JP2002088688A - Anticouterfeit paper having excellent printability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the printability of anticounterfeit paper in which fluorescent ray-emitting particles are used. SOLUTION: In the anticounterfeit paper that includes the fluorescent ray- emitting particles produced by mixing a powdery substance, a fluororescent ray-emitting dye and/or pigments, or the fluorescent ray-emitting particles produced by coating the particles of powdery substance on their surfaces with a fluorescent dye and/or fluorescent pigment, a printability-imparting layer is formed on the paper at such a level that the fluorescent ray-emitting particles can be visually recognized, when the paper is irradiated with ultraviolet rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-counterfeit paper using fluorescent coloring particles and having improved printability.

[0002]

2. Description of the Related Art Various anti-counterfeit papers are known in which a particulate, fibrous, or strip-like substance having a property of emitting visible light of a specific wavelength (irradiating fluorescent light) upon irradiation with ultraviolet light is contained in the paper. ing. This anti-counterfeit paper irradiates the paper with ultraviolet light, such as black light, so that the fluorescent coloring material contained in the paper emits light of a specific wavelength in the visible light region. By detecting the
It has the characteristic that it can be determined whether or not the paper is forged.

[0003] Regarding forgery prevention paper in which a particulate fluorescent coloring material is formed into paper, the applicant of the present invention has disclosed in Japanese Utility Model Laid-Open No. 6-65.
No. 00 (Jpn. Pat. Appln. KOKAI Publication No. 4-51094) proposed a forgery prevention paper in which a substance that emits fluorescent light upon irradiation with ultraviolet light was applied to paper, and the resulting particles were ground and the fluorescent light-emitting particles were formed on the paper.

Further, the present applicant has filed Japanese Patent Application No. 10-2390.
No. 4 proposed an anti-counterfeit paper in which an ionic fluorescent dye was fixed to special ionic and heat-resistant starch particles, and the starch particles were formed into paper.

[0005] Further, the present applicant has filed Japanese Patent Application No. 10-924.
No. 77 proposed anti-counterfeit paper in which water-insoluble pigments that emit fluorescence when irradiated with ultraviolet light were coated on the surface of self-adhesive particles by a high-speed air impact method, and the particles were formed into paper.

[0006] Furthermore, the present applicant has filed Japanese Patent Application No. 11-3472.
No. 37, a fluorescent coloring particle produced by granulation of a mixture of a powdery substance and a fluorescent coloring particle, or a granulated substance of a powdery substance, and a water-insoluble dye which produces a fluorescent color on the surface of the granulated substance And / or the use of fluorescent particles produced by coating pigments.

[0007]

All of the above-mentioned prior arts are forgery prevention papers in which a particulate fluorescent coloring material is contained in the paper. Among these, the anti-counterfeit paper proposed in Japanese Utility Model Application Laid-Open No. 6-6500 appears that the fluorescent coloring particles are present in the paper in the form of irregular and minute flocs, but the size of these particles is controlled. It is difficult and has a problem that an unnecessarily large floc and an unnecessarily small floc are mixed in a sheet.

Further, the anti-counterfeit paper proposed in Japanese Patent Application No. 10-23904 uses fluorescent coloring particles using a fluorescent dye, and therefore necessarily has poorer light resistance than one using a fluorescent pigment. In addition, there is a problem that the intensity of coloring by ultraviolet irradiation is weak. In addition, there is also a problem that only a limited hue can be obtained for the fluorescent hue.

Further, the fluorescent coloring particles used in the anti-counterfeit paper proposed in Japanese Patent Application No. 10-92477 use a fluorescent pigment, so that the fluorescent coloring particles have a higher luminous intensity than the fluorescent coloring particles using a fluorescent dye. Although it has the advantage of being excellent in light fastness, there are problems that an expensive device is required for its production and that the production yield is poor.

On the other hand, there are various problems in including the fluorescent pigment itself in paper. First, since the particle size of commercially available fluorescent pigments is as small as about 0.5 to 3 μm, the presence of individual fluorescent particles cannot be confirmed even when the fluorescent pigment particles are contained in paper by several percent and irradiated with ultraviolet light in a bright room. There is a problem. In order to be able to confirm the presence of the fluorescent pigment, it is necessary to increase the particle size.In that case, however, it is necessary to manufacture a particle having a special particle size. It will be expensive. In addition, since the specific gravity of the inorganic fluorescent pigment is as large as 4 to 5, if the particle size is increased, for example, even if an attempt is made to add the slurry to the slurry to form paper, the fluorescent pigment precipitates during the flow of the slurry.

[0011] In order to solve the above problems, the present applicant disclosed in Japanese Patent Application No. 11-347237 a fluorescent coloring particles or a powdery substance produced by granulating a mixture of a powdery substance and fluorescent coloring particles. And the use of fluorescent particles produced by coating the surface of the granules with a water-insoluble dye and / or pigment that emits fluorescent light. This solves the problem that the fluorescent coloring particles settle during the flow of the slurry by using a powdery substance having a low specific gravity.Furthermore, fluorescent coloring particles having a uniform particle size and a large particle size are obtained, and the counterfeiting prevention effect is obtained. It has become possible to manufacture anti-counterfeit paper with excellent productivity.

As a result of further studies by the present inventors, the forgery prevention paper proposed in Japanese Patent Application No. 11-347237 described above has a problem in that, when an ink with a large tack is used at the time of offset printing, fluorescent coloring particles on the surface of the paper are used. However, it was found that it had a problem that it could easily fall off. To improve this,
The patent proposes that the forgery prevention paper has at least three layers and the inner layer contains fluorescent coloring particles. However, this method has a problem that a paper machine that can be manufactured is limited to a paper machine that can make a multi-layer paper, and cannot be manufactured by a fourdrinier paper machine that can perform high-speed paper making. Also, to use two or more kinds of raw materials,
There is also a problem that productivity is poor and economically disadvantageous. Furthermore, since the paper is not provided with a coating layer, the print quality is far from art paper and coated paper.

On the other hand, it is generally known to provide a printability-imparting layer containing an inorganic powder and a binder as main components in order to improve printability. However, if a printability-imparting layer is provided on the forgery-preventing paper containing the fluorescent coloring particles, the fluorescent coloring particles cannot be confirmed from the external appearance, and the forgery preventing effect cannot be exhibited. This is because the inorganic particles are contained in the printability-imparting layer, so that ultraviolet light, which is indispensable for the coloring of the fluorescent coloring particles, and visible light generated from the fluorescent coloring particles due to the irradiation of the ultraviolet light come out on the paper surface. Is to inhibit For this reason, it has been considered meaningless to provide a printability-imparting layer on forgery-preventing paper containing fluorescent coloring particles.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, provided a printability-imparting layer for improving the printability even if it does not hinder the confirmation of the fluorescent coloring particles. Was found to be possible. In addition, for the printability-imparting layer that does not inhibit the confirmation of the fluorescent coloring particles and has excellent printability, the type, particle size, refractive index, compounding amount, and coating amount of the inorganic powder contained in the printability-imparting layer are important. Was found. Further, they have found that printability can be improved only by using a resin without using an inorganic powder, thereby completing the present invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION As a powdery substance used for fluorescent coloring particles, a typical example is starch. More specifically, natural starches such as potato starch, corn starch, sweet potato starch, tapioca starch, sago starch, rice starch, amaranth starch, taro starch, and Doshojo starch, and their modified starches (dextrin, acid-decomposed starch, oxidized starch, Starch derivatives such as alpha-starch, etherification, esterification, cross-linking,
Grafted starch, heat-moisture treated starch, etc.). Flour such as wheat flour, rice flour and corn flour; water-insoluble powdered cellulose such as powdered cellulose, bacterial cellulose, microfibrous cellulose, crystalline cellulose and the like;
Wood flour; carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose,
Hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose,
Cellulose derivatives such as quaternary cationized hydroxyethylcellulose; alginic acid, agar, seaweed, carrageenan, furceleran, pectin, chitin, chitosan, guar gum, locust bean gum, tamarind gum, arabic gum, tragacanth gum, karaya gum, cod gum, konjac, trollooi, pullulan , Dextran and the like; derivatives thereof; powdered sugars such as glucose, sucrose and lactose; and powdered organic substances such as polyvinyl alcohol having a high degree of polymerization and high saponification degree can also be used as the powdery substance.

Further, a powdered inorganic substance can be used as the powdered substance. Powdered inorganic substances include titanium dioxide, silicates (kaolin, clay, bentonite, talc, synthetic aluminum silicate, synthetic calcium silicate, etc.) and silicic acid (diatomaceous earth, silica powder, hydrous fine silica, anhydrous fine silica, which are known as fillers) ), Calcium carbonate, zinc oxide, magnesium carbonate, calcium magnesium carbonate, aluminum hydroxide, barium sulfate, calcium sulfate, calcium sulfite, iron oxide and the like.

These powdery substances may be used alone,
Two or more kinds may be used as a mixture. When powdery substances having a hydroxyl group such as starch, flour, cellulose, other polysaccharides, sugars, and polyvinyl alcohol are used as the powdery substance, use in combination with a resin binder having a reactive group that reacts with the hydroxyl group. Is effective for imparting water resistance to the fluorescent coloring particles, and also plays a role of increasing the amount of expensive fluorescent dyes and / or pigments because it does not lower the coloring intensity even when coated with a fluorescent dye and / or pigment. Therefore, it can be added to the coating solution when coating the resin binder as long as the object of the present invention is not hindered.

When a forgery prevention paper is manufactured by incorporating fluorescent coloring particles prepared by using starch, powdered saccharide, polyvinyl alcohol, or the like in a powdery material, the place where the particles are present is partially reduced. Tends to be transparent. Since such a transparent portion can be visually recognized under ordinary light, the aesthetic appearance of printing may be impaired when printing on paper.

In order to prevent the fluorescent coloring particles from becoming transparent in the paper, a white pigment may be used in combination with a powdery substance such as starch. This makes it difficult to see the presence of the fluorescent particles in the paper under normal light, not only does not impair the aesthetics of printing and the like, but also makes it difficult to determine that forgery prevention measures are taken. Therefore, the forgery prevention effect can be further enhanced.

As the white pigment, among the above-mentioned powdered inorganic substances, those having high whiteness, such as titanium dioxide, kaolin, clay, talc, calcium carbonate, zinc chloride,
Zinc sulfide, zinc oxide, magnesium carbonate, calcium / magnesium carbonate, aluminum hydroxide, barium sulfate and the like can be used. In the present invention, these white pigments may be used alone or in combination of two or more.

In the present invention, the use of those white pigments having a high light refractive index, that is, those having a refractive index of 2.0 or more, prevents the above-mentioned fluorescent coloring particles from becoming transparent in paper. Great effect. For example, titanium dioxide (refractive index: about 2.6), zinc sulfide (2.3), zinc oxide (2.0), and the like.

The fluorescent coloring particles of the present invention are of a type for granulating a mixture containing all of the particle components such as a powdery substance, a fluorescent dye and / or a fluorescent pigment (mixture type), and a granulated substance containing a powdery substance. And a type (core-shell type) in which a coating layer containing a fluorescent dye and / or a fluorescent pigment is formed on the outside. Mixture type particles have the advantage of being easy to manufacture, but from the viewpoint of fluorescent coloring, from the viewpoint of fluorescent coloring, although fluorescent dyes and fluorescent pigments existing near the particle surface emit fluorescent coloring, Fluorescent coloring tends to be difficult. On the other hand, the core-shell type particles, in which the fluorescent dye and the fluorescent pigment are present only in the outer coating layer of the granulated material serving as the core, all contribute to the fluorescent coloring.
Therefore, when the same amount of fluorescent dye or fluorescent pigment is used, the core-shell type particles have an advantage that a stronger fluorescent coloring intensity can be obtained than the mixture type particles.

The fluorescent agent (fluorescent dye and fluorescent pigment) used in the present invention will be described. The fluorescent agent used in the present invention needs to be insoluble in water. If it is soluble in water, these fluorescent agents are eluted from the fluorescent coloring particles added to the slurry when the anti-counterfeit paper is manufactured, as described later in detail, and the object of the present invention cannot be achieved.

The term "insoluble in water" used in the present invention means not the property of the fluorescent agent alone but means that the fluorescent agent is not eluted in water after the fluorescent particles are produced. That is, even a water-soluble fluorescent dye such as a spirofuran-based fluorescent dye reacts with a water-proofing agent used in combination with the production of fluorescent particles to become water-insoluble, or a type that becomes water-insoluble by reacting with a binder, Any type of fluorescent agent that is fixed to the fluorescent coloring particles and becomes water-insoluble under the influence of the sulfuric acid band added to the slurry when producing the forgery prevention paper falls within the category of the water-insoluble fluorescent dyes and fluorescent pigments of the present invention. Shall enter.

The water-insoluble dye which emits fluorescence upon irradiation with ultraviolet light, ie, the fluorescent dye, used in the present invention, that is, fluorescein, coumarin, oxazole, pyrazoline, thiadiazole, spiropyran, pyrenesulfonic acid, benzoic Well-known fluorescent dyes such as imidazole and diaminostilbene can be used.

An organic or inorganic fluorescent pigment is used as a water-insoluble pigment which emits fluorescent light upon irradiation with ultraviolet rays, that is, a fluorescent pigment. Specific examples of the organic fluorescent pigment include resins such as polyvinyl chloride resin, alkyd resin, polymethacrylate resin, urea resin, and melamine resin, as well as fluorescein, eosin, rhodamine 6G, rhodamine B, basic yellow HG, and the like. And the like, which are uniformly dissolved and pulverized.

Specific examples of the inorganic fluorescent pigment include zinc sulfide activated with copper, silver, manganese, etc .; zinc silicate activated with manganese, etc .; zinc sulfide activated with silver, copper, etc .; Calcium sulfide activated by cadmium, bismuth, etc .; strontium sulfide activated by samarium, cerium, etc .; calcium tungstate activated by lead, etc .; Sr ₅ (PO ₄ ) ₃ C activated by europium, etc.
1; Zn ₂ GeO ₂ activated with manganese or the like; Y ₂ O ₂ S activated with europium or the like; Y ₂ O ₃ activated with europium or the like. If necessary, sensitizers such as anthraquinone and acetophenone may be used in combination.

In the present invention, these fluorescent pigments preferably have an average particle size of usually 0.5 to 5 μm. When the average particle size is less than 0.5 μm, the emission intensity due to the irradiation of ultraviolet rays may be reduced.
If the thickness exceeds μm, the fluorescence of the granulated product obtained by mixing granulation and coating tends to be non-uniform.

These fluorescent pigments may be used alone or in combination of two or more. The hue of the fluorescent color obtained when two or more fluorescent pigments are used in combination shows a phenomenon of so-called "additive color mixing". For example, when a pigment that emits fluorescence in red and a pigment that emits fluorescence in blue-violet are used in combination, it emits fluorescence in indigo blue, and similarly, green + red is yellow, red + blue-violet is red, and red + green + blue-violet is Fluorescent color develops on white. This phenomenon is completely different from "subtractive color mixing", which is a phenomenon when mixing paints. Unlike fluorescent dyes, fluorescent pigments have abundant types of hues that emit fluorescent light, so that the fluorescent colors obtained by using several types of fluorescent pigments in combination are very rich. In the case of producing fluorescent coloring particles using a water-insoluble and organic solvent-soluble fluorescent dye or fluorescent pigment as the fluorescent agent used in the present invention, the following specific effects can be obtained. That is, when the fluorescent coloring particles are included in paper and then printed to produce a forgery-preventive printed matter,
When falsification of the printed display is attempted with an organic solvent, the fluorescent agent soluble in the organic solvent elutes from the fluorescent coloring particles and diffuses to the surroundings, and the trace can be visually recognized by irradiation with ultraviolet rays. Thereby, the presence or absence of tampering can be reliably recognized. As a water-insoluble and organic solvent-soluble fluorescent agent, for example, an aminoketone dye or the like can be preferably used.

In the present invention, in order to impart water resistance to the fluorescent coloring particles, a reactive group that reacts with a hydroxyl group contained in a powdery substance such as starch, flour, cellulose, other polysaccharides, saccharides, and polyvinyl alcohol is used. A resin having two or more resins is used as a binder. This type of resin is referred to herein as a "resin binder". Examples of such a resin binder include polyamine / epichlorohydrin resins, water-soluble alkylated amino resins, water-soluble methylated melamine resins, water-soluble phenol resins, urea resins, epoxidized polyamide resins, and methylolated polyacrylamide resins. Can be mentioned.

In order to impart water resistance to the fluorescent coloring particles by using a resin binder, it is only necessary to mix a resin binder with the constituent components of the fluorescent coloring particles and granulate them, or to obtain a granulated product of components other than the fluorescent agent. The surface may be coated with a fluorescent agent with a resin binder.

In the present invention, as another method for imparting water resistance to the fluorescent coloring particles, an interaction between the anionic binder contained in the granulated material and the cationic substance contained in the coating layer, or A method utilizing the interaction between the cationic binder contained in the granulated material and the anionic substance contained in the coating layer can be employed. That is, the components of the fluorescent coloring particles excluding the fluorescent agent are granulated with an anionic binder, and the anionic binder can be provided with water resistance by coating the surface of the granulated material with a cationic substance.
Alternatively, it is possible to impart water resistance to the cationic binder by granulating the components of the fluorescent coloring particles excluding the fluorescent agent with a cationic binder and coating the surface of the granulated material with the anionic substance.

The anionic binder used in the present invention includes alginic acid, sodium alginate, carboxymethyl cellulose, carboxymethyl starch, carboxymethyl guar gum, carboxymethyl xanthan gum,
Examples include polysaccharides having an anionic group such as carboxymethyl cod gum, low methoxyl pectin, carrageenan, polyacrylic acid, and sodium polyacrylate, or synthetic polymers having anionic group.

The cationic substance to be coated with the fluorescent agent on the surface of the granulated material in order to impart water resistance to the anionic binder includes salts of polyvalent metal ions such as calcium, magnesium, barium, boron, and the like.
Hydrochlorides such as aluminum and titanium, sulfates, carbonates, phosphates, lactates, and hydroxides can be used.

Also, cationic water-soluble polymer substances such as cationic polyacrylamide, polyethyleneimine, polyvinylpyrrolidone, cationic polyamide resin, polyallylamine, cationic polymer-grafted starch, cationized starch, cationized guar gum, Cationized xanthan gum, cationized cod gum and the like can also be used as the cationic substance.

As the cationic binder used in the present invention, the cationic water-soluble high-molecular substances shown above as the cationic substance can be used. That is, cationic polyacrylamide, polyethyleneimine, polyvinylpyrrolidone, cationic polyamide resin, polyallylamine, cationic polymer-grafted starch, cationized starch, cationized guar gum, cationized xanthan gum, cationized cod gum and the like Polymeric substances can be used as the cationic binder.

The anionic substance to be coated with the fluorescent agent on the surface of the granulated material in order to impart water resistance to the cationic binder may be a polysaccharide having an anionic group shown above as the anionic binder or an anionic substance. A synthetic polymer having a group can be used.
That is, alginic acid, sodium alginate, carboxymethyl cellulose, carboxymethyl starch, carboxymethyl guar gum, carboxymethyl xanthan gum, carboxymethyl cod gum, low methoxyl pectin, carrageenan, polyacrylic acid, sodium polyacrylate and the like can be used as the anionic substance.

In the present invention, when granulating a particle component such as a powdery substance, a powdery substance and a white pigment, a powdery substance and a fluorescent agent, and a powdery substance, a white pigment and a fluorescent agent, granules such as starch and the like have conventionally been used. A commonly used method can be employed as the granulation method of the above. That is, a tumbling granulation method, an extrusion granulation method, a spray drying granulation method, a fluidized bed granulation method, a compression granulation method, a melt granulation method, a crush granulation method, a stirring granulation method, or the like can be used. . Among them, the spray drying granulation method has a feature that small spherical particles can be produced.

In the extrusion granulation method, the granulation properties may be insufficient depending on the type and amount of the binder used. In such cases, in order to improve the granulation properties, in addition to the various binders described above, a general binder such as hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, oxidized starch, and dextrin may be used as needed. And kneaded, and extruded and granulated. The granulated product obtained by extrusion granulation is generally used after sizing with a sizing machine, but when the sizing property is poor due to the type and amount of the binder, a surfactant or a lubricant is used. The sizing property of the granulated product can be improved by adding it as needed. In the present invention, when coating the surface of the granulated material with a fluorescent agent or a white pigment, after drying the granulated material, the fluorescent agent or the white pigment is coated with a binder in a liquid (dispersion), Alternatively, a method of coating a fluorescent agent or a white pigment in powder form while spraying a binder with a liquid can be adopted. As a coating device, a device capable of performing a coating process using a granulator used in the above-described granulation method, as well as a dedicated coating machine (for example, a rolling granulator,
Fluidized bed granulator or dryer capable of spraying liquid during drying with a dryer) can be used, and any device other than a dedicated coating machine can be used as long as it can be used for coating treatment. can do.

The shape of the fluorescent coloring particles of the present invention produced by the above-described method differs depending on the granulation method used. For example, after extrusion granulation, the sized product has a columnar shape with sharp corners. The cross section has a circular shape or a shape close to a circle. When the length is the same or almost the same as this diameter, the light appears to emit spherically, and when the length is long, the light appears to be cocoon-shaped. The product obtained by the spray drying granulation method is substantially spherical, the product obtained by the tumbling granulation method and the stirring granulation method is substantially spherical, and the product obtained by the fluidized bed granulation method is However, depending on the conditions, different shapes may be obtained even by the same granulation method.

The particle size of the fluorescent coloring particles is from several μm to several hundred μm.
Although it is possible to appropriately control the particle size, it is preferable in the present invention to adjust the particle size to a range of 50 to 800 μm. If the particle size is less than 50 μm, even if the particles are contained in paper, even if they are irradiated with ultraviolet light under ordinary light, the tendency to visually recognize the light emission becomes large. The larger the particle size, the easier it is to visually recognize, but the swelling of the portion where the particles are present deteriorates the feel and adversely affects printability. In consideration of the balance between the two, it is preferable that the particle size be adjusted to the above range.

In the present invention, the fluorescent coloring particles may be used without coloring, or may be colored. Uncolored fluorescent coloring particles have a hue similar to white or white under normal light, so if they are included in uncolored paper, the fluorescent coloring particles are present in the paper It becomes difficult to see it. When coloring fluorescent coloring particles,
By adjusting the hue of the fluorescent coloring particles so as to approximate the coloring degree of the paper, it becomes difficult to visually recognize the presence of the fluorescent coloring particles in the paper. When colored fluorescent coloring particles are included in uncolored paper, the presence of the fluorescent coloring particles can be visually recognized under ordinary light.

In the present invention, when the fluorescent coloring particles are colored, it is particularly preferable that the particles are colored so pale that the hue cannot be reproduced by a color copier. Even if a counterfeit-proof printed matter (for example, a gift certificate) manufactured using anti-counterfeit paper containing lightly-colored fluorescent coloring particles is attempted using a color copier, the fluorescent coloring particles are copied. This is because if the density adjustment is performed, the density of the copy portion corresponding to the print portion increases, and it is possible to easily determine that the ticket is a counterfeit ticket by itself.

In the present invention, the coloring of the fluorescent particles is preferably a dropout color in optical reading. The surface of anti-counterfeit printed matter such as various gift certificates and tickets is often printed for OMR or OCR reading. These are provided for automatic counting after a gift certificate or ticket is used. OMR stands for "Optical Mark Rec
abbreviation for "authentication", irradiates the paper with light from a light source and receives it with a light-receiving element. By recognizing the position of the mark provided on the paper, the position is compared with numbers and symbols and linked together. And a system used for classification, and the paper used for this is called OMR paper. Also, OCR is "Optical Chara"
It is an abbreviation for "cter Recognition" and is a general term for a system for optically reading letters and numbers in the same manner, and the paper used for this is called OCR paper.

In order to perform OMR and OCR reading,
On the surface of the sheet, predetermined items such as a frame, a ruled line, and a description are often printed in a dropout color. A dropout color is a combination of a light source and a light receiving element. The human eye recognizes a printed portion as a completely different color from a white background, but the light receiving element loses the difference and feels the same as a white background. Such color. In the case of OMR paper or OCR paper, color light in an appropriate wavelength region is set by the combination of the type of light source used and the light receiving element, and the corresponding dropout color is used. JIS C6253 "Print Specifications for Optical Character Recognition" stipulates light receiving devices corresponding to eight types of wavelength regions.

In the present invention, the hue of the fluorescent coloring particles is set as a dropout color in optical reading,
Although the human eye recognizes the part where the particles are present as a completely different color from the white background, the difference disappears and disappears in the light receiving element at the time of OMR or OCR reading, so that the person feels the same as the white background.

The fluorescent coloring particles used in the present invention have a structure in which the hue at the time of coloring by irradiation of ultraviolet rays is different from the hue under ordinary light, so that the unexpectedness is enhanced and the anti-counterfeiting ability is improved. Has the effect of increasing. For example, the fluorescent coloring particles appear to be colored red under ordinary light, and when irradiated with ultraviolet rays, appear to emit green or blue light, thereby increasing the unexpectedness. To color the fluorescent coloring particles, a method of using a coloring agent in various stages when manufacturing the fluorescent coloring particles as described above, or a method of dyeing the fluorescent coloring particles with a dye after the production,
And so on. As the colorant, a color dye such as a direct dye, an acid dye, a basic dye, or an inorganic or organic color pigment can be used. When coloring with light resistance is performed, it is preferable to use an inorganic pigment as a coloring agent.

When a dye insoluble in water and soluble in an organic solvent is used as a coloring agent for the fluorescent particles, the following specific effects can be obtained. In other words, when the colored fluorescent coloring particles are included in the paper and then printed to produce a forgery-preventive printed matter, when an attempt is made to falsify the printed display with an organic solvent, an organic solvent-soluble dye is converted from the fluorescent coloring particles. The trace eluted and diffused to the surroundings can be visually recognized, and the presence or absence of tampering can be reliably recognized.

In the fluorescent coloring particles of the present invention having a structure in which a coating layer containing a fluorescent agent is formed on the surface of a granulated substance containing a powdery substance, a dye insoluble in water and soluble in an organic solvent is granulated together with the powdery substance. And a fluorescent pigment having a hue close to white or white under ordinary light as a fluorescent agent in the coating layer.
In such fluorescent coloring particles, the color of the organic solvent-soluble dye in the granulated material is concealed by the fluorescent pigment having a hue similar to white or white in the coating layer. When printing is performed to produce a forgery-prevention printed matter (for example, a passport), it is difficult to recognize the presence of the fluorescent coloring particles under ordinary light, so that it is difficult to determine that the forgery prevention means has been taken, and the forgery prevention effect is reduced. It can be even higher. Furthermore, when falsification of a printed display is attempted using an organic solvent, traces of the organic solvent-soluble dye eluted from the granulated material, which is the core of the fluorescent coloring particles, and diffused to the surroundings can be visually observed. It is possible to reliably recognize the presence or absence of tampering. As the dye insoluble in water and soluble in an organic solvent, for example, dyes of monoazo type, disazo type, metal complex salt type monoazo type, anthraquinone type, phthalocyanine type and triallylmethane type can be used. The organic solvent in which these dyes are dissolved is described in "Dye Handbook", and the type can be specified by the color index (CI number).

When a dye which is insoluble in water and soluble in an organic solvent as described above is used, if a dye which emits fluorescence when irradiated with ultraviolet rays is used as the dye, the dye is eluted when tampered with the organic solvent. The diffused traces are easily visible under ultraviolet irradiation, so that the presence or absence of tampering can be more reliably recognized. As such a dye, an aminoketone-based dye which is chromatic with ordinary light and develops various hues under irradiation with ultraviolet rays can be used.

In the present invention, it is necessary to provide the printability-imparting layer in a range in which the fluorescent coloring particles can be visually confirmed. The range in which the fluorescent coloring particles can be visually confirmed refers to a range in which the presence of the fluorescent coloring particles can be easily confirmed upon irradiation with ultraviolet rays, and can be determined by the following measurement. 1. After the printability-imparting layer is provided, the state in which the presence of the fluorescent color-developed particles that are colored by irradiating ultraviolet rays can be confirmed as well as before the printability-impartment-imparting layer is determined as 5 points. The state where no confirmation was made at all was defined as one point and classified into five stages by sensory evaluation. 2. Of the samples classified by the above method, three or more points are defined as “the range in which the fluorescent coloring particles can be visually confirmed”. Samples with less than 3 points by the above method have a significantly reduced forgery prevention effect.

The inorganic powder contained in the printability-imparting layer comprises at least one of silicate, silicic acid, calcium carbonate, magnesium carbonate, aluminum hydroxide, satin white, barium sulfate, calcium sulfate and plastic pigment.
More than one kind can be selected and used. The amount of the wavelength that absorbs light differs depending on the type of the inorganic powder. Since the present invention uses fluorescent coloring particles, it is preferable to use an inorganic powder having a small absorption at the wavelength of the ultraviolet portion. Most of the light emitted from an ordinary ultraviolet fluorescent lamp has a wavelength of 280 to 350 nm, and it is particularly desired not to absorb the wavelength. That is, it is necessary to select an inorganic powder that does not absorb ultraviolet light and improves printability. These fillers are silicates,
Silicic acid, calcium carbonate, magnesium carbonate, aluminum hydroxide, satin white, barium sulfate, calcium sulfate, and plastic pigment. Conversely, titanium oxide and zinc oxide are known as inorganic powders that absorb ultraviolet rays. Titanium oxide absorbs a wavelength of 350 nm at 90% for the rutile type and 67% for the anatase type. Zinc oxide absorbs a large amount of light having a wavelength of 200 to 400 nm. For this reason, when these inorganic powders are contained in the printability-imparting layer, when irradiated with an ultraviolet fluorescent lamp, ultraviolet rays are absorbed by the inorganic powders, and ultraviolet rays necessary for the emission of fluorescent coloring particles cannot be obtained, As a result, visual confirmation of the fluorescent coloring particles becomes impossible.

It is necessary that the printability-imparting layer provided in the present invention not only absorbs a small amount of ultraviolet light but also scatters light in the visible light region. If the light is scattered too much, light in the visible light region emitted from the fluorescent coloring particles cannot be confirmed. The particle diameter of the inorganic powder contained in the printability-imparting layer is 0.3 μm
As described above, more preferably 0.5 μm or more, the scattering of light in the visible light region is small, and visual confirmation of the fluorescent coloring particles is facilitated. This is because the particle size is closely related to light scattering.

Usually, the inorganic powder scatters light and hinders light transmission. These principles are used to improve the opacity of the paper by the internal filler used in the paper and the inorganic powder in the paint. Light scattering by these inorganic powders
The maximum is obtained with an inorganic powder having a particle diameter of about half of the light.
Since the light in the visible light region is 400 to 700 nm, the light intensity of the light is within 0.1 nm.
The inorganic powder having a particle diameter of 2 to 0.3 μm scatters a large amount of light in the visible light region.

Conversely, if the particle size exceeds 20 μm, a dense surface cannot be formed, and the printability will be significantly reduced. Therefore, the inorganic powder contained in the printability-imparting layer is 0.3 to 20 μm.
Preferably, the particle size is m.

When the particle diameter is 0.1 μm or less, the particles are too small, so that they do not inhibit visible light and ultraviolet light. In general, such fine particles of inorganic powder increase the cost, but can enable clear printing, and can be used depending on the application.

The light transmission of the inorganic powder greatly affects the refractive index of the inorganic powder itself. The higher the refractive index, the more irregularly the light is reflected and the more difficult it is to transmit light. Therefore, the refractive index is 2.
It is preferable to use 0 or less inorganic powder.

If the amount of the inorganic powder is less than 40 parts by weight, the inorganic powder is insufficient to improve the vividness of printing, and
If the amount exceeds 8 parts by weight, the surface strength of the coating layer becomes weak, and the printability deteriorates in strength.

Examples of the binder for the inorganic powder include synthetic rubber latex such as styrene / butadiene copolymer latex, methyl methacrylate / butadiene copolymer latex, vinyl acetate latex, nitrile / butadiene latex, acrylic latex, urethane latex, and the like.
Examples include synthetic resin emulsions such as polyacrylate emulsions and polyvinyl acetate emulsions, and natural or synthetic pastes such as starch, modified starch, casein, and polyvinyl alcohol. These adhesives may be mixed and blended in two or more types as needed.

Further, dispersants, defoamers, lubricants, preservatives,
A waterproofing agent, a dye, a flow modifier, a fixing agent for inkjet, and the like can be used as needed.

The printability-imparting layer is 5 g / m ^{2 to} 30 g / m
When it is m ² , it is possible to improve printability without hindering visual confirmation of the fluorescent coloring particles. 5g / m
^If it is less than ^2, it is insufficient to improve printability, and 20 g
/ M ² , even when the inorganic powder under the above conditions is used,
Confirmation of the fluorescent coloring particles becomes difficult.

As described above, the printability-imparting layer, which has excellent printability and does not hinder the visual confirmation of the fluorescent coloring particles, has the following features: (1) low absorption of ultraviolet rays; (2) no scattering of visible light; It is necessary to have excellent printability.
That is, it is necessary to have these three conditions. In the conventional techniques, it has been considered impossible to provide a printability-imparting layer on paper containing fluorescent coloring particles for the reasons 1 and 2 described above. However, by adjusting the type, particle diameter, refractive index, and coating amount of the inorganic powder, it is possible to provide a printability-imparting layer even on paper containing fluorescent coloring particles, which was conventionally considered impossible. became.

As the printability-imparting layer of the present invention, a layer composed of only a resin can be provided. A printability-imparting layer composed of only a resin layer is disadvantageous in offset printing or the like because absorption of a vehicle or the like in the ink is poor, but, for example, in the case of thermal transfer printing, excellent printability can be imparted. These resins are also required to not absorb ultraviolet light and transmit light in the visible light region. These resins include styrene / butadiene copolymer latex, methyl methacrylate / butadiene copolymer latex, vinyl acetate latex,
Synthetic rubber latex such as nitrile-butadiene latex, acrylic latex, urethane latex,
Examples include synthetic resin emulsions such as polyacrylate emulsions and polyvinyl acetate emulsions, and natural or synthetic pastes such as starch, modified starch, casein, and polyvinyl alcohol. These resins may be mixed and blended in two or more types as necessary.

If the resin layer is less than 5 g / m ^2, it is not enough to improve the printability, and if it exceeds 20 g / m ² , it does not contribute to the improvement in printability and is not only economically disadvantageous. However, the flexibility of the conventional paper is hindered, and the printability on the transport surface is deteriorated.

The printability-imparting layer provided in the present invention is not limited to those which improve the printability of offset printing and thermal transfer printing as described above. For example, a printability-imparting layer for improving printability such as gravure printing, flexographic printing, letterpress printing, intaglio printing, and electronic printing (inkjet printing, thermal printing, dry electrophotographic printing, wet electrophotographic printing, wet electrocoagulation printing), etc. As long as it does not hinder the visual confirmation of the fluorescent coloring particles, it can be used.

Further, it is also possible to have a two-layer structure of a printability-imparting layer composed of only a resin and a filler coating layer containing inorganic powder. For example, if a filler coating layer for improving printability is provided on a resin layer capable of imparting water resistance, it is possible to simultaneously improve water resistance and printability. Also, by providing a resin layer, to improve the smoothness of the filler coating layer,
It is possible to further improve printability

The production of anti-counterfeit paper having excellent printability using the fluorescent coloring particles of the present invention will be described below. That is, the anti-counterfeit paper excellent in printability of the present invention is softwood bleached kraft pulp (NBKP), hardwood bleached kraft pulp (LBKP), softwood bleached sulphite pulp (N
BSP), thermomechanical pulp (TMP) and other papermaking pulp, and if necessary, cotton,
Non-wood pulp such as hemp, bamboo, straw, and kenaf or synthetic fiber is appropriately used in combination, and the dry paper strength enhancer, wet paper strength enhancer, sizing agent, fixing agent, retention improver, drainage improver, Preparation of paper stock by appropriately adding foaming agents, dyes, coloring pigments, etc.,
Fluorescent coloring particles are added to this stock using a chest or the like, and the freeness is usually 550 to 250 ml. S. F. , Using a well-known paper machine such as a fourdrinier paper machine or a round paper machine, and then providing a printability-imparting layer. In this case, the fluorescent coloring particles are ubiquitous over the entire surface of the paper.

On the other hand, when the fluorescent coloring particles are unevenly distributed in the form of a band or a stripe in the paper, the forgery prevention effect can be further enhanced. In order to cause the fluorescent coloring particles to be unevenly distributed in the form of a band or a streak in the paper, a method proposed in Japanese Patent Publication No. 6-63200, that is, a method in which the liquid surface of the stock in the mesh tank of the mesh machine and the mesh are used. A method is provided in which a nozzle with a hose is installed above the boundary, a stock containing fluorescent coloring particles is poured in, and a certain width is applied to an arbitrary portion.
A known method such as a method of distributing fluorescent coloring particles in a streak shape by a streak pouring device installed on a wire part of a fourdrinier paper machine as proposed in the above issue is adopted.

As a method for providing the printability-imparting layer, generally known coating apparatuses such as a blade coater, an air knife coater, a roll coater, a reverse roll coater, a bar coater, a curtain coater, a die slot coater, a gravure coater, and a bill blade coater ,
Apparatuses such as a short dwell coater, a gate roll coater, and a cast coater can be appropriately used in combination.

For the production of anti-counterfeit paper containing fluorescent coloring particles, which is excellent in printability, in addition to the base paper in which the fluorescent coloring particles have been previously added to the stock as described above, a fourdrinier paper machine or a circular netting machine. For base paper made by adding fluorescent coloring particles in the course of feeding paper stock in a paper machine, or base paper made by feeding fluorescent coloring particles into a vat of a round paper machine, and paper on wire Base paper produced by a method of sprinkling fluorescent coloring particles intermittently or in a stripe shape using a nozzle can also be used. At this time, starch, polyvinyl alcohol,
It is also possible to apply various surface sizing agents and the like with a size press device or the like.

Further, if necessary, a base paper having improved smoothness by a super calender can be used. In addition, after providing the printability-imparting layer, the smoothness can be improved by a super calender.

Further, the base paper of the anti-counterfeit paper excellent in printability of the present invention can be produced by a so-called impregnation method. That is, adding fluorescent coloring particles to a known binder such as a synthetic rubber latex or a synthetic resin emulsion,
This may be impregnated into paper.

[0073]

The present invention will be described in more detail with reference to the following examples. In the examples, parts by weight and% by weight mean dry parts by weight and dry weight%, respectively.

Example 1 20 parts by weight of NBKP, LBK
P80 parts by weight to 250 ml C.I. S. F. Beat this to
10 parts by weight of clay, paper strength agent (trade name "Polystron"
191 ", manufactured by Arakawa Chemical Industry Co., Ltd.) 0.3 parts by weight
Agent (trade name “Size Pine E”, Arakawa Chemical Industry Co., Ltd.)
1.0 parts by weight and an appropriate amount of a sulfuric acid band to prepare a stock.
Was. Fluorescent particles produced by the following method
And 0.5% by weight of the paper.
Using a Fourdrinier paper machine, basis weight 100g / m^Two Forgery prevention
Paper was manufactured in a conventional manner. After passing through the drying zone of the paper machine
After machine calendering, touch the surface of the paper with your hand.
However, the presence of the fluorescent particles could not be detected. Obtained
Kaolin (trade name "UW90", Engelha
90 parts by weight, starch (trade name “MS-46”)
00, manufactured by Nippon Food Processing Co., Ltd.)
Box (trade name "Smartex 750", Mitsui Chemicals, Inc.)
Coating: 15 parts by weight of water and 150 parts by weight of water
The liquid was applied so that the solid content of the coating layer was 10 g / m. ^TwoCoating to become
Then, a sample was obtained. Production method of fluorescent coloring particles: corn starch 100 weight
Part, fluorescent pigment (Mn-activated Zn_Two GeO_Two Particles, average
15 parts by weight, water-soluble methylated melamine
Resin [resin binder] ("SUMITEX RES
IN M-3 ", manufactured by Sumitomo Chemical Co., Ltd.) 10 parts by weight, water 3
0 parts by weight, and polyoxyethylene stearyl ether
1 part by weight of [lubricant] is mixed and stirred with a kneader for 10 minutes.
Stirred.

This mixture was extruded into a columnar granule having a diameter of 500 μm using an extrusion granulator (“Dome Gran”, manufactured by Fuji Paudal Co., Ltd.). This granulated product is treated with a granulator (“Malmerizer”, manufactured by Fuji Paudal Co., Ltd.)
The particles were sized in a spherical or cocoon shape with / D = 3 or less, and then dried to obtain fluorescent coloring particles.

Example 2 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 100 parts by weight of crystalline cellulose (“Avicel”, manufactured by Asahi Kasei Corporation), 10 parts by weight of zinc oxide [white pigment], fluorescent pigment (Mn-activated Zn ₂
5 parts by weight of GeO ₂ particles, average particle diameter of 3.0 μm, 5 parts by weight of fluorescent pigment (Eu activated St ₅ (PO ₄ ) ₃ Cl particles, average particle diameter of 4.5 μm), fluorescent pigment (Eu activated Y ₂₎ O
₂ S particles, an average particle diameter of 2.2 [mu] m) 5 parts by weight, and water-soluble methylated melamine-based resin [resin binder] ( "S
UMITEX RESIN M-3 ") 10 parts by weight,
Hydroxypropyl starch [general binder]
("Piostarch H", manufactured by Nisseki Chemical Co., Ltd.), and a granulating / coating apparatus ("High Speed Mixer", manufactured by Fukae Kogyo Co., Ltd.) using 25 parts by weight of a 10% by weight size liquid as a binder. Granulated and dried.

Example 3 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 100 parts by weight of corn flour is spray-dried with 10 parts by weight of polyethyleneimine [cationic binder] (“Epomin P-1000”, manufactured by Nippon Shokubai Co., Ltd.) as a binder, and fine granular starch is dried. Obtained.

On the surface of this fine granular starch, a fluorescent pigment (Eu
Activated St ₅ (PO ₄ ) ₃ Cl particles, average particle size 0.8 μm
m) A coating liquid in which 20 parts by weight and 2 parts by weight of carboxymethyl starch [anionic substance] are dispersed in 50 parts by weight of water is applied to a fluidized bed granulation coating apparatus ("Flow Coater", manufactured by Freund Corporation). The resultant was subjected to fluidized bed coating to obtain true spherical fluorescent coloring particles having a particle size of 200 to 500 μm.

Example 4 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 100 parts by weight of crystalline cellulose (“Avicel”) and 10 parts by weight of zinc oxide [white pigment] are hydroxypropyl starch [general binder]
Using 30 parts by weight of a 10% by weight paste solution ("Piostarch H") as a binder, the mixture was granulated with a granulating / coating apparatus ("High Speed Mixer") and dried.

5 parts by weight of a fluorescent pigment (Mn-activated Zn ₂ GeO ₂ particles, average particle size 1.0 μm), a fluorescent pigment (Eu-activated St ₅ (PO ₄ ) ₃ Cl particles, 5 parts by weight of an average particle diameter of 0.8 μm, 5 parts by weight of a fluorescent pigment (Eu-activated Y ₂ O ₂ S particles, average particle diameter of 2.2 μm) and a water-soluble methylated melamine-based resin [resin binder] (“SUMITEX”) RESIN M-3 ") 10
A coating liquid in which parts by weight were dispersed in 30 parts by weight of water was coated with a granulating / coating apparatus (“High Speed Mixer”) to obtain fluorescent coloring particles having a particle size of 300 to 1000 μm.

Example 5 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method.
100 parts by weight of flour and calcium carbonate [white pigment] 15
Parts by weight of hydroxypropylcellulose [general binder] (“HPC-L”, manufactured by Nippon Soda Co., Ltd.)
The fluidized-bed granulation / coating apparatus ("Nummarmerizer", manufactured by Fuji Paudal Co., Ltd.) was used for the fluidized-bed granulation using 30 parts by weight of the paste solution of 30% by weight as a binder.

20 parts by weight of a fluorescent pigment (Eu-activated Y 2 O 2 S particles, average particle size of 2.2 μm) was coated on the surface of this granulated product with a polyamine / epichlorohydrin resin [resin binder] (“WS564”, Nippon PCM Corporation). 2 parts by weight, dextrin [general binder] 5 parts by weight, 10 parts by weight
A coating solution dispersed in 50 parts by weight of water together with 1 part by weight of a sodium hydroxide solution by weight is subjected to the above-mentioned fluidized bed granulation.
Fluidized bed coating with coating equipment, particle size 20
0 to 400 μm spherical fluorescent coloring particles were obtained.

Example 6 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 20 parts by weight of kaolin [white pigment] and hydroxypropylcellulose [general binder] 1 on a surface of 100 parts by weight of spherical fine granular starch ("Graffeo M", manufactured by Nissei Chemical Co., Ltd.) Parts by weight of a coating liquid dispersed in 40 parts by weight of water is applied to a centrifugal flow type coating granulator (“centrifugal flow type coating granulator CF”,
By spraying with Freund Sangyo Co., Ltd.) to form a kaolin coating layer on the surface of the fine granular starch.

Subsequently, on the kaolin coating layer, 20 parts by weight of a fluorescent pigment (Eu-activated Y ₂ O ₂ S particles, average particle size of 2.2 μm) was added to a polyamine / epichlorohydrin resin [resin binder] (“WS564”). ") 2 parts by weight, corn starch [powder substance added to the coating liquid] 5 parts by weight, 1 part by weight of a 10% by weight sodium hydroxide solution and 50 parts by weight of a coating liquid dispersed in 50 parts by weight of the above-mentioned centrifugal flow type coating granulation. Coating was performed with an apparatus to obtain fluorescent coloring particles having a particle size of 200 to 400 μm.

Example 7 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 100 parts by weight of corn starch, 15 parts by weight of titanium dioxide [white pigment], 30 parts by weight of water, 1 part by weight of sodium alginate [anionic binder] and 1 part by weight of hydroxypropylcellulose [general binder] Is added, and 1 part by weight of polyoxyethylene stearyl ether [lubricant] is added.
The mixture was mixed and stirred for 10 minutes. This mixture was extruded into a columnar granule having a diameter of 500 μm using an extrusion granulator (“Dome Gran”). The granulated product was sized into a spherical shape or a cocoon shape having an L / D of 3 or less using a sizing machine (“Malmerizer”), and then dried.

The granulated product was put into the above-mentioned sizing machine and tumbled while adding a fluorescent pigment (Mn-activated Zn ₂ Ge) to 25 parts by weight of a 5% by weight calcium chloride solution [cationic substance].
A coating liquid in which 15 parts by weight of O ₂ particles (average particle size: 3.0 μm) was dispersed was spray-coated, and then dried.

Example 8 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: lactose 70% by weight and crystalline cellulose 30% by weight were granulated using a centrifugal flow type coating granulator with a particle diameter of 180 to 300 μm (“Nonparel-105”, Freund Corporation ( Co., Ltd.)
50 parts by weight, and spherical granules having a particle size of 350 to 500 μm (“Nonparel-101”, granulated from 65 to 85% by weight of purified sucrose and 15 to 35% by weight of corn starch using a centrifugal flow type coating granulator). 50 parts by weight of a Freund Corporation (Freund Sangyo Co., Ltd.) was mixed with a fluorescent pigment (Eu-activated Y ₂ O).
20 parts by weight of ₂ S particles, average particle size of 2.2 μm) were used as a polyamine / epichlorohydrin resin [resin binder]
("WS564") 4 parts by weight, amaranth starch [powder added to coating solution] 30 parts by weight, 2 parts by weight of 10% by weight sodium hydroxide solution, 50 parts by weight of water, and 50 parts by weight of ethanol dispersed in ethanol To a fluidized bed coating and drying system with an inner cylinder ("Gro-
MAX ", manufactured by Fuji Paudal Co., Ltd.).

Example 9 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: kaolin [white pigment] is applied on the surface of 100 parts by weight of spherical fine granular starch (“Graffeau M”)
A coating liquid obtained by dispersing 20 parts by weight and 1 part by weight of hydroxypropylcellulose [a general binder] in 40 parts by weight of water is sprayed by a centrifugal flow type coating granulator ("centrifugal flow type coating granulator CF"). do it,
A kaolin coating layer was formed on the surface of the fine granular starch.

Subsequently, on the kaolin coating layer, 20 parts by weight of a fluorescent pigment (Eu-activated Y ₂ O ₂ S particles, average particle size of 2.2 μm) and a blue phthalocyanine pigment (trade name “TB-700 Blue”) GA ", manufactured by Dainichi Seika Kogyo Co., Ltd.) 0.6 parts by weight of polyamine / epichlorohydrin resin [resin binder] (" WS564 ") 2
Parts by weight, corn starch [powder substance added to coating liquid] 5 parts by weight, 10% by weight sodium hydroxide solution 1
The coating liquid dispersed in 50 parts by weight of water together with parts by weight was coated with the above-mentioned centrifugal flow type coating granulator to obtain fluorescent coloring particles having a particle diameter of 200 to 400 μm.

Example 10 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 100 parts by weight of flour and 15 parts by weight of calcium carbonate [white pigment] are combined with hydroxypropylcellulose [general binder] (“HPC-L”).
Was fluidized bed granulated with a fluidized bed granulator / coating apparatus ("New Marmerizer") using 30 parts by weight of the size liquid of 10% as a binder.

On the surface of the granules, 1.5 parts by weight of a thiophene-based fluorescent dye, 20 parts by weight of a polyamine / epichlorohydrin-based resin [resin binder] (“WS564”), 50 parts by weight of dextrin [general binder], Red inorganic coloring pigment (trade name “TB-200 Red G
Y ", manufactured by Dainichi Seika Kogyo Co., Ltd.) 0.5 parts by weight together with 10 parts by weight of a 10% by weight sodium hydroxide solution and water 500
The coating liquid dispersed in parts by weight is subjected to fluidized bed coating by the above fluidized bed granulating / coating apparatus, and the particle size is 2
Spherical fluorescent coloring particles of 00 to 400 μm were obtained.

Example 11 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 100 parts by weight of flour and 15 parts by weight of calcium carbonate [white pigment] are combined with hydroxypropylcellulose [general binder] (“HPC-L”).
Was fluidized bed granulated with a fluidized bed granulator / coating apparatus ("New Marmerizer") using 30 parts by weight of the size liquid of 10% as a binder.

A fluorescent dye (rhodamine: trade name “Kayacryl Rhodamine BL-ED”, manufactured by Nippon Kayaku Co., Ltd., red by ordinary light and red by irradiation with ultraviolet light) 1 part by weight, polyamine / epichlorohydrin resin [resin binder] (“WS564”) 20
Coating solution prepared by dispersing 50 parts by weight of dextrin [a general binder] and 500 parts by weight of water together with 10 parts by weight of a 10% by weight sodium hydroxide solution in a fluidized bed granulation / coating apparatus is subjected to fluidized bed coating. And spherical fluorescent coloring particles having a particle diameter of 200 to 400 μm.

Example 12 A sample was obtained in the same manner as in Example 1 except that the fluorescent particles were produced by the following method. Production method of fluorescent coloring particles: 100 parts by weight of flour, 15 parts by weight of calcium carbonate [white pigment], water-insoluble and organic solvent-soluble red dye (trade name “Kayaset Red S”)
F-4G ", manufactured by Nippon Kayaku Co., Ltd.), 2 parts by weight of hydroxypropylcellulose [general binder] (" HP
CL)) was used as a binder, and fluidized bed granulation was carried out using a fluidized bed granulating / coating apparatus ("Nummarmerizer").

On the surface of the granulated product, a polyamine / epichlorohydrin-based resin [resin binder] (“WS56
4 ") 20 parts by weight, dextrin [general binder]
50 parts by weight of a white inorganic fluorescent pigment (Eu activated St ₅
(PO ₄ ) ₃ Cl particles, average particle size 0.8 μm) A coating liquid obtained by dispersing 10 parts by weight in 500 parts by weight of water is subjected to fluidized bed coating by the above fluidized bed granulating / coating apparatus, and the particle size is 200 to 200 μm. 400 μm spherical fluorescent coloring particles were obtained.

[Example 13] Kaolin (trade name "UW90", manufactured by Engelhard Co., Ltd.) as a printability-imparting layer was changed to aluminum hydroxide (trade name, "Heidilite H42", manufactured by Showa Denko KK). Except for the above, a sample was obtained in the same manner as in Example 1.

[Example 14] Except that kaolin (trade name "UW90", manufactured by Engelhard Co., Ltd.) of the printability-imparting layer was changed to calcium carbonate (trade name "Softon 1800", manufactured by Shiraishi Calcium Co., Ltd.) A sample was obtained in the same manner as in Example 1.

[Example 15] Except that kaolin (trade name “UW90”, manufactured by Engelhard Co., Ltd.) of the printability-imparting layer was changed to silicic acid (trade name “Fine Seal X37”, manufactured by Tokuyama Corporation) A sample was obtained in the same manner as in Example 1.

Example 16 Except that kaolin (trade name “UW90”, manufactured by Engelhard Co., Ltd.) of the printability-imparting layer was changed to magnesium carbonate (trade name “Vensei”, manufactured by Kamishima Chemical Industry Co., Ltd.) A sample was obtained in the same manner as in Example 1.

Example 17 Kaolin (trade name “UW90”, manufactured by Engelhard Co., Ltd.) as a printability-imparting layer was converted into Sachin White (trade name “SW-BL”, Shiraishi Kogyo Co., Ltd.)
Sample) was obtained in the same manner as in Example 1 except that the sample was manufactured.

[Example 18] Kaolin (trade name "UW90", manufactured by Engelhard Co., Ltd.) as a printability-imparting layer was converted into a plastic pigment (trade name, "Grosdale, L Series 840L", manufactured by Mitsui Chemicals, Inc.). A sample was obtained in the same manner as in Example 1, except that

Example 19 20 parts by weight of NBKP, LB
KP80 parts by weight was added to 350 ml C.I. S. F. 10 parts by weight of clay, 0.3 parts by weight of paper strength agent (trade name "Polystron 191"), 1.0 part by weight of sizing agent (trade name "Size Pine E"), appropriate amount of sulfate band Was added to prepare a stock.

Using this stock, 100 g of fourdrinier paper machine
/ M ² paper is sprinkled over the entire surface of wet paper web formed on a papermaking net with 0.5% by weight of the fluorescent coloring particles obtained by the following manufacturing method based on the paper. To obtain anti-counterfeit paper. When machine calendering was performed after passing through the drying zone of the paper machine, the presence of the fluorescent particles could not be detected even when the paper surface was touched with the hand. 90 parts by weight of kaolin (trade name “UW90”, manufactured by Engelhard Co., Ltd.) and starch (trade name “MS-460”) were added to the obtained base paper.
0, manufactured by Nippon Food Processing Co., Ltd.), 7.5 parts by weight, latex (trade name “Smartex 750”, Mitsui Chemicals, Inc.)
15 parts by weight) and 150 parts by weight of water were mixed, and a coating solution was applied so that the solid content of the coating layer was 10 g / m ² to obtain a sample. Production method of fluorescent coloring particles: 100 parts by weight of corn starch, fluorescent pigment (Mn-activated Zn ₂ GeO ₂ particles, average
15 parts by weight of a water-soluble methylated melamine-based resin [resin binder] (“SUMITEX RES”)
IN M-3 ", manufactured by Sumitomo Chemical Co., Ltd.) 10 parts by weight, water 3
0 parts by weight and 1 part by weight of polyoxyethylene stearyl ether [lubricant] were mixed and stirred in a kneader for 10 minutes.

[Example 20] An acrylic resin (trade name "Cybinol E") was used instead of the filler coating layer for the printability-imparting layer.
K-112B "(manufactured by Seiden Chemical Co., Ltd.) was coated in the same manner as in claim 1 except that the solid content was 10 g / m ² .

Example 21 The structure of the printability-imparting layer was
Latex (trade name "Nipol Z400S", manufactured by Nippon Zeon Co.) layer is 10 g / m ² coated on solids, except for forming further filler coating layer 15 g / m ² coated according to claim 1 A sample was obtained in the same manner as in claim 1.

Comparative Example 1 NBKP 20 parts by weight, LBK
P80 parts by weight to 250 ml C.I. S. F. 10 parts by weight of clay, 0.3 parts by weight of a paper strength agent (trade name "Polystron 191", manufactured by Arakawa Chemical Industry Co., Ltd.), a sizing agent (trade name "Size Pine E", Arakawa Chemical Industry Co., Ltd.
1.0 parts by weight) and an appropriate amount of a sulfuric acid band were added to prepare a stock. Fluorescent particles produced by the method described below were added to the stock so as to be 0.5% by weight based on the paper.
Using a fourdrinier paper machine, anti-counterfeit paper having a basis weight of 100 g / m ² was manufactured by a conventional method to obtain a sample. Production method of fluorescent coloring particles: 100 parts by weight of corn starch, fluorescent pigment (Mn-activated Zn ₂ GeO ₂ particles, average
15 parts by weight of a water-soluble methylated melamine-based resin [resin binder] (“SUMITEX RES”)
IN M-3 ", manufactured by Sumitomo Chemical Co., Ltd.) 10 parts by weight, water 3
0 parts by weight and 1 part by weight of polyoxyethylene stearyl ether [lubricant] were mixed and stirred in a kneader for 10 minutes.

The mixture was extruded into a columnar granule having a diameter of 500 μm using an extrusion granulator (“Dome Gran”, manufactured by Fuji Paudal Co., Ltd.). This granulated product is treated with a granulator (“Malmerizer”, manufactured by Fuji Paudal Co., Ltd.)
The particles were sized in a spherical or cocoon shape with / D = 3 or less, and then dried to obtain fluorescent coloring particles.

[Comparative Example 2] Kaolin (trade name "UW90", manufactured by Engelhard Co., Ltd.) as a printability-imparting layer was replaced with titanium oxide (trade name, "A-220", manufactured by Ishihara Sangyo Co., Ltd.).
A sample was obtained in the same manner as in Example 1, except that

Comparative Example 3 A sample was obtained in the same manner as in Example 1, except that the coating amount of the printability-imparting layer was adjusted to 40 g / m ² in solid content.

[Comparative Example 4] [0110] Claim 1 except that the coating amount of the printability-imparting layer is adjusted to ² g / m2 in solid content.
A sample was obtained in the same manner as described above.

The samples obtained by the above methods were evaluated for printability and forgery prevention effects according to the following methods. Evaluation of printability Using an RI printing tester (manufactured by Mei Seisakusho), 1.0 g of ink for offset sheet-fed printing (trade name "TK Hi-Echo Sumi", manufactured by Toyo Ink Co., Ltd.) was spread and printed. After the print density was evaluated, the coated paper was adhered to the printing surface at a constant pressure 5 minutes after printing, and the state of ink transfer to the coated paper was evaluated. Then, the ink was changed to a special ink for surface strength measurement (trade name "S
MX Tack Grade 20 ", manufactured by Toyo Ink Co., Ltd.)
Instead of 0 g, the surface of the paper was evaluated for burrs. Comprehensively evaluated the color developability, settability, and surface strength evaluated by the above method, and evaluated the sample on a five-point scale with five samples having excellent printability and one sample determined to be unable to perform offset printing. A score greater than or equal to the score was passed.

Removal of Fluorescent Coloring Particles onto Blanket Also, when printing with 1.0 g of a special ink for surface strength measurement (trade name “SMX Tack Grade 20”, manufactured by Toyo Ink Co., Ltd.), it adhered to the blanket. Fluorescent particles
Black light (Product name "FL15BLB 15W",
It was confirmed by irradiating ultraviolet rays with Toshiba Corporation.

Thermal transfer printing quality Test printing was performed using a thermal transfer printing machine (trade name “MD-1000”, manufactured by Alps), and the print quality was visually evaluated by sensory evaluation. 5 samples with good print quality and 1 sample with bad print quality
A five-point evaluation was made as a point, and three or more points were judged to be acceptable.

Evaluation of anti-counterfeiting effect Fluorescent coloring particles in the sample, which can be confirmed visually, were confirmed by irradiating ultraviolet rays with black light. The evaluation was made on the assumption that the fluorescent coloring particles could be confirmed to have a higher forgery prevention effect. Five points were evaluated for the sample in which the fluorescent coloring particles could be easily confirmed visually and one point was determined for the sample that could not be visually confirmed. Three or more points were judged as acceptable.

The evaluation results are shown in Tables 1 to 5.

[0116]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[0117]

According to the present invention as described above, first, the following effects can be obtained in terms of preventing forgery by the effect of the fluorescent coloring particles.

1) Since the fluorescent coloring particles of the present invention can maintain their particle shape without dissolving even at a high temperature such as in a drying zone of a paper machine, for example, when these particles are mixed into paper, they can be irradiated with ultraviolet rays. Particles of a specific shape that develop a specific hue can be visually recognized, and can be suitably used for anti-counterfeit paper.

2) In the case where fluorescent coloring particles using a powdery substance having a hydroxyl group at the end as a powdery substance are incorporated into a paper, the fluorescence particles between the cellulose fiber, which is the main component of the paper, and the hydroxyl group of the powdery substance are mixed. Hydrogen bonds are generated, and the fluorescent particles are fixed in the paper. This leads to the advantage that the fluorescent particles do not fall off in the subsequent printing step.

3) Even if an attempt is made to incorporate particulate fluorescent pigment itself into the paper, the specific gravity of the inorganic fluorescent pigment is as large as about 4 to 5, so that the pigment precipitates during the flow of the slurry containing the pigment. There is a major drawback that the particle size is as small as 0.5 to 5 μm, and the emission is not visible even when irradiated with ultraviolet light under ordinary light. There is also. On the other hand, the fluorescent coloring particles obtained by the present invention have a specific gravity in the range of 1.2 to 1.8, and particles having a particle size of 50 μm or more can be easily obtained, so that the above-mentioned disadvantage can be solved. .

4) When a fluorescent pigment is used as the fluorescent agent of the fluorescent coloring particles of the present invention, a much higher coloring intensity can be obtained as compared with conventional fluorescent coloring particles obtained by dyeing starch particles with a fluorescent dye. Can be

5) By using a substance having a hydroxyl group as a powdery substance and using a resin having a reactive group that reacts with the hydroxyl group as a binder, fluorescent coloring particles having excellent water resistance can be obtained. Furthermore, by utilizing the interaction between an anionic binder and a cationic substance or between the cationic binder and a cationic substance, fluorescent coloring particles having excellent water resistance can be obtained.

6) As a powdery substance, when starches that are colored by an aqueous solution containing iodine and fluorescent coloring particles using polyvinyl alcohol are used for forgery prevention paper, detection of starches and polyvinyl alcohol in the paper is performed. This makes it possible to easily specify the source of the paper.

7) By using a white pigment as a component of the fluorescent coloring particles, the opacity of the particles can be increased. When such fluorescent coloring particles are used in the forgery prevention paper, it becomes difficult to visually recognize the presence of the fluorescent coloring particles under ordinary light, and it is difficult to determine that the forgery preventing means is taken. Therefore, the forgery prevention effect can be further enhanced.

8) In the present invention, a coloring agent may be used in combination with the production of the fluorescent coloring particles, or the fluorescent coloring particles may be colored and included in the paper. In this case, under normal light, particles colored in a specific hue can be visually recognized, and it can be made to develop a different hue by irradiating ultraviolet rays. Can be manufactured. Further, by using a colorant as a dropout color in optical reading, forgery prevention paper suitable for OCR reading and OMR reading can be manufactured.

9) Fluorescent coloring particles are produced by using a water-insoluble and organic solvent-soluble fluorescent dye or fluorescent pigment as a fluorescent agent used in the present invention. When the prevention printed matter is manufactured, traces of the fluorescent agent soluble in the organic solvent eluted from the fluorescent coloring particles and diffused to the surroundings when the tampering is attempted with the organic solvent can be visually recognized by irradiation with ultraviolet rays. Utilizing this property, the anti-counterfeit paper of the present invention can be suitably used for anti-counterfeit printed matter which is easily falsified.

10) Coloring the fluorescent particles using a coloring agent comprising a dye insoluble in water and soluble in an organic solvent, including the particles in paper, and then performing printing to produce a forgery-preventive printed material. When tampering is attempted, traces of the colorant dye eluted from the fluorescent particles and diffused around can be visually recognized. Utilizing this property, the anti-counterfeit paper of the present invention can be suitably used for anti-counterfeit printed matter which is easily falsified.

11) In the fluorescent coloring particles of the present invention having a structure in which a coating layer containing a fluorescent agent is formed on the surface of a granulated material containing a powdery substance, a dye insoluble in water and soluble in an organic solvent is formed together with the powdery substance. In the case where a fluorescent pigment having a hue close to white or white under ordinary light is used as a fluorescent agent in the coating layer, such fluorescent coloring particles are contained in the granulated material. Since the color of the organic solvent-soluble dye is concealed by the coating layer, when the particles are included in paper and then printed to produce a forgery-prevented printed matter,
Under ordinary light, it is difficult to visually recognize the presence of the fluorescent coloring particles, so that it is difficult to determine that the forgery prevention means is taken, and the forgery prevention effect can be further enhanced. Furthermore, when tampering is attempted using an organic solvent, traces of the organic solvent-soluble dye eluted from the granulated material, which is the core of the fluorescent coloring particles, and diffused to the surroundings can be visually observed. Can be reliably recognized.

12) The fluorescent coloring particles of the present invention are added at the time of manufacturing a nonwoven fabric or at the time of manufacturing a twisted yarn by utilizing the above-mentioned characteristics, thereby giving a nonwoven fabric having a fashionable characteristic. And fabrics.

Further, according to the printability-imparting layer of the present invention,
The following effects can be obtained without impairing the effects described above. 13) The anti-counterfeit paper excellent in offset printing can be manufactured by the printability-imparting layer of the present invention. 14) The printability-imparting layer of the present invention enables the manufacture of anti-counterfeit papers compatible with various printings other than offset printing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D21H 21/28 D21H 21/30 21/30 23/28 23/28 B41M 5/26 HF term (Reference) 2C005 HA04 HA30 JA09 JB40 2H111 AA07 CA03 CA04 CA30 CA31 CA33 CA41 4L055 AA02 AA03 AC06 AG08 AG10 AG12 AG17 AG18 AG20 AG23 AG27 AG45 AG47 AG48 AG56 AG71 AG81 AG94 AG98 AH01 AH02 AH37 AH50 AJ03 AJ04 GA12 EA14 FA14

Claims (32)

[Claims] The present invention relates to a forgery prevention paper in which a fluorescent coloring particle comprising a granulated mixture of a water-insoluble dye and / or pigment and a powdery substance which emits a fluorescent color when irradiated with ultraviolet light is contained in the paper. An anti-counterfeit paper excellent in printability, characterized in that a printability-imparting layer is provided within a range in which fluorescent coloring particles can be visually confirmed when the surface is irradiated with ultraviolet rays. 2. The method according to claim 1, wherein the fluorescent coloring particles comprise a granulated substance of a powdery substance and a coating layer of a water-insoluble dye and / or pigment which forms a fluorescent color when irradiated with ultraviolet light formed on the surface of the granulated substance. The anti-counterfeit paper excellent in printability according to claim 1 characterized by the above-mentioned. 3. The method according to claim 1, wherein the fluorescent particles are formed of a mixture of a water-insoluble dye and / or a pigment, a powdery substance and a white pigment, which emits a fluorescent color when irradiated with ultraviolet rays.
An anti-counterfeit paper excellent in printability according to claim 1. 4. A granulated product of a mixture of a powdery substance and a white pigment in which fluorescent coloring particles are formed, and a coating of a water-insoluble dye and / or pigment which emits fluorescence when irradiated with ultraviolet light formed on the surface of the granulated product. The anti-counterfeit paper excellent in printability according to claim 1, comprising a layer. 5. A granulated substance of a powdery substance in which fluorescent coloring particles are formed, a coating layer of a white pigment formed on the surface of the granulated substance,
2. A forgery prevention excellent in printability according to claim 1, further comprising a water-insoluble dye and / or pigment coating layer formed on the outside of said white pigment coating layer and which emits a fluorescent color when irradiated with ultraviolet rays. Paper. 6. The fluorescent coloring particles have a powdery substance having a hydroxyl group, a water-insoluble dye and / or a pigment which emits a fluorescent color when irradiated with ultraviolet rays, and two or more reactive groups which react with the hydroxyl group contained in the powdery substance. The anti-counterfeit paper excellent in printability according to claim 1, comprising a granulated product of a mixture with a resin binder. 7. A powdery substance having a hydroxyl group, a white pigment, a water-insoluble dye and / or a pigment which emits a fluorescent color when irradiated with ultraviolet light, and a reactive group which reacts with a hydroxyl group contained in the powdery substance. The anti-counterfeit paper excellent in printability according to claim 1, comprising a granulated product of a mixture with at least one resin binder. 8. A granulated substance of a powdery substance whose fluorescent coloring particles have a hydroxyl group, a water-insoluble dye and / or pigment which emits fluorescence by irradiation of ultraviolet rays formed on the surface of the granulated substance, and the powdery substance The anti-counterfeit paper excellent in printability according to claim 1, comprising a coating layer of a mixture with a resin binder having two or more reactive groups reacting with a hydroxyl group contained in the paper. 9. A granulated product of a mixture of a powdery substance in which fluorescent coloring particles having a hydroxyl group and a white pigment, and a water-insoluble dye and / or a fluorescent dye formed by irradiation of ultraviolet light formed on the surface of the granulated material. The anti-counterfeit paper with excellent printability according to claim 1, comprising a coating layer of a mixture of a pigment and a resin binder having two or more reactive groups that react with a hydroxyl group of the powdery substance. 10. A granulated product of a powdery substance in which fluorescent coloring particles have a hydroxyl group, a coating layer of a white pigment formed on the surface of the granulated product, and an ultraviolet ray formed outside the coating layer of the white pigment. A coating layer comprising a mixture of a water-insoluble dye and / or pigment which emits fluorescence upon irradiation and a resin binder having two or more reactive groups which react with hydroxyl groups contained in the powdery substance. 2. Forgery-preventing paper having excellent printability according to 1. 11. A granulated product of a mixture of a powdery substance and an anionic binder in which fluorescent coloring particles are formed, and a water-insoluble dye and / or pigment which emits fluorescence when irradiated with ultraviolet light formed on the surface of the granulated product. The anti-counterfeit paper excellent in printability according to claim 1, comprising a coating layer of a mixture with a cationic substance. 12. A granulated product of a mixture of a powdery substance, a white pigment, and an anionic binder, wherein a fluorescent color-forming particle is formed of a mixture of a powdery substance, a white pigment, and an anionic binder; The anti-counterfeit paper excellent in printability according to claim 1, wherein the anti-counterfeit paper comprises a coating layer made of a cationic substance of a pigment. 13. A granulated product of a mixture of a powdery substance and a cationic binder in which fluorescent coloring particles are formed, and a water-insoluble dye and / or pigment which emits fluorescence when irradiated with ultraviolet light formed on the surface of the granulated product. The anti-counterfeit paper excellent in printability according to claim 1, comprising a coating layer made of an anionic substance. 14. A granulated product of a mixture of a powdery substance, a white pigment, and a cationic binder, wherein a fluorescent color-forming particle is formed of a mixture of a powdery substance, a white pigment, and a cationic binder; The anti-counterfeit paper excellent in printability according to claim 1, comprising a coating layer formed of a pigment anionic substance. 15. The anti-counterfeit paper excellent in printability according to claim 1, wherein the dye and / or pigment contained in the fluorescent coloring particles is soluble in an organic solvent. 16. The anti-counterfeit paper excellent in printability according to claim 1, wherein the fluorescent coloring particles are colored. 17. The color copying machine according to claim 1, wherein the color is colored so pale that the hue cannot be reproduced.
6. An anti-counterfeit paper excellent in printability according to 6. 18. The method according to claim 16, wherein the coloring is a dropout color in optical reading.
Item 17. An anti-counterfeit paper excellent in printability according to items 17. 19. The method according to claim 16, wherein the coloring is carried out with a dye insoluble in water and soluble in an organic solvent.
20. An anti-counterfeit paper excellent in printability according to any one of Items 1 to 18. 20. The anti-counterfeit paper excellent in printability according to claim 1, wherein the fluorescent particle diameter is 50 to 800 μm. 21. A granulated substance in which the fluorescent coloring particles contain a powdery substance and a water-insoluble and organic solvent-soluble dye, and the color of the granulated substance becomes white or close to white under the ordinary light formed on the surface of the granulated substance. The anti-counterfeit paper excellent in printability according to any one of claims 1 to 20, comprising a coating layer containing a water-insoluble dye and / or pigment which has a hue and emits fluorescence when irradiated with ultraviolet light. 22. The anti-counterfeit paper excellent in printability according to claim 1, wherein a portion where the fluorescent coloring particles are present is opaque. 23. The anti-counterfeit paper having excellent printability according to claim 1, wherein the printability-imparting layer is formed of only a resin. 24. The anti-counterfeit paper with excellent printability according to claim 23, wherein the printability-imparting layer is formed only of a resin, and the coating amount is 5 to 20 g / m ² . 25. The printability-imparting layer is a filler coating layer comprising an inorganic powder and a binder.
23. An anti-counterfeit paper excellent in printability according to any one of items 22 to 22. 26. The printability according to claim 1, wherein the printability-imparting layer has a two-layer structure of a layer formed of only a resin and a filler coating layer. Excellent forgery prevention paper. 27. The anti-counterfeit paper excellent in printability according to claim 25 or 26, wherein the refractive index of the inorganic powder is 2.0 or less. 28. The inorganic powder having an average particle size of 0.3 to 2
The anti-counterfeit paper excellent in printability according to claim 25 or 26, which has a thickness of 0 µm. 29. An inorganic powder having an average particle diameter of 0.1 μm
The anti-counterfeit paper excellent in printability according to claim 25 or 26, wherein: 30. The inorganic powder is at least one selected from silicate, silicic acid, calcium carbonate, magnesium carbonate, aluminum hydroxide, satin white, barium sulfate, calcium sulfate, and plastic pigment. The forgery-prevention paper excellent in printability according to any one of claims 25 to 29. 31. A printability-imparting layer which is a filler-coated layer containing the inorganic powder in a solid content of 40 to 95% by weight with respect to the coating layer, and has a coating amount of 5 to 30 g / m2. excellent anti-falsification paper printability of any one of claims 25 to 30, which is a ^2. 32. The paper according to claim 1, wherein said fluorescent coloring particles are contained in a strip or streak in the paper.
The forgery prevention paper excellent in printability according to any one of the above.