JP2001115053A - Hot water-insoluble functional particle and special paper having ability for identifying oneself and others - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain white functional particles which elute a specific color tone dye, when brought into contact with an organic solvent, and to obtain special paper which uses the while functional particles and has an ability to identify oneself and others. SOLUTION: The hot water-insoluble functional particles are obtained by forming organic solvent-permeable white shell layers on the surfaces of core particles, respectively, carrying a coloring dye which is insoluble in water and soluble in organic solvents. The characteristic of the special paper having an ability to identify oneself and others is to contain the functional particles. When it is tried to falsify the paper with an organic solvent, the dye contained in the functional particles is eluted. Thereby, the signs of the falsification can be detected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to functional particles insoluble in hot water and to special papers having self-other discrimination ability. In detail, it looks white in a normal state, and when it is brought into contact with an organic solvent, a hot water-insoluble functional particle having a property that a dye of a specific hue elutes, and the particles are included in paper. Therefore, when falsification is attempted using an organic solvent, it is required to use forgery-prevention paper that has the property that traces of falsification can be easily detected, and to be able to identify self and others. ) Special paper that can be used for paper.

[0002]

2. Description of the Related Art It is preferable that tampering of passports, bills, checks, and the like can be easily detected even if the tampering is attempted using various chemicals, and various methods have been proposed. For example, Patent No. 78774 and Patent No. 77
No. 962 proposes a security paper in which a manganese ferrocyanide is included in a paper, and when the characters written in the money amount column are erased by ink erasing and falsification is attempted, the falsified portion turns brown.

Further, Japanese Patent No. 136286 proposes a tamper-proofing paper in which a substance that changes color by an oxidizing agent, tannin and a penetrant are processed into paper, and if the tamper is attempted by erasing the ink, a color that does not disappear is obtained. There is.

Further, Japanese Patent No. 1414483 proposes a safety paper which contains a reactive fluorescent dye based on a water-soluble metal salt of pyrenesulfonic acid in a paper and gives a fluorescent color when the ink is erased or tampered with a weak alkali. There is.

Japanese Patent Application Laid-Open No. 57-21660 discloses that even if a microcapsule containing a solvent for an erasable ink is contained on the surface of a paper and attempted to be tampered with an eraser or the like, the capsule is broken by the pressure and the ink is broken. There is a proposal of a forgery prevention paper in which paper is eluted and permeated into a paper layer so that traces of tampering remain.

Japanese Patent Application Laid-Open No. 63-182496 discloses that
A color-developing layer containing a leuco dye, a phenolic substance and a binder as main components is provided on the paper surface, and even if an attempt is made to falsify with an organic solvent, the leuco dye and the phenolic substance are eluted by the permeation of the solvent, and the two react chemically to form a color. There is a proposal for falsification prevention paper.

Further, the present applicant has filed Japanese Patent Application No. 10-29779.
No. 22 proposed anti-counterfeit paper in which fluorescent dye particles which are insoluble in water and soluble in an organic solvent are contained in the paper. This paper is characterized in that traces of tampering with an organic solvent can be easily visually recognized by irradiation with ultraviolet light even in a bright room.

[0008] On the other hand, when paper or paper products are shipped to the market and a trouble occurs at the end user, these papers and paper products are identified by their own and other discriminating ability (the paper or paper products are their own products, It may be preferable to have the ability to later identify when they were manufactured. For example, OCR paper is manufactured by multiple companies and used for gift certificates. If a counterfeit ticket is circulated, the paper used for the counterfeit ticket is analyzed by some means and the source of the paper is determined. If it has a function that can identify a forgery, it is possible to respond quickly to a crime and the effect of preventing forgery is further enhanced.

In the case of manufacturing various types of paper, if it is possible to detect the self-other discrimination ability for each lot, it is possible to specify when this paper was manufactured in the event of trouble in the market. It will be possible to respond quickly to troubles.

Means for imparting self-other discrimination to paper and paper products are as follows:
Basically, some kind of invisible code may be attached to these and detected by physical or chemical means. For example, Japanese Patent Publication No. 54-36686 discloses that in a paper product manufacturing process, 0.0001 to 1% of finely colored particles of 1 to 3 μm are added to a stock or paint and a microscopic code is added to the paper product. A method for facilitating identification has been proposed. This method is characterized in that colored fine fibers in a paper product can be detected by physical means such as microscopic observation.

Japanese Patent Publication No. 56-16238 proposes a forgery prevention paper in which fluorescent dyed fibers are incorporated in a paper at 50% or less, preferably 5% or less. This method is characterized in that the coloring of fluorescent dyed fibers in paper can be detected by physical means such as irradiation with ultraviolet light.

[0012]

Various means have been known for providing self-other discrimination to paper. The present inventors have studied to obtain a special paper having self-other discrimination ability completely different from those conventionally known methods. That is, the present invention obtains functional water-insoluble particles which are not conventionally available by using a water-insoluble and organic solvent-soluble coloring dye, and the self-other discrimination ability conventionally proposed by using the particles. It is an object of the present invention to develop a sheet having a completely different configuration from a sheet having a sheet.

[0013]

Means for Solving the Problems A first invention of the present invention is:
Hot water-insoluble functional particles, characterized in that a white shell layer having the property of penetrating an organic solvent is formed on the surface of core particles carrying a water-insoluble and organic solvent-soluble coloring dye. is there. Further, the second invention of the present invention
Special paper having self-other discrimination ability, characterized by containing the functional particles.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a detailed description will be given of a forgery prevention paper which is a typical application of the present invention. The functional particles of the present invention have a core structure as a core and a shell layer as a shell formed on the surface of the core. That is, first, hot water-insoluble core particles (particles serving as nuclei) carrying a water-insoluble and organic solvent-soluble coloring dye (hereinafter simply referred to as “coloring dye” in the present invention) are first produced, and then the core particles are produced. A white shell layer (a layer serving as a shell) having a property of transmitting an organic solvent is formed on the surface of the substrate.

First, an example of a method for producing hot water-insoluble core particles (hereinafter, simply referred to as “core particles” in the present invention) carrying a coloring dye will be described first. Here, “supported” means either a state in which the core particle contains the coloring dye and / or a state in which the coloring dye is supported on the surface of the core particle.

One example of the core particles first produced in the present invention is:
Forming a colored dye layer on the surface of a core particle composed of a granular material of only a coloring dye, a core particle composed of a granulated material of a mixture of a coloring dye and a powdery substance, and a granulated substance of a mixture of a coloring dye and a powdery substance Core particles, a core particle having a colored dye layer formed on the surface of a granulated substance of a powdery substance, and the like.

The core particles composed of a granulated product of a mixture of a coloring dye and a powdery substance can be produced by mixing a coloring dye and a powdery substance and granulating the mixture. At this time, secondary materials such as white pigments and fluorescent pigments can be used in combination as long as the object of the present invention is not impaired. The manufacturing method will be specifically described below.

Further, one example of the core particle of the present invention comprises a granulated substance of a powdery substance and a colored dye layer formed on the surface of the granulated substance. Can be produced by granulating and then coating the surface of the granulated material with a coloring dye. At this time, the above-mentioned auxiliary materials can be used in combination as long as the object of the present invention is not impaired.

In the present invention, a core particle carrying a coloring dye can be produced by using a resin binder having two or more reactive groups which react with a hydroxyl group contained in a powdery substance at the time of granulation or coating.

That is, the core particles of the present invention are a resin binder having two or more reactive groups that react with a powdery substance, a coloring dye, and a hydroxyl group contained in the powdery substance (hereinafter referred to as “resin binder” in the present invention). The core particles can be produced by mixing a powdery substance, a coloring dye, and a resin binder, and granulating the mixture.

Further, the core particles of the present invention comprise a granulated product of a mixture of a powdery substance, a white pigment, a coloring dye and a resin binder. It can be produced by mixing a dye and a resin binder and granulating the mixture.

Further, the core particles of the present invention are composed of a granulated substance of a powdery substance and a coating layer of a colored dye formed on the surface of the granulated substance with a resin binder. It can be produced by granulating a powdery substance and coating the surface of the granulated substance with a coloring dye with a resin binder.

Further, the core particles of the present invention comprise a granulated product of a mixture of a powdery substance and a white pigment, and a coating layer of a colored dye formed on the surface of the granulated product with a resin binder. The core particles can be produced by mixing a powdery substance and a white pigment, granulating the mixture, and coating the surface of the granule with a coloring dye with a resin binder.

Further, in the present invention, at the time of granulation or coating, the interaction between the anionic binder or the cationic binder contained in the granulated material and the cationic substance or the anionic substance contained in the coating layer. The core particles can be produced by utilizing the above.

That is, the core particle of the present invention comprises a granulated substance of a powdery substance with an anionic binder and a coating layer of a coloring dye formed on the surface of the granulated substance. It can be produced by granulating a powdery substance with an anionic binder and coating the surface of the granulated substance with a colored dye with a cationic substance.

Further, the core particles of the present invention comprise a granulated substance of a powdery substance and a white pigment by an anionic binder and a coating layer of a cationic substance of a coloring dye formed on the surface of the granulated substance. The core particles can be produced by granulating a powdery substance and a white pigment with an anionic binder, and coating the surface of the granulated substance with a coloring dye with a cationic substance.

Further, the core particle of the present invention comprises a granulated substance of a powdery substance with a cationic binder, and a coating layer of a colored dye formed on the surface of the granulated substance with an anionic substance, The core particles can be produced by granulating a powdery substance with a cationic binder and coating the surface of the granulated substance with a coloring dye with an anionic substance.

Further, the core particles of the present invention comprise a granulated substance of a powdery substance and a white pigment by a cationic binder, and a coating layer of a colored dye formed on the surface of the granulated substance by an anionic substance. The core particles can be produced by granulating a powdery substance and a white pigment with a cationic binder, and coating the surface of the granulated substance with a coloring dye with an anionic substance.

Next, the powdery substance used in the present invention will be described. Representative examples of the powdery substance used in the present invention include starch. Specifically, potato starch,
Corn starch, sweet potato starch, tapioca starch, sago starch,
Natural starches such as rice starch, amaranth starch, taro starch, and ginseng starch; modified starches thereof (dextrin, acid-decomposed starch, oxidized starch, pregelatinized starch, starch derivatives such as etherification, esterification, cross-linking, grafting) Starch, moist heat-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; carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl. Cellulose derivatives such as cellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and quaternary cationized hydroxyethylcellulose; alginic acid, agar, fungi, carrageenan, furceleran, pectin, chitin, chitosan, guar gum, locust bean gum, tamarind gum, gum arabic, gum tragacanth ,
Polysaccharides such as karaya gum, tara gum, konjac, trolloay, pullulan, dextran and 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 can also be used as the powdery substance.

The coloring dye used in the present invention must have a chromatic color (appears colored) under ordinary light such as room light and natural light, and must be water-insoluble and soluble in an organic solvent. . This is because if it is water-soluble, the colored dye will be dissolved in water during paper production, and the object of the present invention cannot be achieved. Further, if the solvent is not soluble in the organic solvent, the trace of the tampering cannot be visually recognized when the tampering is attempted with the solvent.

As the coloring dye used in the present invention, any dye can be used as long as it is insoluble in water and soluble in an organic solvent. Monoazo, disazo, metal complex type monoazo, anthraquinone, phthalocyanine, and Dyes such as allylmethane type are usually used. These dyes are described in “Dye Handbook” as to which organic solvent they dissolve, and the type can be specified by the color index (CI number).

To give just one example, C.I. I. 26110
Is insoluble in water and is soluble in organic solvents such as acetone, ethyl cellosolve, methyl ethyl ketone, ethyl acetate and toluene. C. I. The orange dye 111920 is insoluble in water and is soluble in organic solvents such as ethanol, benzene, acetone and oleic acid. C. I. 11390
The yellow dye is insoluble in water, ethanol, acetone,
Dissolves in organic solvents such as benzene and toluene. C. I.
42563B blue dye is insoluble in water and is soluble in organic solvents such as ethanol, acetone, ethyl acetate, benzene, toluene, oleic acid and stearic acid. C.
I. The brown dye 11360 is insoluble in water and soluble in organic solvents such as ethanol, xylol and benzene.
C. I. The 61100 purple dye is insoluble in water and soluble in organic solvents such as acetone, pyridine, methanol, and ethanol. C. I. The 26150 black dye is insoluble in water and soluble in organic solvents such as acetone, cyclohexane, benzene, toluene and xylene.

In the present invention, dyes such as aminoketones which are chromatic under ordinary light rays and emit light in various hues upon irradiation with ultraviolet rays can also be used. When this kind of coloring dye is used in the present invention, it is possible to obtain a unique effect that elution of the coloring dye due to the organic solvent can be detected by irradiation of ultraviolet rays. Color dyes of this kind are also sold by dye manufacturers, but one example is (product name "Yellowflu"
or G ", manufactured by Sumitomo Chemical Co., Ltd .: yellow under a normal light source, and yellow when irradiated with ultraviolet rays.
ayset Flavine FN ", manufactured by Nippon Kayaku Co., Ltd.): yellow under a normal light source, yellowish when irradiated with ultraviolet light, (trade name" Kayaset Flavi "
ne FG ", manufactured by Nippon Kayaku Co., Ltd .: yellow under a normal light source, and yellow when irradiated with ultraviolet rays.
yaset Yellow SF-G ", manufactured by Nippon Kayaku Co., Ltd.): yellow under a normal light source, yellowish when irradiated with ultraviolet rays, (trade name" Kayaset Orange ").
ge SF-R ", manufactured by Nippon Kayaku Co., Ltd .: orange color under a normal light source, and orange color when irradiated with ultraviolet light." (trade name "Kayaset Red SF-
B ", manufactured by Nippon Kayaku Co., Ltd .: Red under normal light source,
(Colors red when irradiated with ultraviolet light), (trade name “Kayase
tRed SF-4G ", manufactured by Nippon Kayaku Co., Ltd .: red under an ordinary light source, and red when irradiated with ultraviolet rays.

In the present invention, one or more of these coloring dyes are used. Some coloring dyes do not dissolve in specific organic solvents, but for the purpose of anti-counterfeiting anti-counterfeit paper, combine several kinds of coloring dyes and dissolve in all commonly available organic solvents. It is preferable to do so. By doing so, the falsification prevention effect is further enhanced.

Further, by using two or more combinations of different soluble organic solvents as coloring dyes, a spot of a specific hue appears in a certain organic solvent, and a spot of a specific hue appears in another organic solvent. Paper having the unique effect that the appearance of appears. For example, the red coloring dye of CI27291 is soluble in ethanol and insoluble in ethyl acetate, benzene and toluene. The blue colored dye of CI42563B is soluble in ethanol, ethyl acetate, benzene and toluene. When these two types of coloring dyes are used together to produce functional particles and include them in paper, purple spots appear when immersed in ethanol, and blue spots appear when immersed in ethyl acetate, benzene, and toluene. Can be manufactured. These coloring dyes are distributed simultaneously or separately inside and / or on the surface of the core particles.

As the white pigment used in the present invention, those having high whiteness among powdery inorganic substances, for example, titanium dioxide, kaolin, clay, talc, calcium carbonate, zinc chloride, zinc sulfide, zinc oxide, carbonate Magnesium, 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 functional particles of the present invention, it is necessary to further form a white shell layer having the property of penetrating an organic solvent on the surface of the above-mentioned hot water-insoluble core particles carrying the coloring dye. . The white shell layer functions to mask the color of the core particles caused by the coloring dye and to make the core particle look white. By doing so, it is possible to make it difficult to visually recognize that the functional particles are contained in the paper. That is,
Since the functional particles are synchronized with the hue (white) of the paper, it is difficult to visually recognize that the functional particles are contained in the paper. It is to be noted that the meaning of the above “white” is, of course, white, and a white substantially similar to the color of paper is also included in the category. For example, OCR paper has a light cream color, but is included in the category of “white”.

In the present invention, when a white pigment having a high light refractive index, that is, a white pigment having a refractive index of 2.0 or more, is used, the effect of concealing the color of the core particles becomes large. For example, titanium dioxide (refractive index: about 2.6), zinc sulfide (2.3), zinc oxide (2.0), and the like can be suitably used in the present invention.

It is necessary that the white shell layer formed on the surface of the core particles has a property of permeating an organic solvent. This is because when the organic solvent penetrates into the functional particles, the coloring dye carried in the functional particles elutes, and it becomes possible to detect traces of tampering.

As will be described later, when the functional particles of the present invention are contained in paper to produce anti-counterfeit paper, if the functional particles are added to the stock during the paper making process, the functional paper will not function as wet paper in the paper making process. When sprinkling the functional particles, furthermore, when adding the functional particles to the coating liquid and coating the paper surface, etc., it has water resistance to prevent the functional particles from collapsing in water. Need to be. Further, depending on the temperature of the drying zone of the paper machine, it is necessary that the functional particles have a hot water insolubility such that the functional particles do not dissolve and collapse.

In the present invention, in order to impart water resistance and hot water insolubility to the functional particles, the functional particles react with hydroxyl groups of powdery substances such as starch, flour, cellulose, other polysaccharides, sugars, and polyvinyl alcohol. A resin having two or more reactive groups is used as a binder. In the present invention, this type of resin is referred to as a “resin binder”. Examples of such a resin binder include a polyamine / epichlorohydrin resin, a water-soluble alkylated amino resin, a water-soluble methylated melamine resin, a water-soluble phenol resin,
Examples include urea resins, epoxidized polyamide resins, and methylolated polyacrylamide resins.

In order to impart water resistance and hot water insolubility to functional particles by using a resin binder, a resin binder may be mixed with a component of the functional particles and granulation may be performed. What is necessary is just to coat a white pigment with a resin binder.

In the present invention, as another method for imparting water resistance and hot water insolubility to the functional particles, an interaction between the anionic binder contained in the core particles and the cationic substance contained in the shell layer is considered. A method utilizing the action or the interaction between the cationic binder contained in the core particles and the anionic substance contained in the shell layer can be employed. That is, water resistance and hot water insolubility can be imparted to the anionic binder by granulating the components of the core particles with an anionic binder and coating the surface of the core particles with a white pigment with a cationic substance. Alternatively, water resistance and hot water insolubility can be imparted to the cationic binder by granulating the components of the core particles with a cationic binder and coating the surface of the core particles with a white pigment with an 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.

In order to impart water resistance and hot water insolubility to the anionic binder, the cationic substance to be coated with the white pigment on the surface of the granulated material may be a salt of a polyvalent metal ion, for example, calcium, magnesium, barium. , Boron, aluminum, titanium and other hydrochlorides, sulfates, carbonates, phosphates, lactates, and hydroxides.

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 as the above-mentioned cationic substances 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.

In order to impart water resistance and hot water insolubility to the cationic binder, the anionic substance coated with the white pigment on the surface of the core particles includes the polysaccharide having an anionic group described above as the anionic binder. Alternatively, a synthetic polymer having an anionic 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 the core particles, a method generally used conventionally for granulating starch or the like can be employed. That is, rolling granulation,
Extrusion granulation, spray drying granulation, fluidized bed granulation, compression granulation, melt granulation, crush granulation, stirring granulation, and 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 core particles with a white pigment, the core particles are dried and then the white pigment is coated with a binder in a liquid (dispersion), or the binder is coated with a liquid. A method of coating a white pigment in a powdery form while spraying the same. 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 liquid granulating device such as a tumbling granulator, a fluidized bed granulator, or a drying machine). Can be used, and any device other than a dedicated coating machine can be used as long as it can be used for the coating process.

The shape of the functional particles of the present invention produced by the above-mentioned method varies 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 circular shape. When the length is the same or almost the same as this diameter, it looks spherical, and when the length is long, it looks like a cocoon. Also,
Those obtained by the spray-drying granulation method are substantially spherical, those obtained by the tumbling granulation method and the stirring granulation method are substantially spherical, and those obtained by the fluidized-bed granulation method are similar to compei sugar. However, depending on the conditions, different shapes may be obtained by the same granulation method.

The particle size of the functional particles can be appropriately controlled from several μm to several hundred μm, but in the present invention, the particle size is preferably adjusted within the range of 50 to 800 μm. If the particle size is less than 50 μm, it becomes more difficult to visually recognize traces of tampering with an organic solvent when the particles are contained in paper. 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, any method may be employed as a method for incorporating the functional particles into the paper. Hereinafter, an example will be described. In the present invention, these functional particles may be used alone or in combination of two or more.

Production Example 1 of Special Paper Having Self-Other Discrimination Ability
In the production of special paper having self-other discrimination ability of the present invention,
Normally bleached softwood kraft pulp (NBKP), hardwood bleached kraft pulp (LBKP), softwood bleached sulphite pulp (NBSP), thermo-mechanical pulp (TMP)
A slurry mainly containing paper pulp such as is prepared, and various internal fillers, a dry paper strength enhancer, a sizing agent, a fixing agent,
A paper-making auxiliary material such as a retention aid, a drainage improver, an antifoaming agent, a dye, and a coloring pigment is appropriately used in combination, and usually has a freeness of 550.
~ 250 ml C.I. S. F. A slurry is prepared, and the above-mentioned functional particles are added thereto, and the paper is made using a well-known paper machine such as a round paper machine or a fourdrinier paper machine.

Production example 2 of special paper having self-other discrimination ability Function during the flow of slurry for making paper to paper machine
Method of adding an aqueous suspension of functional particles using a pump or the like A well-known paper machine such as a round paper machine or a fourdrinier machine using the slurry to which the functional particles are not added in Production Example 1 described above. When the paper is made by using the above method, the functional particles are suspended in water in a flow box of a fourdrinier paper machine or in a vat of a circular net paper machine, and added using a pump or the like to make the paper.

Production example of special paper having self-other discrimination ability 3 Function as wet paper on paper-mesh net when making paper with Fourdrinier paper machine
Method of Sprinkling Functional Particles When making a paper using a Fourdrinier paper machine using the slurry to which the functional particles are not added in Production Example 1, the wet paper on the paper net of the Fourdrinier paper machine is used. The functional particles are sprinkled on the entire surface or in a streak shape using a sprinkling device or the like, and then paper is made according to a conventional method.

Production example 4 of special paper having self-other discrimination ability When wet paper is formed on a fourdrinier paper machine
Method of Sprinkling Aqueous Suspension of Functional Particles When making a paper using a Fourdrinier paper machine by using the slurry to which the functional particles are not added in Production Example 1 described above, The functional particles suspended in water are sprinkled on the upper wet paper over the entire surface or in a streak shape using a sprinkler or a nozzle sprayer, and thereafter the paper is made according to a conventional method.

Production Example 5 of Special Paper Having Self- Other Discrimination Ability Method of Using Functional Particles in Combination with Size Press Liquid etc. Using the slurry of Production Example 1 described above without adding functional particles, a fourdrinier paper machine When paper making is performed using a size press, functional particles are suspended in a size press solution such as modified starch, polyacrylamide, or polyvinyl alcohol, and coated on the surface of a wet paper. Make paper according to the method.

Production Example 6 of special paper having self-other discrimination ability Water-based paint using a coater such as an air knife coater
Method of using functional particles in combination when applying the above, using the slurry to which the functional particles are not added in Production Example 1, after making a fourdrinier paper machine or a circular net paper machine,
The functional particles are added to a coating solution for producing art paper or coated paper, and the paper is manufactured using a coating machine such as an air knife coater or a blade coater.

Production Example 7 of Special Paper Having Self- Other Identification Function When printing on paper, functional particles are added to the water-based ink.
The functional particles are added to the aqueous ink, and predetermined characters and patterns are printed on paper using a printing machine. Printing may be performed during papermaking with a papermaking machine (on-machine printing using a flexographic printing machine or the like), or may be performed using a gravure printing machine or the like after papermaking (off-machine printing). ). For example, if the character "VOID" is printed, the character "VOID" can be made to emerge when tampering is attempted with an organic solvent.

In the present invention, among the above-mentioned various methods, the fact that the yield of the functional particles is good (when the particles are added to the slurry, the particles have a small particle size so that the particles can easily flow out of the papermaking net) and Since it does not contaminate etc., a method of using functional particles in combination with a size press liquid, etc., a method of using the particles in combination with a water-based paint using a coater such as an air knife coater, printing on paper At this time, it is preferable to adopt a method of adding the particles to the aqueous ink.

[0063]

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. The organic solvent is a typical example, and it goes without saying that the coloring dye is eluted in other organic solvents.

Example 1 Production Example 1 of Functional Particle 1 100 parts by weight of corn starch, water-soluble methylated melamine resin (trade name “SUMITEX”) as a resin binder
RESIN M-3 ", manufactured by Sumitomo Chemical Co., Ltd., 10 parts by weight, a water-insoluble organic solvent-soluble red dye (CI.
26110) 2 parts by weight, 30 parts by weight of water, and 1 part by weight of polyoxyethylene stearyl ether [lubricant]
The mixture was mixed and stirred with a kneader for 10 minutes. This mixture was extruded into a granulator (Domegran, Fuji Paudal Co., Ltd.)
Production), a columnar granule having a diameter of 500 μm was extruded and granulated. The granulated product is sized in a spherical or cocoon shape having an L / D of 3 or less using a sizing machine (“Malmerizer”, manufactured by Fuji Paudal Co., Ltd.), and then dried to produce core particles. did. Next, a white pigment (anatase-type titanium dioxide, average particle diameter 0.4 μm) 2 was added to the surface of the core particles.
A coating solution obtained by dispersing 0 parts by weight and 2 parts by weight of carboxymethyl starch [anionic substance] in 50 parts by weight of water was applied to a fluidized bed granulation coating apparatus (apparatus name "Flow Coater", manufactured by Freund Corporation). Fluid bed coating was performed to form a shell layer in which the hue of the core particles was concealed and appeared white. 5 parts by weight of the obtained functional particles were dispersed in 100 parts by weight of water, and 10 parts at a rotation speed of 300 rpm.
Stirred for minutes but did not disintegrate.

Example 2 Production Example 2 of Functional Particles 100 parts by weight of crystalline cellulose (trade name “Avicel”, manufactured by Asahi Kasei Corporation), zinc oxide [white pigment] 10
Parts by weight, a water-insoluble and organic solvent-soluble blue dye (C.I.
I. 42563B) 2 parts by weight, water-insoluble and organic solvent-soluble red dye (CI. 27291) 2 parts by weight, and water-soluble methylated melamine-based resin as a resin binder (trade name "SUMITEX RESIN M-3") 1
Granulation / coating using 0 parts by weight of 25 parts by weight of a hydroxypropyl starch [general binder] (trade name "Piostarch H", manufactured by Nissei Chemical Co., Ltd.) 25 parts by weight as a binder The granules were granulated and dried in a device ("High Speed Mixer", manufactured by Fukae Kogyo Co., Ltd.) to produce core particles having a particle size of 300 to 800 [mu] m. Next, 20 parts by weight of a white pigment (rutile-type titanium dioxide, average particle size 0.35 μm) and 2 parts by weight of carboxymethyl starch [anionic substance] were dispersed on 50 parts by weight of water on the surface of the core particles. The liquid was subjected to fluidized bed coating using a fluidized bed granulating and coating apparatus (apparatus name "Flow Coater", manufactured by Freund Corporation) to form a shell layer in which the hue of the core particles was concealed and appeared white. 5 parts by weight of the obtained functional particles were added to water 1
The mixture was dispersed in 00 parts by weight and stirred at a rotation speed of 300 rpm for 10 minutes, but did not disintegrate.

Example 3 Production Example 3 of Functional Particles 100 parts by weight of cornflower, 5 parts by weight of a red coloring dye (trade name “Kayaset Red SF-4G”, manufactured by Nippon Kayaku Co., Ltd.), polyethyleneimine [cation Binder] (trade name “Epomin P-1000”, manufactured by Nippon Shokubai Co., Ltd.) was spray-dried using 15 parts by weight as a binder to obtain core particles. On the surface of this core particle,
White pigment (calcium carbonate, average particle size 0.4 μm) 2
A coating solution obtained by dispersing 0 parts by weight and 2 parts by weight of carboxymethyl starch [anionic substance] in 50 parts by weight of water was applied to a fluidized bed granulation coating apparatus (apparatus name "Flow Coater", manufactured by Freund Corporation). Fluid bed coating was performed to form a shell layer in which the hue of the core particles was concealed and appeared white, to obtain spherical functional particles having a particle size of 50 to 500 μm. 5 parts by weight of the functional particles are added to 100 parts of water.
It was dispersed in parts by weight and stirred at a rotation speed of 300 rpm for 10 minutes, but did not disintegrate.

Example 4 Production Example 4 of Functional Particles 100 parts by weight of corn flour, polyethyleneimine [cationic binder] (trade name “Epomin P-100”)
0 ", manufactured by Nippon Shokubai Co., Ltd.) and spray-dried using 15 parts by weight as a binder. Continuously C.I. I. 26150, 5 parts by weight of a black colored dye, polyethyleneimine [cationic binder] (trade name “Epomin P-1000”,
Spray drying was performed using 15 parts by weight of a binder (manufactured by Nippon Shokubai Co., Ltd.) to produce core particles. A white pigment (kaolin, average particle size 0.55 μm) 2
A coating solution obtained by dispersing 0 parts by weight and 2 parts by weight of carboxymethyl starch [anionic substance] in 50 parts by weight of water was applied to a fluidized bed granulation coating apparatus (apparatus name "Flow Coater", manufactured by Freund Corporation). Fluid bed coating was performed to form a shell layer in which the hue of the core particles was concealed and appeared to be white, and spherical functional particles having a particle size of 200 to 800 μm were obtained. 5 parts by weight of these functional particles are added to water 10
The mixture was dispersed in 0 parts by weight and stirred at a rotation speed of 300 rpm for 10 minutes, but did not disintegrate.

Example 5 Production of special paper having self-other discrimination ability
Example 1 350 ml of 20 parts by weight of NBKP and 80 parts by weight of LBKP
C. 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 1.0 parts by weight manufactured by Chemical Industry Co., Ltd.)
An appropriate amount of a sulfuric acid band was added to prepare a slurry. To the slurry, 0.1 parts by weight of the functional particles of Example 1 was added and dispersed. Using this slurry, a special paper having a basis weight of 100 g / m ^{2 and} a self-other discrimination ability was produced using a fourdrinier paper machine in accordance with a conventional method. At this time, 0.2% by weight of polyvinyl alcohol by a size press installed in the middle of the drying zone.
The aqueous solution was applied. The presence of the functional particles was not visible even when the obtained special paper having self-other discrimination ability was observed under fluorescent lamp illumination, but when acetone, methyl ethyl ketone, ethyl acetate, toluene, etc. were dropped, the paper surface was A red spot appeared on the surface.

Example 6 Production of special paper having self-other discrimination ability
Example 2 350 parts of 20 parts by weight of NBKP and 80 parts by weight of LBKP
C. 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 1.0 parts by weight manufactured by Chemical Industry Co., Ltd.)
An appropriate amount of a sulfuric acid band was added to prepare a slurry. Using this slurry in a Fourdrinier paper machine according to a conventional method, the basis weight is 100 g / m.
² of the paper 0.2 wt% aqueous solution of polyvinyl alcohol in a size press apparatus which is installed in the middle of the drying zone in the paper making, coating the solution was functional particles is 0.04 wt% dispersion of Example 2 Then, the paper was dried according to a conventional method to produce a special paper having self-other discrimination ability. The presence of the functional particles could not be visually recognized in the obtained special paper having the self-other discrimination ability even when observed under fluorescent light illumination, but when ethanol was dropped, purple spots appeared on the paper surface. When ethyl acetate, benzene, toluene, etc. were dropped, blue spots appeared.

Example 7 Production of special paper having self-other discrimination ability
Example 3 350 ml of 20 parts by weight of NBKP and 80 parts by weight of LBKP
C. 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 1.0 parts by weight manufactured by Chemical Industry Co., Ltd.)
An appropriate amount of a sulfuric acid band was added to prepare a slurry. Using this slurry in a Fourdrinier paper machine according to a conventional method, the basis weight is 100 g / m.
² base paper was made. Next, kaolin (trade name “UW
-90 ", 75 parts by weight manufactured by Engelhard Co., Ltd., 25 parts by weight of calcium carbonate (trade name" TP-222HS ", manufactured by Okutama Industry Co., Ltd.), starch as a binder (trade name" MC-3000 ", Shikishima) Starch Co., Ltd. 6
Parts by weight, SBR latex (trade name "Nipol LX40
7C "(manufactured by Nippon Zeon Co., Ltd.), an aqueous paint (concentration: 35% by weight) containing 12 parts by weight as a main component was prepared according to a conventional method, and the functional particles of Example 3 were added to the paint solids at 0 .
06% by weight was added. Apply this paint to both sides of the base paper
Each g / m ^{2 was} coated using an air knife coater, dried, and then subjected to a super calender treatment to produce special paper having self-other discrimination ability. Although the presence of the functional particles was not visible in the obtained special paper having self-other discrimination ability even when observed under fluorescent light illumination, red spots appeared on the paper surface when acetone was dropped. Further, when irradiated with ultraviolet light (black light) in a dark room, a red fluorescent color could be visually recognized.

[0071]

The functional particles of the present invention and the special paper having the ability to discriminate between self and others are constituted as described above, and have remarkable effects as described below. 1) Since the functional particles of the present invention are white and can maintain the particle shape without dissolving even at a high temperature such as in a drying zone of a paper machine, they have self-other discrimination ability including the functional particles. The special paper does not show the presence of particles, and when it comes into contact with an organic solvent, the coloring dye carried in the functional particles elutes to exhibit a unique effect of producing colored spots. .

2) Many of the powdery substances used in the production of the functional particles of the present invention have a hydroxyl group at the terminal, and when the functional particles produced using this as a nucleus are incorporated into the paper, A hydrogen bond is generated between the cellulose fiber as the main component and the functional particles are fixed in the paper. This means
This leads to the advantage that the functional particles do not fall off in the subsequent printing process.

3) The use of a dye that emits a fluorescent color upon irradiation with ultraviolet rays as a water-insoluble and organic solvent-soluble dye has the unique effect that traces of the dye eluted with the organic solvent can be detected in a dark room. Can be.

4) By using two or more combinations of different soluble organic solvents as coloring dyes, spots of a specific hue appear in one kind of organic solvent, and other kinds of hue appear in other organic solvents. A special paper having a unique effect of appearing can be manufactured.

5) When a fluorescent pigment is used as an auxiliary material,
Since the fluorescent color of the fluorescent pigment is much richer in hue than the fluorescent dye and has a higher intensity of fluorescent coloring, functional particles that emit fluorescent light in various hues can be obtained.

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

7) As a powdery substance, when starches that are colored in an aqueous solution containing iodine or fluorescent coloring particles using polyvinyl alcohol are used for special paper having the ability to discriminate between themselves and starch, the starch in the paper There is a feature that it is possible to easily detect types and polyvinyl alcohol, and even if this feature is used, the source of the paper can be easily specified.

8) A forgery-preventive printed matter can be obtained by performing a predetermined printing on the special paper having the self-other discrimination ability of the present invention. For example, passports, travelers checks,
Checks, bills, identification cards, etc. are often written with a ballpoint pen using oil-soluble ink, but the special paper of the present invention that has the ability to identify itself and others is used for such types of anti-counterfeit printed matter. It can be used suitably. That is,
When tampering is performed using an organic solvent, the coloring dye is eluted from the functional particles contained in the paper, and it looks like a spot, so that traces of tampering can be easily detected.

9) Since there are many types of dyes which are insoluble in water and soluble in organic solvents, for example, the types and amounts of the dyes are changed for each lot and added to paper. The specialty paper having the ability to discriminate between the functional particles of the present invention and the self and others can also be suitably used for applications in which it is possible to judge whether or not this is the case.

Claims (5)

[Claims] 1. A hot-water-insoluble, water-insoluble, white shell layer having a property of penetrating an organic solvent is formed on the surface of a core particle carrying a coloring dye which is insoluble in an organic solvent. Functional particles. 2. The hot water-insoluble functional particles according to claim 1, wherein the water-insoluble and organic solvent-soluble coloring dye emits a fluorescent color when irradiated with ultraviolet rays. 3. The combination of water-insoluble and organic solvent-soluble coloring dyes in which a soluble organic solvent is different from the color dye.
The hot water-insoluble functional particles according to claim 1, wherein the functional particles are at least one kind. 4. The functional particles having a particle size of 50 to 800.
4. The method according to claim 1, wherein the diameter is μm.
The hot water-insoluble functional particles according to the above item. 5. A special paper having self-other discrimination ability, comprising the hot water-insoluble functional particles according to claim 1. Description: