JPH05127572A - Information recording paper - Google Patents

Abstract

PURPOSE:To provide an information recording paper which has excellent preservability after forming an image and can be utilized as confidential documents. CONSTITUTION:The image 3 consisting of decolorizing toner is formed on a paper 2 having the same color as the decolorizing toner whose color is eliminated by light irradiation (a). The decolorizing toner contains decolorizing dyestuff, binding resin and pigment having a color different from the color of the surface of the paper 2. In such a state, the image can not be read. By irradiating the information recording paper 1 with light having wavelength by which the decolorizing dyestuff decolorizes, the decolorizing dyestuff decolorizes and becomes transparent, and the image 3 gets the color of the pigment from chromatic color because the decolorizing toner contains the pigment (b). As a result, the image 3 formed on the paper 2 can be read.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information recording paper, and more particularly to an information recording paper that can be used as a confidential document.

[0002]

2. Description of the Related Art Recent improvements in the performance of copying machines and their widespread use have made it possible for anyone to easily obtain a large number of copies faithful to the original. Under such circumstances, confidential documents that contain important information such as documents and various certificates that should not be copied are copied, or a copy in which some of the document contents have been tampered with is the original copy. There is a risk that the image information will be determined and transmitted.

As a means for preventing this, for example, the following method has been considered.

(1) The transfer paper on which an image is formed is colored with a dye or a pigment so that the irradiation light beam is absorbed equally in the non-image area and the image area to prevent re-copying by eliminating image exposure on the photoreceptor. Method (Japanese Patent Laid-Open No. 54-52538).

(2) A copy prevention method in which a copy-forgery-inhibited pattern is copied and made difficult to read by forming images in different colors on a transfer paper having a camouflage pattern (Japanese Patent Laid-Open No. 59-770).
47 publication).

(3) A method in which a fluorescent substance is present on the surface of a transfer paper on which an image has been formed, and excitation light is irradiated to detect the presence or absence of the emitted light to stop the copying operation (JP-A-58-18496).
No. 7).

However, in the method (1), since the transfer paper itself is colored by using at least one of a dye and a pigment during or after the papermaking process, the manufacturing work becomes complicated and the documents to be prepared become expensive. Become. In the method (2), a camouflage pattern having the same reflectance in the non-image area and the image area is created by a printing method or another method, which takes time and is costly. In the method (3), since a fluorescent substance is used, there is a problem in terms of safety, and in order to stop the copying operation, a detecting means and a control mechanism for stopping the copying operation are required, which is a special copying machine. Only applicable.

[0008] In any of the methods, it is difficult to completely prevent re-copying and to create a document that is sufficiently visible, and by making re-copying impossible, it is possible to prevent falsification of the document. However, if the document itself can be read, confidential information will be leaked even though it was created as copy protection paper.

As a method for solving these problems, JP-A-63-262674 and JP-A-63-21 are available.
Japanese Patent No. 0879 discloses a method of forming a white toner image on a white diazo photosensitive paper and forming an objective image by coloring the diazo photosensitive paper to make it blue when the image is read.

[0010]

However, in the above method, since diazo photosensitive paper is used, the storability after forming the target image is poor.

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems, and an object thereof is to provide an information recording paper which has good storability after forming an image and can be used as a confidential document.

[0012]

The information recording paper of the present invention comprises:
An information recording paper in which an image made of a decolorizable toner is formed on a paper of the same color as the color of the decolorizable toner capable of being decolorized by light irradiation, wherein the decolorizable toner is a decolorizable dye, It is characterized in that it contains a binder resin and a colorant having a color different from the color of the surface of the paper, whereby the above object can be achieved.

Further, the information recording paper of the present invention has an image composed of a color-erasable toner and a color which is the same as that of the color-erasable toner on a paper which is not the same color as the color of the color-erasable toner which can be color-erased by light irradiation. An information recording paper on which an image composed of a non-decolorizable toner is formed, wherein the decolorizable toner contains at least a decolorizable dye and a binder resin, which results in the above problems. Can be achieved.

[0014]

In the information recording paper of the present invention, an image made of decolorizable toner of the same color as that of the paper is formed on the paper before irradiation with light, so the image cannot be read in this condition. .. When this information recording paper is irradiated with light having a wavelength such that the erasable dye is erased, the erasable dye becomes bleached and becomes transparent, and the erasable toner has a color different from the surface color of the paper. Since it contains a colorant, the image is colored to the color of the colorant. Therefore, since an image of a color different from the color of the surface of the paper is formed on the colored paper, the image can be read.

Further, the other information recording paper of the present invention, when the light having a specific wavelength is radiated on the paper which is not the same color as the color of the erasable toner, it is absorbed and erased, and becomes transparent. An image made of a decolorizable toner containing a dye and an image made of a non-decolorizable toner having the same color as the color of the decolorizable toner are formed. That is, when two types of images are formed on the paper in the same color and one image is mixed in the other image, it is difficult to read only one image.

In order to make it easy to read only one of the images, the information recording paper is irradiated with light having a wavelength such that the decolorizable dye is decolorized, and the decolorizable dye is erased and becomes transparent. Therefore, only the image made of the decolorizable toner is changed from colored to transparent, and the image of the non-decolorizable toner having the same color as the color of the decolorizable toner formed on the paper can be read. When the color-erasable toner contains a colorant having a color different from that of the color-erasable dye, the color of the image formed by the color-erasable toner is the same as that of the color-erasable toner. Since the color is different from the color toner image, this image can be read.

[0017]

EXAMPLES Next, the present invention will be described in detail based on examples.

First, the information recording paper of the first invention of the present application will be described.

The information recording paper of the present invention has an image formed of decolorizable toner formed on the paper.

The paper used in the present invention is usually used as a recording paper, and examples thereof include those having excellent storability, and the surface color of this paper is the same as that of the decolorizable toner. It is necessary and it is preferable to select the color tone of the paper and the color tone of the decolorizable toner.

The decolorizable toner used in the present invention contains at least a decolorizable dye, a binder resin and a colorant.

The above-described decolorizable dye is colored in the state where it is not irradiated with light having a specific wavelength, but it is absorbed when it is irradiated with light in the presence of a salt of a compound serving as a counter ion. It disappears and becomes transparent. As the decolorizable dye,
Blue decolorizable dyes are preferable, and cyanine dyes are particularly preferable.

The decolorizable dye is preferably a cyanine dye, and the following compounds can be exemplified.

[0024]

[Chemical 1]

[0025]

[Chemical 2]

[0026]

[Chemical 3]

[0027]

[Chemical 4]

[0028]

[Chemical 5]

(In the formula, X represents a halogen atom).

When a cyanine dye is used as the above decolorizable dye, it is necessary to allow the salt of the organic boron compound to be present in order to impart the decolorizing function. It typically has an absorption maximum in the range of 780 to 880 nm, and particularly absorbs light in the vicinity of 820 nm, and is blue when it is not exposed to light in the near infrared wavelength, but is irradiated with light in the near infrared wavelength. When absorbed, it absorbs and disappears,
It becomes transparent.

Further, in this case, in each of the above formulas, X has a structure in which the organic boron compound residue is substituted.

Examples of the organic boron compound include:
Butyl triphenyl borate _{(Ph 3 B-nC 4 H} 9) . Examples of the salts thereof, for example, ammonium salts. That is, as a salt of an organic boron compound, an ammonium salt of butyltriphenylborate (eg, tetrabutylammoniumbutyltriphenylborate)
Is used, instead of X in each of the above formulas, Ph ₃
The structure is such that B ⁻ −nC ₄ H ₉ exists as a counter ion.

In this case, the mixture of the cyanine dye represented by Formula 1 and the salt of the organic boron compound has an absorption maximum for light having a wavelength of 820 nm, and the cyanine dye represented by Formula 2 and the organoboron compound are mixed. 828 with a mixture of
The mixture of the cyanine dye and the salt of the organic boron compound represented by Formula 3 has an absorption maximum for light having a wavelength of 8 nm, and the mixture has the absorption maximum for light having a wavelength of 819 nm and is represented by Formula 4. The mixture of the cyanine dye and the salt of the organic boron compound has an absorption maximum for light having a wavelength of 874 nm, and the mixture of the cyanine dye and the salt of the organic boron compound represented by Formula 5 has a wavelength of 785 nm. It has an absorption maximum for the light it has.

When a cyanine dye is used as the erasable dye, the ratio of the cyanine dye and the salt of the organic boron compound can be changed, thereby adjusting the erasing speed of the erasable toner. You can When the content of the salt of the organic boron compound is large, the color erasing speed of the resulting color erasable toner becomes high. The content of the salt of the organic boron compound is preferably 0.5 to 50% by weight with respect to the decolorizable toner. When the content of the organic boron compound is less than 0.5% by weight, the color erasing speed of the resulting decolorizable toner becomes slow, while the content of the salt of the organic boron compound is 50.
When the content is more than 5% by weight, the resulting decolorizable toner tends to have low charge stability.

The content of the decolorizable dye in the decolorizable toner is preferably 0.5 to 50% by weight based on the decolorizable toner. When the content of the above-described decolorizable dye is less than 0.5% by weight, the resulting decolorable toner tends to have a poor hiding property. On the other hand, the content of the above decolorizable dye is 50% by weight.
If it exceeds, the resulting decolorizable toner tends to have low charge stability and environmental stability.

As the binder resin, a resin material conventionally used as a binder resin for electrophotographic toner can be used. For example, polystyrene, polystyrene-butadiene copolymer, styrene-based copolymers such as styrene-acrylic copolymer, polyethylene, polyethylene-vinyl acetate copolymer, ethylene-based copolymers such as polyethylene-vinyl alcohol copolymer, Examples thereof include phenolic resins, epoxy resins, allyl phthalate resins, polyamide resins, polyester resins, maleic acid resins. These compounds may be used alone or in combination of two or more kinds.

The colorant is not the same color as the color of the surface of the paper, and in the case of a white colorant, for example, zinc oxide, titanium oxide and the like can be mentioned.

If necessary, the decolorizable toner contains additives such as a charge control agent and a release agent.

As the above-mentioned charge control agent, one which does not adversely affect the color tone of the toner and which itself is colorless or blue is used. For example, Bontron E-8
4, Bontron E-85 (manufactured by Orient Chemical Co.).

Examples of the releasing agent include silicone oil, low molecular weight olefin resins, various waxes and the like.

The decolorizable toner can be obtained by the so-called melt-kneading method, spray-drying method or polymerization method. In the melt-kneading method, the above components are melt-kneaded,
After cooling, the decolorizable toner is obtained by pulverizing and classifying the powder. The spray drying method can be obtained by dispersing another toner composition in a binder resin solution and then spray granulating the composition. In addition, the polymerization method is obtained by polymerizing a polymerizable monomer that is a material of a binder resin, a decolorizable dye, and other toner compositions.

The polymerizable monomer used when producing the decolorizable toner by the above-mentioned polymerization method is a polymerizable monomer capable of synthesizing the above-mentioned thermoplastic resin, for example, styrene, chlorostyrene, vinylstyrene and the like. Styrenes: ethylene, propylene, butylene, isobutylene and other monoolefins: vinyl acetate, propylene vinyl,
Vinyl esters such as vinyl benzoate and vinyl butyrate: methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as: vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether such as vinyl butyl ether: vinyl methyl ketone,
Vinyl ketones such as vinyl hexyl ketone and vinyl isopropenyl ketone: ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-
Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,4
-Polyhydric alcohols such as bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropyleneized bisphenol A: ethylenediamine, tetramethylenediamine, pentamethylenediamine, piperazine, hexamethylenediamine Polyamine such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, etc. Acids or their anhydrides or esters with lower alcohols:
Examples thereof include aliphatic, alicyclic and aromatic diisocyanates. In the case of the above-mentioned polyhydric alcohol, polyhydric amine, polyhydric carboxylic acid, and diisocyanate, the polymer which has a hydroxyl group, an amino group, a carboxyl group, and an isocyanate group substantially at both ends can be illustrated. These compounds may be used alone or in combination of two or more.

The information recording paper of the present invention can be obtained by using an electrophotographic copying machine to form an image corresponding to the original image on the paper using decolorizable toner. Figure 1
As shown in (a), the obtained information recording paper 1 is one in which the image portion 3 of the decolorizable toner is formed on the paper 2 of the same color as the decolorizable toner. Contains an erasable dye and a pigment having a color different from the color of the surface of the paper.
Since the color of the paper 2 and the color of the image portion 3 are the same, the image portion 3 formed on the information recording paper 1 cannot be read.

When the image on the information recording paper is read, the information recording paper is irradiated with light having a wavelength such that the decolorizable dye absorbs and erases the color and becomes transparent. When the decolorizable dye is blue, it is irradiated with light having a near infrared wavelength. Then, as shown in FIG. 1B, the decolorizable dye in the decolorizable toner of the image portion 3 is decolored and becomes transparent, and the decolorizable toner is a colorant which is not the same color as the surface color of the paper 2. Since it contains and, this image part changes from colored to the color of the coloring agent,
Since the non-image portion remains colored, the image on the information recording paper can be read.

Further, since the information recording paper of the present invention uses a paper having good storability, the information recording paper after forming an image can be satisfactorily stored.

Next, the second invention of the present application will be described.

On the information recording paper of the present invention, an image made of a decolorizable toner and an image made of a non-decolorable toner which is not the same color as the color of the decolorizable toner are formed on the paper.

The paper used in the present invention may be the same paper having excellent storage stability as described above, and it is necessary that the color of the surface of this paper is not the same as that of the decolorizable toner.

The decolorizable toner used in the present invention contains at least a decolorizable dye and a binder resin.

The above-mentioned decolorizable dye is colored in the state where it is not irradiated with light having a specific wavelength, but it is absorbed when it is irradiated with light in the presence of a salt of a compound serving as a counter ion. It disappears and becomes transparent. As the decolorizable dye,
The same as those mentioned above can be mentioned. When a cyanine dye is used, in order to impart a decolorizing function, it is necessary to allow a salt of an organic boron compound to be present. Compounds similar to are mentioned.

When a cyanine dye is used as the erasable dye, the ratio of the cyanine dye and the salt of the organic boron compound can be changed, and thereby the erasing speed of the erasable toner can be adjusted. You can When the content of the salt of the organic boron compound is large, the color erasing speed of the resulting color erasable toner becomes high. The content of the salt of the organic boron compound is preferably 0.5 to 50% by weight with respect to the decolorizable toner. When the content of the organic boron compound is less than 0.5% by weight, the color erasing speed of the resulting decolorizable toner becomes slow, while the content of the salt of the organic boron compound is 50.
When the content is more than 5% by weight, the decolorizable toner obtained tends to have low charge stability.

The content of the decolorizable dye in the decolorizable toner is preferably 0.5 to 50% by weight based on the decolorizable toner. When the content of the above-described decolorizable dye is less than 0.5% by weight, the resulting decolorable toner tends to have a poor hiding property. On the other hand, the content of the above decolorizable dye is 50% by weight.
If it exceeds, the resulting decolorizable toner tends to have low charge stability and environmental stability.

As the binder resin, the same resins as mentioned above can be mentioned.

If necessary, the decolorizable toner contains additives such as colorants, charge control agents and release agents.

It is necessary that the colorant is not the same color as the color of the decolorizable dye, and the white colorant includes, for example, the same colorants as described above.

The decolorizable toner can be obtained by a so-called melt-kneading method, spray-drying method, polymerization method or the like. In the melt-kneading method, the above components are melt-kneaded,
After cooling, the decolorizable toner is obtained by pulverizing and classifying the powder. The spray drying method can be obtained by dispersing another toner composition in a binder resin solution and then spray granulating the composition. In addition, the polymerization method is obtained by polymerizing a polymerizable monomer that is a material of a binder resin, a decolorizable dye, and other toner compositions.

Examples of the above-mentioned polymerizable monomer include the same monomers as described above.

The non-decolorizable toner that is not the same color as the color of the decolorizable toner contains a binder resin and a colorant. A conventionally known resin is used as the binder resin, and the pigment needs to be a pigment having the same color as the color of the decolorizable toner.

The information recording paper of the present invention uses an electrophotographic copying machine to form an image corresponding to the original image on the paper with a decolorizable toner and a non-decolorizable color that is not the same color as the color of the decolorizable toner. It is obtained by forming an image corresponding to another original image with toner. As shown in FIG. 2A, the obtained information recording paper 4 has an image portion 6 made of colored decoloring toner on the paper 5 of the same color as the decoloring toner, and the color of the colored decoloring toner. Image part 7 using non-decolorizable toner that is not the same color as
The color of the paper 5 is the same as the color of the image portion 6 made of the decolorizable toner and the color of the image portion 7 made of the non-decolorable toner that is not the same color as the color of the decolorizable toner. The color of the image portion 6 that does not exist and is made of the decolorizable toner is the same as the color of the image portion 7 that is made of the non-decolorable toner that is not the same color as the color of the decolorizable toner. Therefore, it is difficult to read each of the image portions 6 and 7.

When reading an image on this information recording paper, the information recording paper 4 is absorbed by the erasable dye and is erased,
Irradiate with light having a wavelength that makes it transparent. When the decolorizable dye is blue, it is irradiated with light having a near infrared wavelength. Then, as shown in FIG. 2B, since the decolorizable dye contained in the decolorizable toner forming the image portion 6 is decolored and becomes transparent, the image portion 6 changes from colored to transparent,
Since the image portion 7 remains colored, the image portion 7 on the information recording paper 4 can be read. Therefore, a confidential document can be used as a confidential document by forming an image with normal toner and a camouflage document with an erasable toner.

Further, the decolorizable toner may contain a colorant having a color different from the color of the decolorizable dye, and in this case, a wavelength which makes the decolorable dye absorb and decolorize and become transparent is obtained. When it is irradiated with the light, the color of the image portion formed by the color erasable toner and the color of the image portion formed by the non-color erasable toner that is not the same as the color of the color erasable toner are different, so both images can be read.

Further, since the information recording paper of the present invention uses a paper having good storability, the information recording paper after forming an image can be satisfactorily stored.

[0063]

As is apparent from the above description, according to the present invention, it is possible to easily obtain an information recording paper which has good storability and can be used as a confidential document.

[Brief description of drawings]

FIG. 1A is a top view of an information recording sheet of the present invention. FIG. 1B is a top view of the information recording paper of FIG. 1A after irradiating the information recording paper with light having a wavelength such that the decolorizable dye erases the color.

FIG. 2A is a top view of the information recording paper of the present invention. FIG. 2B is a top view of the information recording paper of FIG. 2A after the information recording paper is irradiated with light having a wavelength such that the decolorizable dye erases the color.

[Explanation of symbols]

 1 information recording paper 2 paper 3 image part 4 information recording paper 5 paper 6 image part 7 non-image part

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masatomi Funato 1-2-2 Tatamazo, Chuo-ku, Osaka Mita Industrial Co., Ltd. (72) Inventor Masai Inoue 1-228 Tamatsukuri, Chuo-ku, Osaka Mita Kogyo Co., Ltd. (72) Inventor Kazuhiko Yamamura 1-22 Tamatsukuri, Chuo-ku, Osaka Mita Kogyo Co., Ltd.

Claims (2)

[Claims] 1. An information recording paper, wherein an image composed of a decolorizable toner is formed on a paper of the same color as the color of the decolorizable toner capable of being decolorized by irradiation with light. Information recording paper containing a decolorizable dye, a binder resin, and a colorant having a color different from the color of the surface of the paper. 2. An image composed of a color-erasable toner and an image composed of a non-color-erasable toner having the same color as the color of the color-erasable toner on a paper which is not the same color as the color of the color-erasable toner which can be color-erased by light irradiation. An information recording paper on which is formed, wherein the decolorizable toner contains at least a decolorizable dye and a binder resin.