inorganic base material and a resin base material manufactured by using a sol-gel method, and a resin base material is preferably used from the viewpoint of flexibility and adhesiveness with a print substrate. Can be

In a dot impact type printer or a stamp type printer, it is desirable to use a uniform solution in order to obtain clear prints and to prevent clogging of nozzles and the like when printing with an ink jet printer. As a solvent capable of dissolving an organic fluorescent dye, a ketone solvent or the like has been used. However, with ketone solvents,
Since the organic fluorescent dye cannot be formed into a granular material in a bulk state, and the dye is dissolved and comes into contact with the outside air in a molecular state, storage stability, that is, light stability, in the state of a fluorescent composition or an ink composition, and further in the state of a printed matter And the weather resistance is remarkably deteriorated. Also,
Such a solvent invades an ink absorbing member that absorbs ink, that is, a cloth ribbon made of a resin resin in a dot impact type printer, or a urethane foam resin in a stamp type printer, and significantly lowers its durability. In addition, this solvent generates vapor harmful to the human body, and is restricted in use in offices and the like.

In one preferred embodiment of the present invention, a solvent containing 94% by weight or more of water and / or ethanol is used. From the viewpoint of environmental friendliness, a solvent containing 95% by weight or more of water and / or ethanol is more preferably used. More preferably, it is only water or / and ethanol, most preferably only water. When another solvent is used in a proportion of 6% by weight or less, the other solvent is preferably one in which the organic fluorescent dye is insoluble.
As long as the organic fluorescent dye can be present as particulate matter in a bulk state in a combined system with ethanol and ethanol, it can be used without any particular limitation.

When the above-mentioned water or / and ethanol is used as a solvent, the base material is preferably one having low reactivity with an organic fluorescent dye and improving printability and durability of a printed layer. Although those which dissolve in the above-mentioned solvent of the present invention are used, in some cases, those which are emulsified and dispersed may be used. Specific examples of such resins include polyvinyl alcohol, phenolic resin, polyester resin, acrylic resin, cellulose resin, polyamide,
Maleic resin and the like can be mentioned. Among them, polyvinyl alcohol which is dissolved in the solvent of the present invention and has an excellent effect of dispersing the organic fluorescent dye is preferably used. The amount of the base resin used depends on the type, but the amount of the organic fluorescent dye 1
Usually, 50 to 100,000 parts by weight,
Preferably 100 to 100,000 parts by weight (in this case,
The content of the organic fluorescent dye is adjusted to be 0.1 to 50% by weight. Particularly preferably, 100 to 5,000 parts by weight, more preferably 200 to 3,000 parts by weight, and most preferably 500 to 5,000 parts by weight, based on 100 parts by weight of the organic fluorescent dye.
It is 3,000 parts by weight.

When water or / and ethanol is used as the solvent, the resin as the base material is a resin having an oxygen permeability coefficient of 1 × 10 ⁻¹⁹ (m ² · S ⁻¹ · Pa ⁻¹ ) or less. It is particularly preferred to contain at least one kind. When such a resin having low oxygen permeability is used, the organic fluorescent dye is covered with the resin, and the dye is effectively prevented from being oxidized and degraded by oxygen in the air in the print layer. Can be prevented. Although quinones are usually used as an antioxidant, it is better to use the above-described resin having a low oxygen permeability than the quinones in the case of a fluorescent composition or a printed matter without a solvent that is constantly exposed to the air. It is more effective in preventing oxidation of the organic fluorescent dye.

The oxygen permeability coefficient is 1 × 10 ⁻¹⁹ (m ² · S ⁻¹⁾
Examples of the resin having a ^{value of} Pa ^-1 or less include polyvinyl alcohol resin, polyvinyl alcohol-based resin (such as vinyl alcohol-vinyl acetate copolymer), polyvinyl resin, cellulose resin, and polyether. There are a tell-based resin, a polyester-based resin, a polyimide-based resin, a polyamide-based resin, and the like, and one or more of these are used.

Considering the solubility in a solvent, the stability of the ink, and the dispersibility of the organic fluorescent dye, polyvinyl alcohol
Or a polyvinyl alcohol-based resin is most preferred. Since the oxygen permeability coefficient depends on the degree of saponification of the polyvinyl alcohol-based resin, by adjusting the degree of saponification, a resin having a desired oxygen permeability coefficient can be easily obtained. Generally, a polyvinyl alcohol-based resin having a degree of saponification of 0.2 or more has an oxygen permeability coefficient of 1 × 10 ⁻¹⁹ (m ² · S ^-1 · P
a ^-1 ) At the same time, the solubility in an aqueous solvent is extremely high, which is desirable when applied to an ink jet ink.

The oxygen permeability coefficient is 1 × 10 ⁻¹⁹ (m ²
(S ^-1 · Pa ^-1 ), together with a resin having an oxygen permeability coefficient of more than 1 × 10 ^-19 (m ² · S ^-1 · Pa ^-1 ), for example, polyvinyl butyral, polyvinyl pyrrolidone, vinyl A polyvinyl resin such as a pyrrolidone-vinyl acetate copolymer may be used in combination. In addition, urethane resins containing a large amount of hydroxyl groups in the molecular chain and soluble in water and / or ethanol, such as urethane resins and acrylic / urethane graft copolymers, are also effective in improving the adhesion to pet films. Therefore, it is preferably used.

In the present invention, the oxygen permeability coefficient is 1 × 10
The amount of the resin of ^-19 (m ² · S ^-1 · Pa ^-1 ) or less is preferably 0.05 to 30% by weight, and preferably 0.5 to 20% by weight based on the total weight of the ink composition. More preferably, 1-1
5% by weight is more preferred. This range is preferred because
If the content is less than 0.05% by weight, the oxygen permeation inhibiting effect is reduced, and if the content is more than 30% by weight, the viscosity of the ink becomes too high, and the nozzles are easily clogged.

In the present invention, the oxygen permeability coefficient of the resin can be measured and evaluated in accordance with ASTM-D1434-75 (a method for measuring gas permeability coefficient in plastic films and sheets).

In another preferred embodiment of the present invention, as the solvent for the ink composition, a medium which is a hardly volatile medium having a boiling point of 200 ° C. or higher and in which the organic fluorescent dye is insoluble or has low solubility is used. This makes it possible to make the above-mentioned pigment into a bulk granular material having a particle size of 10 to 2,000 nm, and furthermore, there is no fear of generating harmful vapor to the human body, and it can be used in offices and the like. It is possible to prepare an ink composition without any restrictions on the use environment.

Among the above-mentioned non-volatile media having a boiling point of 200 ° C. or more, from the viewpoint of environmental friendliness, the boiling point of 250 vol.
C. or higher is preferred. Examples of such a medium include higher fatty acids that are liquid at room temperature, such as oleic acid, linoleic acid, and linolenic acid, castor oil, liquid paraffin, machine oil, polyoxyethylene (POE), and polyoxypropylene (POP). , Alkyl ether, POP alkyl ether, POE alkyl ether, polyethylene glycol, polypropylene glycol, glycerin, sorbitan ester, benzyl alcohol and the like. As the other medium, those in which the organic fluorescent dye is insoluble are preferable. As long as it can be used, it can be used without any particular limitation.

In the above-mentioned embodiment using a non-volatile medium, the resin base material is preferably one having low reactivity with an organic fluorescent dye and capable of improving printability and durability of a printed layer. Although those that dissolve in are used,
In some cases, a type capable of emulsification and dispersion may be used. Specific examples include rosin resin, phenol resin, ceramic resin, ketone resin, alkyd resin, maleic resin, and rosin-modified maleic resin. Among these, a rosin resin, a rosin-modified maleic resin, and the like, which dissolve in the above-mentioned solvent of the present invention and have an excellent effect of dispersing the organic fluorescent dye, are preferably used. The amount of the resin base material to be used depends on the kind thereof, but is usually 50 to 100,000 parts by weight, preferably 100 to 100,000 parts by weight (in this case, 100 parts by weight of the organic fluorescent dye). Content is 0.1 to 50% by weight).
Particularly preferably, 100 to 5,000 parts by weight, more preferably 20 parts by weight, per 100 parts by weight of the organic fluorescent dye.
0-3,000 parts by weight, most preferably 500-3.0 parts by weight
00 parts by weight. The above range is preferable because when the amount is less than 50 parts by weight, the adhesion strength of the printing layer is weak, and
If the amount exceeds the weight part, the luminous intensity of the fluorescent composition or printed matter becomes weak.

In the present invention, the above solvent is
An organic fluorescent dye is added together with the resin base material, and the mixture is well dispersed and mixed by a dispersing machine such as a ball mill or a sand mill to obtain a uniform ink composition in which the particulate matter of the dye is not settled.

The amount of the organic fluorescent dye used depends on the solvent 10
The amount is usually 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight based on 0 parts by weight. This range is preferable because the light emission intensity is low when the content is less than 0.01 part by weight, and the light emission intensity is not increased due to concentration quenching when the content exceeds 30 parts by weight. The particle size of the organic fluorescent dye before dispersion is usually 10 to 50 μm.
Dispersion and pulverization are performed simultaneously to obtain a granular material of 0 to 2,000 nm. When the particle size after dispersion is less than 10 nm, the dye becomes close to a dissolved state, and the deterioration proceeds with time, making it difficult to maintain the light emission output for a long time.
The dispersibility and dispersion stability of the granular material are deteriorated, sedimentation occurs, it is difficult to print uniformly, and clogging is liable to occur when printing with an ink jet printer or the like. For this reason, the lower limit of the particle size after dispersion is particularly preferably 50 nm or more, and more preferably 100 nm or more. The upper limit of the particle size after dispersion is particularly 800
nm or less, more preferably 600 nm or less,
500 nm or less is more preferable. Note that the upper limit of the particle size of the dye that can stably maintain a dispersed state in the ink composition is mainly determined by the viscosity of the solvent, and when a low-viscosity solvent such as water and / or ethanol is used. Is 800n
m or less is preferable.

In the present invention, the organic fluorescent dye composed of such particulate matter has a particle size after dispersion of 10 to 2.0.
It may be in the range of 00 nm, and not all of the granules need to have a uniform particle size. The particle size of the organic fluorescent dye refers to a sample prepared by diluting the ink composition about 1,000-fold with the same ratio of solvent, put it in a cell having a diameter of 12 mm, and perform dynamic light scattering method at room temperature. Medium, 5mW He-N
This is a value measured using an e-laser under the conditions of a measurement angle of 90 degrees and a cumulative number of 100 times.

In order to improve the dispersibility of the organic fluorescent dye, the ink composition of the present invention may contain a surfactant together with the above resin base material. In order to further suppress the deterioration of the organic fluorescent dye, a suitable amount of a phosphorus-based organic compound or the like can be used as an additive. further,
When used as an ink for an ink jet printer, an appropriate amount of a charge adjusting agent, a pH adjusting agent, and the like can be included.

For example, a Li salt such as LiNO ₃ , a K salt such as KSCN, a phosphonium salt or an ammonium salt represented by the following formula (1) can be added as a charge control agent. Among them, phosphonium salts and ammonium salts are more preferable because of high dispersion stability of the ink composition. The added amount of these charge control agents is 0.05 to 5 based on the total weight of the ink composition.
%, More preferably 0.1 to 5% by weight. This addition amount range is preferably 0.
If the amount is less than 05% by weight, the charge control effect is insufficient, and if it exceeds 5% by weight, the effect is saturated.

[0039] (In the formula, A is N or P, and R ^{1 to} R ⁴ are a hydrogen atom or a linear or cyclic hydrocarbon group having 1 to 14 carbon atoms, which may be the same or different. Often,
And at least two of R ^{1 to} R ⁴ may be bonded to each other to form a ring)

When printing on a plastic sheet, bag, bottle or the like, it is desirable to add 0.05 to 0.5% by weight of a fluorine-based surfactant. When the fluorine-based surfactant is added as described above, the dot diameter is reduced to about 40% as compared with the case where no fluorine-based surfactant is added. The reason why the above-mentioned addition amount range is preferable is that if the content is less than 0.05% by weight, the effect of reducing the dot diameter is small, and if it exceeds 0.5% by weight, the ink composition tends to foam.

In the present invention, such an ink composition is used, and it is used as a book, postcard, etc. by using a marker pen, an ink jet printer, a dot impact printer, a stamp printer or a stamp. A printed layer made of a desired mark such as a park is formed by printing on the surface of various articles such as postal items. At that time, since the ink composition contains the above-mentioned solvent, it is safe for the human body, is not limited in the use environment, and can be safely operated even in a closed office.

In the printed matter produced in this manner, since the organic fluorescent dye in the printed layer does not have a light-emitting and light-absorbing component in the visible light region, the printed layer is invisible or hardly recognizable. Absent. Moreover, when the printed matter is irradiated with ultraviolet light, the dye in the print layer is excited and emits light in the visible light region, which can be visually recognized, and can be used as a silicon photo diode as a photoelectric conversion element.
If the mark information is detected by a reading reader, the desired mark information can be read with high sensitivity. Further, the most significant feature of the present invention is that the above-mentioned organic fluorescent dye is present as fine particles in the ink state and the print layer state, and has excellent storage stability, that is, excellent light resistance and weather resistance. Therefore, the above mark information can be detected with high sensitivity over a long period of time.

[0043]

Next, an embodiment of the present invention will be described in more detail. However, the present invention is not limited only to the following examples. Hereinafter, “parts” means “parts by weight”.

Example 1 In 90 parts of water, 5 parts of polyvinyl alcohol (PVA manufactured by Kuraray Co., Ltd.) was dissolved as a base resin, and this was substantially invisible or difficult to recognize in the visible light region. And 0.5 part of a dye that emits light when excited by ultraviolet light (trade name: "CD335" manufactured by Rieder DeHaan Co., Ltd., excitation wavelength: 365 nm, emission wavelength: 615 nm) is added for 4 hours by a planetary ball mill. After the dispersion treatment, the pigment has a particle size of 210 to 4
An ultraviolet-excited ink composition was prepared which was present as 10 nm granules.

Example 2 The pigment had a particle size of 120 to 230 in the same manner as in Example 1 except that the dispersion treatment time with a planetary ball mill was changed to 8 hours.
An ultraviolet-excited ink composition was prepared, which was present as nanometer particles.

Comparative Example 1 The same dye as in Example 1 was added to 90 parts of methyl ethyl ketone.
5 parts were dissolved, and an acrylic resin (trade name "Dianal BR-1" manufactured by Mitsubishi Rayon Co., Ltd.) was further added as a resin base material.
06 ") 9.5 parts, and well stirred and mixed to dissolve,
An ultraviolet excitation type ink composition was prepared.

Comparative Example 2 In 3 parts of methyl ethyl ketone, 0.5 part of the same dye as in Example 1 was dissolved. Next, this dye solution was added to 77 parts of water as inorganic particles of silica particles 10 having an average particle size of 100 nm.
Parts, and 9.5 parts of polyvinyl alcohol (PVA manufactured by Kuraray Co., Ltd.) as a resin base material were mixed in a slurry, which was well stirred and mixed to obtain an ultraviolet-excitation ink composition. Prepared.

Each of the ink compositions of Examples 1 and 2 and Comparative Examples 1 and 2 was allowed to stand for 24 hours.
2 and each of the ink compositions of Comparative Examples 1 and 2,
Sedimentation of the organic fluorescent dye was observed. From these results, it was found that the ink compositions of Examples 1 and 2 and Comparative Examples 1 and 2 can be used as marker pens and ink jet inks.

Next, the respective ink compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were obtained by the following method.
The state of the ink and the intensity of the fluorescent light when the printed matter was obtained were measured. These results were as shown in Table 1.

<Fluorescence Emission Intensity in Ink State> Initially and after storage at a high temperature of the ink composition (400
After storage for a time, the fluorescence emission intensity was measured using a fluorescence spectrophotometer (“FP750” manufactured by JASCO Corporation), and Example 1 was obtained.
Are relative values with the initial light emission intensity taken as 100%.

<Fluorescence emission intensity of printed matter> The ink composition was packed in a marker pen and used to form a printed layer on white paper. About this printed matter, 3
The fluorescence emission intensity after storage for one month was measured by a fluorescence spectrophotometer ("FP750" manufactured by JASCO Corporation), and the relative emission intensity was shown as a relative value with the initial emission intensity of Example 1 being 100%.

[0052]

As is clear from the results shown in Table 1, both ink compositions of Examples 1 and 2 have an organic fluorescent dye present in the form of particles in a bulk state, so that the initial fluorescence emission intensity is high. In addition, the decrease in the strength after storage at high temperatures is suppressed, and the printed matter printed using the same has a reduced decrease in the strength after long-term storage. It can be seen that the storage stability is remarkably excellent even in the state described above.

On the other hand, the ink composition of Comparative Example 1
Since the organic fluorescent dye is present in a state of being completely dissolved in the solvent, the initial fluorescence emission intensity is low, the intensity is further deteriorated after high-temperature storage, and the intensity is further reduced when the print is in a state. In addition, deterioration after long-term storage is remarkable. In addition, the ink composition of Comparative Example 2 has an effect of improving the fluorescence emission intensity to some extent as compared with Comparative Example 1 by adsorbing the organic fluorescent dye on the surface of the inorganic particles. Compared with the printed matter, the printed matter is remarkably inferior, and particularly the printed matter has remarkably poor long-term storage characteristics.

Example 3 In 90 parts of water, an oxygen permeability coefficient was 5 × 10 ⁻²⁰ (m ² · S ^−1).
・ Pa ^-1 ) polyvinyl alcohol (Kuraray PV
A) 5 parts were dissolved, and the resulting product was used as an organic fluorescent dye under the trade name "CD335" manufactured by Rieder DeHaan (excitation wavelength: 3).
(65 nm, emission wavelength: 615 nm, ligand: thenoyl trifluoroacetone) (0.5 part) was added, and the mixture was dispersed for 4 hours by a planetary ball mill to give the dye having a particle size of 210 to 4
An ultraviolet-excited ink composition was prepared which was present as 10 nm granules. In this ink composition, the organic fluorescent dye was 0.52% by weight, the resin (polyvinyl alcohol) was 5.24% by weight, and the solvent (water) was 94.24.
% By weight, and the proportion of water and / or ethanol in the solvent is 100% by weight.

Example 4 Oxygen permeability coefficient was 5 × 10^-20(M^Two・ S^-1・ Pa^-1)of
Replaced 5 parts of polyvinyl alcohol (Kuraray PVA)
The oxygen permeability coefficient is 7 × 10^{-twenty two}(M^Two・ S ^-1・ Pa
^-1) Polyvinyl alcohol (Kuraray's PVA) 5
Except for using the organic fluorescent part,
The pigment is present as particulate matter having a particle size of 210 to 410 nm
An ultraviolet excitation type ink composition was prepared.

Example 5 Oxygen permeability coefficient was 5 × 10^-20(M^Two・ S^-1・ Pa^-1)of
Replaced 5 parts of polyvinyl alcohol (Kuraray PVA)
The oxygen permeability coefficient is 3 × 10^{-twenty three}(M^Two・ S ^-1・ Pa
^-1) Polyvinyl alcohol (Kuraray's PVA) 5
Except for using the organic fluorescent part,
The pigment is present as particulate matter having a particle size of 210 to 410 nm
An ultraviolet excitation type ink composition was prepared.

Example 6 The same procedure as in Example 3 was carried out except that the dispersion treatment time using a planetary ball mill was changed to 8 hours.
An ultraviolet-excited ink composition was prepared that was present as particulate matter of ~ 250 nm.

Example 7 An organic fluorescent dye having a particle diameter of 80 was prepared in the same manner as in Example 3 except that the dispersion treatment time by a planetary ball mill was changed to 16 hours.
An ultraviolet-excited ink composition was prepared that was present as granules of ~ 190 nm.

Example 8 The oxygen permeability coefficient was 5 × 10^-20(M^Two・ S^-1・ Pa^-1)of
Replaced 5 parts of polyvinyl alcohol (Kuraray PVA)
The oxygen permeability coefficient is 4 × 10^-20(M^Two・ S ^-1・ Pa
^-1Except that 5 parts of polyoxyethylene were used
In the same manner as in Example 3, the organic fluorescent dye has a particle size of 210 to 410.
UV-excited ink composition present as nanometer particles
Was prepared.

Example 9 "Fluora" manufactured by 3M Co., Ltd. as a fluorosurfactant
UVFC430 was prepared in the same manner as in Example 3 except that 0.1 part of "FC430" was added.

Reference Example 1 Oxygen permeability coefficient is 5 × 10^-20(M^Two・ S^-1・ Pa^-1)of
Replaced 5 parts of polyvinyl alcohol (Kuraray PVA)
The oxygen permeability coefficient is 3 × 10^-19(M^Two・ S ^-1・ Pa
^-15) Polyvinyl acetate (UCC)
Example 3 except that 90 parts of ethanol were used.
And the organic fluorescent dye is granular with a particle size of 210 to 410 nm.
To prepare an ultraviolet-excited ink composition
Was.

Reference Example 2 An acrylic / urethane graft was used instead of 5 parts of polyvinyl alcohol (PVA manufactured by Kuraray Co., Ltd.) having an oxygen permeability coefficient of 5 × 10 ^-20 (m ² · S ^-1 · Pa ^-1 ). Except for using 15 parts of a polymer [“3DR-057” manufactured by Taisei Kako Co., solid content 35% by weight, oxygen permeability coefficient 3 × 10 ⁻¹⁸ (m ² · S ⁻¹ · Pa ⁻¹ )] In the same manner as in Example 3, an ultraviolet-excitation ink composition in which the organic fluorescent dye was present as particles having a particle size of 90 to 180 nm was prepared.

Reference Example 3 An organic fluorescent dye having a particle diameter of 900 was prepared in the same manner as in Example 3 except that the dispersion treatment time using a planetary ball mill was changed to 1 hour.
A UV-excited ink composition was prepared which was present as granules of 〜1,400 nm.

Comparative Example 3 In 90 parts of methyl ethyl ketone, 0.5 part of the same organic fluorescent dye as in Example 3 was dissolved, and an acrylic resin ["Dianal BR-106" manufactured by Mitsubishi Rayon Co., Ltd .; 9.5 parts with a coefficient of 9 × 10 ⁻¹⁹ (m ² · S ⁻¹ · Pa ⁻¹ )], and well stirred and mixed to prepare an ultraviolet-excitation ink composition.

Comparative Example 4 In 3 parts of methyl ethyl ketone, 0.5 part of the same organic fluorescent dye as in Example 3 was dissolved. In 77 parts of water, 10 parts of silica particles having an average particle diameter of 100 nm as inorganic particles were added to 77 parts of water and the oxygen transmission coefficient was 5 × 10 ^-20 (m ² · S ^-1 · Pa ^-1 ).
9.5 polyvinyl alcohol (Kuraray PVA)
The resulting mixture was blended into a slurry prepared by mixing the components, and the mixture was thoroughly stirred and mixed to prepare an ultraviolet-excitation ink composition.

When the ink compositions of Examples 3 to 9, Reference Examples 1 to 3 and Comparative Examples 3 and 4 were allowed to stand for one day and night, Examples 3 to 9, Reference Examples 1 and 2, and Comparative Examples In each of the ink compositions of Nos. 3 and 4, no sedimentation of the organic fluorescent dye was observed, but in the ink composition of Reference Example 3, sedimentation of the organic fluorescent dye was clearly observed. From these results, Examples 3 to
9, the ink compositions of Reference Examples 1 and 2 and Comparative Examples 3 and 4 can be used as marker pens, but the ink composition of Reference Example 3 cannot be used for the above applications. I knew there was. However, this evaluation is for applications that require low viscosity ink, such as marker pens.
Even the one having the particle diameter of Reference Example 3 can be used in applications such as Examples 10 to 12 described below.

Next, the above-mentioned usable embodiments 3 to
9, the ink state of each of the ink compositions of Reference Examples 1 and 2 and Comparative Examples 3 and 4 was measured in the same manner as described above, and the fluorescence emission intensity of the printed material was measured. However,
The fluorescence emission intensity of the printed matter was measured initially, after storage for 3 months indoors, and after storage for 1 month outdoors, and expressed as a relative value with the initial emission intensity of Example 3 taken as 100%. If the fluorescence emission intensity of the printed matter after being stored outdoors for one month is 30% or more, it can be read by a bar code reader. These results were as shown in Table 2.

[0069]

As is clear from the results in Table 2 above, in each of the ink compositions of Examples 3 to 9 and Reference Examples 1 and 2, an organic fluorescent dye having a particle size of 10 to 800 nm is present as a bulk particulate material. Therefore, the initial fluorescence emission intensity is high, and the decrease in the intensity after storage at high temperature is small. Also,
The printed matter printed using this has a fluorescence emission intensity after storage at room temperature at a practical level (30% or more), and can be read by a bar code reader. Further, printed matter using each of the ink compositions of Examples 3 to 9 containing at least one resin having an oxygen permeability coefficient of 5 × 10 ⁻¹⁹ (m ² · S ⁻¹ · Pa ⁻¹ ) or less, The luminescence intensity after outdoor storage is maintained at a high level. From these results, it can be seen that the ink composition of the present invention has high light resistance and weather resistance not only in an ink state but also in a printed state and under severe conditions such as an outdoor environment.

On the other hand, the ink composition of Comparative Example 3 was
Since the organic fluorescent dye is present in a state of being completely dissolved in the solvent, the initial fluorescence emission intensity is low, the intensity is further deteriorated after high-temperature storage, and the intensity is further reduced when the print is in a state. In addition, deterioration after long-term storage is remarkable. Further, the ink composition of Comparative Example 4 had a certain effect of improving the fluorescence emission intensity as compared with Comparative Example 3 by adsorbing the organic fluorescent dye on the surface of the inorganic particles. Compared with the printed matter, the printed matter is remarkably inferior, and particularly the printed matter has remarkably poor long-term storage characteristics.

Next, with respect to the ink compositions of Example 5 and Reference Example 1 described above, a heat treatment was performed on the printed matter printed using the ink compositions to evaluate the preservability of the ink composition indoors and outdoors. Went. That is, after applying both ink compositions on a glass plate and drying,
C. for 5 minutes (heat treatment A), 100.degree. C. for 5 minutes (heat treatment B) or 150.degree. C. for 5 minutes (heat treatment C), and the fluorescence emission intensity of the printed material after the heat treatment was measured by the following method. The results are shown in Table 3 together with the crystallinity of the resin in the printed layer after each heat treatment.

<Fluorescence Emission Intensity of Printed Material> The printed material after the heat treatment was initially stored after being stored in a room for 6 months and outdoors.
The fluorescence emission intensity after storage for one month was measured by a fluorescence spectrophotometer ("FP750" manufactured by JASCO Corporation), and was shown as a relative value with the initial emission intensity of Example 5 being 100%.

[0074]

As is clear from the results in Table 3 above, the printed matter of Example 5 in which the degree of crystallinity of the resin was increased to 0.1 or more by heat treatment was severe in indoor storage for 6 months and outdoor storage for 3 months. Even under mild storage conditions, the decrease in emission intensity is considerably smaller than that of the printed matter of Reference Example 1 in which the crystallinity after heat treatment is less than 0.1, and the light resistance and weather resistance are further increased. You can see that there is.

Next, with respect to each of the ink compositions of Examples 3 and 9, ink droplets were dropped on a white pet film, and the dot diameter and adhesion were evaluated. Table 4 shows the results.
It was shown to. With respect to the dot diameter, when the dot diameter of the ink composition of Example 3 was set to 100, the dot diameter was shown as a relative value. As is evident from the results in Table 4, the dot diameter of Example 9 in which the fluorine-based surfactant was contained was smaller than that of Example 3 in which the fluorine-based surfactant was not contained. Understand.

[0077]

Example 10 A rosin ester resin (manufactured by Arakawa Chemical Co., Ltd.) was used as a resin base material in 50 parts of castor oil and 40 parts of sorbitan acid alkyl ester ("OP-80" manufactured by NOF CORPORATION) at a boiling point of 200 ° C. or higher. Was added and heated and dissolved to prepare a vehicle. to this,
Substantially invisible or difficult to recognize in the visible light range,
And a dye that emits light when excited by ultraviolet light (trade name “CD335” manufactured by Rieder DeHaan, excitation wavelength: 36)
(5 nm, emission wavelength: 615 nm)
Dispersion for 4 hours.
An ultraviolet-excited ink composition was prepared which was present as particulates of 0-410 nm.

Example 11 The dye had a particle size of 120 to 23 in the same manner as in Example 10 except that the dispersion treatment time by a planetary ball mill was changed to 8 hours.
An ultraviolet-excited ink composition was prepared which was present as 0 nm granules.

Example 12 The same procedure as in Example 10 was carried out except that the dispersion treatment time using a planetary ball mill was changed to 1 hour, and the particle size of the pigment was 1,000 to 1,000.
An ultraviolet-excited ink composition was prepared which was present as 1600 nm granules.

Comparative Example 5 Example 1 was added to 90 parts of methyl ethyl ketone (boiling point: 80 ° C.).
Dissolve 1 part of the same pigment as in Example 0, add 9 parts of an acrylic resin (trade name "Dianal BR-106" manufactured by Mitsubishi Rayon) as a resin base material, and stir and mix well to dissolve. Then, an ultraviolet excitation type ink composition was prepared.

Comparative Example 6 The dye had a particle size of 2,20 in the same manner as in Example 10 except that the dispersion treatment time by a planetary ball mill was changed to 0.5 hour.
An ultraviolet-excited ink composition was prepared which was present as particles of 0 to 2,900 nm.

Comparative Example 7 One part of the same dye as in Example 10 was dissolved in 5 parts of methyl ethyl ketone. Next, castor oil (boiling point 200 ° C. or more) 77
In a resin solution obtained by heating and dissolving 9.5 parts of a rosin ester resin (“Ester Gum AAL” manufactured by Arakawa Chemical Co., Ltd.) as a resin base material, 10 parts of silica particles having an average particle diameter of 100 nm were added as inorganic particles and mixed. Thus, a silica dispersion slurry was obtained. The above-mentioned dye solution was blended with this slurry, and this was mixed well by stirring to prepare an ultraviolet-excitation ink composition.

The above Examples 10 to 12 and Comparative Examples 5 to
When each of the ink compositions of Nos. 7 and 7 was allowed to stand for one month, in each of the ink compositions of Examples 10 to 12 and Comparative Examples 5 and 7, sedimentation of the organic fluorescent dye was observed. In the ink composition of Example 6, sedimentation of the organic fluorescent dye was clearly observed. Further, each of the above ink compositions,
When filled into a urethane sponge having continuous pores and used as a stamp ink, the ink composition of Comparative Example 5 eroded the urethane sponge of the ink occluding body, making printing impossible, and the ink of Comparative Example 6 In the compositions, there were many drops and blurs of the printed matter, which were considered to be caused by the sedimentation of the pigment. However, the ink compositions of Examples 10 to 12 and Comparative Example 7 did not have such a problem.

Next, for each of the ink compositions of Examples 10 to 12 and Comparative Examples 5 to 7, the fluorescence emission intensity in the ink state was measured in the same manner as described above. 10 as a relative value with the initial emission intensity being 100%). In addition, the fluorescence emission intensity when a printed material was formed using each ink composition was measured by the following method. These results were as shown in Table 5.

<Fluorescence intensity of printed matter> The ink composition was used as a stamp ink, and a printing layer was formed on white paper using the ink composition. The fluorescence intensity of this printed matter, initially and after storage for 3 months in a room, was measured with a fluorescence spectrophotometer (“FP750” manufactured by JASCO Corporation).
It is shown as a relative value with the initial light emission intensity of Example 10 being 100%. In Comparative Example 5, the measurement was impossible because the urethane resin of the ink occluding body was damaged and printing was impossible, and in Comparative Example 6, the printed matter was often missing and blurred.

[0087]

As is clear from the results shown in Table 5 above, in each of the ink compositions of Examples 10 to 12, since the organic fluorescent dye was present as particulate matter in a bulk state, the initial fluorescence emission was The strength has been increased, and the decrease in strength after high-temperature storage has been suppressed.Moreover, for printed matter printed using this, the decrease in strength after long-term storage has been reduced, and only the ink state has been reduced. On the other hand, it can be seen that the storage stability is remarkably excellent even in a printed state.

On the other hand, the ink composition of Comparative Example 5 was
Since the organic fluorescent dye exists in a state of being completely dissolved in the solvent, the initial fluorescence emission intensity is low, and the intensity is more significantly deteriorated after storage at a high temperature. In addition, the ink composition of Comparative Example 7 had a certain effect of improving the fluorescence emission intensity compared to Comparative Example 5 by adsorbing the organic fluorescent dye on the surface of the inorganic particles. Compared with the printed matter, the printed matter is remarkably inferior, and particularly the printed matter has remarkably poor long-term storage characteristics.

[0090]

As described above, in the present invention, the organic fluorescent dye which is substantially invisible or difficult to recognize in the visible light region and emits light in the visible light region when excited by ultraviolet light is used in the bulk state. The presence of the particulate matter allows the desired mark to be printed on the article without impairing its appearance, and the printed mark can be detected with high sensitivity over a long period of time. To provide a UV-excited fluorescent composition, an ink composition, and a printed material thereof that are safe to use and are not subject to any restrictions on the use environment.

Continuing from the front page (72) Inventor Yuyuki Mitsubashi 1-1-88 Ushitora, Ibaraki City, Osaka Prefecture Inside Hitachi Maxell Co., Ltd. (72) Inventor Yukinori Yamada 1-1-88 Ushitora, Ibaraki City, Osaka Hitachi Maxell Co., Ltd. (72) Inventor Tomohisa Nishimoto 1-88 Ushitora, Ibaraki-shi, Osaka F-term in Hitachi Maxell Co., Ltd. (reference) 2C056 EA13 FC02 FD20 2H086 BA52 BA56 4J039 AB02 AB08 AB09 AD06 AD10 AD14 AE01 AE02 AE06 AE08 BC07 BC09 BC19 BC20 BC59 BE02 CA06 EA10 EA15 EA28 EA34 EA35 EA44 EA45 GA05 GA07 GA24

Claims (19)

[Claims] 1. A fluorescent composition comprising a base material and an organic fluorescent dye that emits light in the visible light region when excited by ultraviolet light, wherein the organic fluorescent dye is formed of a particulate material. object. 2. The phosphor composition according to claim 1, wherein the base material comprises a resin. 3. The fluorescent composition according to claim 1, wherein the organic fluorescent dye is substantially invisible in a visible light region. 4. The organic fluorescent dye particles having a particle size of 10 to 10.
The fluorescent composition according to any one of claims 1 to 3, which has a thickness of 2,000 nm. 5. The fluorescent composition according to claim 1, wherein the organic fluorescent dye is a europium compound having europium as an emission center. 6. The resin base material has an oxygen permeability coefficient of 1 × 1.
At least one resin of 0 ^-19 (m ² · S ^-1 · Pa ^-1 ) or less
The fluorescent composition according to any one of claims 2 to 5, which contains a species. 7. The fluorescent composition according to claim 1, wherein the content of the organic fluorescent dye is 0.1 to 50% by weight. 8. An ink composition containing a resin, a solvent and an organic fluorescent dye, wherein the organic fluorescent dye has a particle size of 10 to 10.
An ink composition comprising 2,000 nm particulate matter. 9. The ink composition according to claim 8, wherein the organic fluorescent dye is a granular material having a particle size of 10 to 800 nm. 10. The ink composition according to claim 8, wherein the organic fluorescent dye is substantially invisible in a visible light region. 11. The ink composition according to claim 8, wherein the organic fluorescent dye is a europium compound having europium as an emission center. 12. The ink composition according to claim 8, wherein the ink composition is contained in a solvent in which the organic fluorescent dye is essentially insoluble. 13. The ink composition according to claim 9, wherein the solvent is water and / or ethanol. 14. The ink composition according to claim 8, wherein the solvent is hardly volatile with a boiling point of 200 ° C. or higher. 15. A printed matter having a printed layer containing an organic fluorescent dye which is excited by ultraviolet light and emits light in a visible light region on an article, wherein the organic fluorescent dye has a particle size of 10 to 2,000.
Printed matter comprising a 0 nm granular material. 16. The printed matter according to claim 15, wherein the organic fluorescent dye is substantially invisible in a visible light region. 17. The printed matter according to claim 15, wherein the organic fluorescent dye is a europium compound having europium as an emission center. 18. The printing layer having an oxygen permeability coefficient of 1 × 10
^-19(M^Two・ S^-1・ Pa ^-1) At least one of the following resins
The printed matter according to any one of claims 15 to 17, wherein the printed matter is contained. 19. The printed matter according to claim 15, wherein the content of the organic fluorescent dye in the print layer is 0.1 to 50% by weight.