JPH0939452A - Multicolor thermal recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multicolor thermal recording medium capable of forming a multicolored print image easily and clearly in which there is no hem due to coloring difference and temperature difference around the printing part by change in printing energy, in a card in which the multicolored print image is to be provided. SOLUTION: On one face of a base material sheet 1, a coloring layer 2, a thermal coloring layer 3, a thermal print thin film layer 4 which works with an energy lower than the thermal coloring layer 3, and a protective layer 5 are layered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multicolor thermosensitive recording medium, and more specifically, to easily perform multicolor printing on a magnetic card or the like by changing the coloring energy applied in multiple steps. , A thermosensitive coloring layer on the base material sheet, an image is printed in a portion where the thin film of the thermosensitive printing thin film layer in which the coloring layer is partially heated and destroyed is removed, or the colored image is partially erased Thus, the present invention relates to a multicolor heat-sensitive recording medium that enables clear printing of multicolor.

[0002]

2. Description of the Related Art Conventionally, as a method for printing multicolor printing on a thermosensitive recording medium such as a magnetic card, a combination of a leuco dye layer and a developer and a decoloring layer having different coloring temperatures or a diazo dye layer and a basic layer is used. It is known that a material layer and a thermosensitive coloring layer composed of the material layer are laminated.

[0003]

However, in a combination of a leuco dye layer and a developer and a decoloring layer having different coloring temperatures, the developer and the decoloring agent act on the leuco dye layer and the diazo dye layer. As a result, the base fogging phenomenon and the phenomenon that the storage stability of color development deteriorates occur, and the desired color development in high energy printing is framed by the hue at the printing temperature that corresponds to low energy around the printing area. There is a problem that the desired two colors cannot be completely separated. The thermosensitive coloring layer, which is formed by laminating a diazo dye layer and a basic material layer, requires a fixing step of irradiating the image with ultraviolet rays after printing, which causes a problem that the apparatus becomes complicated. In addition, when a multicolor thermosensitive recording medium is provided on the magnetic layer, there is a problem that the layer thickness becomes thick and it becomes difficult to read the magnetism. INDUSTRIAL APPLICABILITY The present invention makes it possible to easily and clearly obtain a multi-colored printed image without causing edging around the printed part due to a change in printing energy, and to print on a magnetic recording layer. The present invention is intended to provide a multicolor thermosensitive recording medium such as a card that can be used.

[0004]

A card provided with a multicolored printed image of the present invention has a colored layer on one surface of a base sheet,
It is a multicolor thermosensitive recording medium in which a thermosensitive coloring layer, a thermosensitive printing thin film layer and a protective layer are laminated in this order. The second invention is laminated on one surface of the substrate sheet with a coloring layer, a decoloring layer that acts at higher energy than the thermosensitive coloring layer, a thermosensitive coloring layer, and a thermal printing thin film layer and a protective layer. It is a multicolor thermal recording medium. A third invention is the multicolor thermosensitive recording medium according to the first and second inventions, wherein a magnetic recording layer is provided on at least one surface of the substrate sheet of the multicolor printing recording medium. A fourth invention is a card provided with the multicolor printing of the first, second and third inventions, wherein a pattern layer and a coloring layer or a pattern layer is formed on one surface of the base sheet. It is a color thermosensitive recording medium.

As shown in FIG. 1, the multicolor thermosensitive recording medium of the present invention is provided with a coloring layer 2 and a thermosensitive coloring layer 3 on one surface of a substrate sheet 1, and further has a thermosensitive printing thin film layer 4 and a protective layer. 5 and 5 are sequentially laminated.

When an image is printed on the multicolor recording medium, as shown in FIG. 2, in the low energy printing portion 10, the thermal printing thin film layer 4 becomes a destructive printing thin film layer 41 and is colored in order to be transparent. An image is formed only by the "printed coloring layer 23", which is the layer 2 bordered by the destructive printing thin film layer 41.
With this printing energy, the thermosensitive coloring layer 3 is held in a transparent state without coloring. In the high-energy printing unit 20, the heat-sensitive printing thin film layer 4 becomes the destructive printing thin-film layer 41 and becomes transparent, and at the same time, the heat-sensitive coloring layer 3 develops color to form the printing coloring layer 33. The image is formed by "color mixing with the layer 33".
That is, when the low temperature energy 10 is applied to the base material sheet 1, the image formed by the printing coloring layer 23 and the high temperature printing portion 20 are printed.
In the case of (1), an image is clearly printed by color mixing with the print coloring layer 33 and the print coloring layer 23, which are the thermosensitive coloring layers.

In the second invention, as shown in FIG. 3, a coloring layer 2, a decoloring layer 6 which acts with higher energy than the thermosensitive coloring layer 3, a thermosensitive coloring layer 3, on one surface of the substrate sheet 1, The thermal printing thin film layer 4 and the protective layer 5 are laminated in this order. The magnetic recording layer 26 of the third invention and / or the pattern layer 21 of the fourth invention is formed on the surface of the base sheet 1. The pattern layer 21 can be provided together with the coloring layer or can be provided with only the pattern layer. Further, the magnetic recording layer can also serve as two kinds of functions as a coloring layer.

When an image is printed on the multicolor thermosensitive recording medium, as shown in FIG. 4, in the low energy printing section 10, the thermal printing thin film layer 4 becomes a transparent destructive printing thin film layer 41, and at the same time, printing color is developed. The layer 33 is formed, and an image is printed by the color mixture of the print coloring layer 23 and the print coloring layer 33. At this low printing energy, the erasing layer 6 is not activated and is maintained as a transparent layer. Further, in the high energy printing portion 20, the thermal printing thin film layer 4 is the destructive printing thin film layer 41.
At the same time, the printed coloring layer 33 becomes transparent and becomes the decolored coloring layer 34 by decoloring by the activated active decoloring layer 61,
An image is formed on the print portion by the print coloring layer 23 that is bordered by the destructive print thin film layer 41. That is, the low temperature energy 10 forms an image on the base sheet 1 by the color mixture of the print coloring layer 23 and the print coloring layer 33, and the high temperature printing section 20 clearly prints the image by the print coloring layer 23. Is.

As shown in FIG. 5, the base sheet 1 is provided with a thermosensitive coloring layer 3, a fine pattern as a pattern layer 21, and a thermosensitive printing thin film layer 4 and a protective layer 5 in this order. A thermal recording medium can also be constructed. Then, as shown in FIG. 6, in the low energy printing portion 10, the print pattern layer 24 framed by the destructive print thin film layer 41 of the thermal print thin film layer 4 is formed.
The color pattern can be directly expressed on the base material sheet 1, and in the high energy printing section 20, the print pattern layer 24 can be expressed on the print coloring layer 33.

[0010]

As described above, the present invention provides a colored layer, a thermosensitive coloring layer that develops color in high-energy printing, and a heat-sensitive printing thin film layer of low energy destruction provided in a layer near the heating printing portion, and a protective layer. It consists of each layer. Therefore, in low-energy printing, the image formed by the "printed coloring layer" bordered by the destructive printing thin-film layer can be clearly formed, and in high-energy printing, the image formed by "mixing of the printed coloring layer and the printing coloring layer" can be clearly formed. is there. Further, a second invention is that in a low energy printing portion, by using a colored layer, a low energy coloring layer and a decolorizing layer activated by high energy in combination,
Destructive printing The image by "color mixing of the printing coloring layer and the printing coloring layer" bordered by the thin film layer, and in the high energy printing section, the printing layer used together has the effect of making the printing coloring layer transparent, An image formed by the "colored layer" can be clearly formed without edging due to other colors. Since the thermosensitive coloring layer is provided as a single layer, there is no difference in hue due to temperature difference,
It has an effect of forming an image in which hues are clearly separated. And, in order to use together a method for producing different printing effects of a thermosensitive coloring layer, a thermosensitive printing thin film layer, a coloring layer, and a decoloring layer,
There is no color development in different hues, and mutual color development does not affect the printing process, and a clear image can be formed.
In addition, the layer thickness for expressing multiple colors can be made thin, and even when laminated on a magnetic card or the like provided with a magnetic recording layer, magnetic reading can be accurately and easily performed. Then, it is possible to express an image rich in changes not only in the colored layer but also in the pattern layer in the printing portion.

[0011]

Embodiments of the present invention will now be described in more detail with reference to the drawings. (Example 1) As shown in FIG. 7, a primer layer 16 (acrylic varnish) was applied by a gravure printing method on one surface of a biaxially stretched polyester sheet having a thickness of 188 μm as a base material sheet 0.3 g. / M ² (solid content, the coating amount in the present specification is described as solid content), red colored layer 2
2 g / m ² and a primer layer 17 similar to the above for a heat-sensitive printing thin film layer with an acrylic varnish. Next, the primer layer 17 was provided with 5 g / m ^{2 of} a high-energy coloring thermosensitive coloring layer 3 composed of “thermosensitive coloring layer coating liquid 1” having a black color composition shown below, and a primer layer 18 similar to the above.
Was provided. Then, the thermal printing thin film layer 4 was formed by providing tin with a thickness of 500 Å by a vacuum deposition method. Further, a varnish composed of a two-component reaction type linear polyester isocyanate, an antistatic agent and a lubricant is used as a protective layer 5 as a protective layer 5 through a primer layer 19 made of a vinyl chloride / vinyl acetate copolymer varnish containing a carbonyl group. An m ² gravure coating method was used to form a card provided with the multicolor thermosensitive recording medium of Example 1. "Thermal coloring layer coating solution 1" -Dispersion liquid A 3- (N-ethyl-N-amylamino) -6-methyl-7-anilinofluorane 10 parts Polyvinyl alcohol (10% aqueous solution) 10 parts Water 30 parts-Dispersion Liquid B Bisphenol A 10 parts Polyvinyl alcohol (10% aqueous solution) 10 parts Water 30 parts Dispersion A / dispersion B = 1/5.

When an image is provided on the multicolor recording medium,
As shown in FIG. 8, in the low-energy printing unit 10, a printing color layer bordered by the destructive printing thin film layer 41 due to destruction of the thermal printing thin film layer 4 by applying a printing energy of 0.8 mJ / dot to the thermal head. 23 was printed. Next, in the high-energy printing unit 20, a printing energy of 1.0 mJ / dot is applied to the thermal head to break the thermal printing thin film layer 4 to form a transparent broken printing thin film layer 41, and the coloring layer 2 Was used as the printing coloring layer 23, and an image mixed with the printing coloring layer 33 was printed. That is,
Two images of a light red "printing coloring layer 23" and a "color mixture of the printing coloring layer 23 and the printing coloring layer 33" by the coloring layer 2 formed in the transparent portion of the destructive printing thin film layer 41 on the base material sheet 1 Is to be printed clearly.

(Example 2) As shown in FIG. 9, a magnetic recording layer 26 also provided with a function of a coloring layer on one surface of YUPO FPG 130 manufactured by Oji Yuka Synthetic Paper Co. A coating amount of 30 g / m ² and a primer layer 16 of polyester varnish for the heat-sensitive printing thin film layer 4 were provided on the entire surface by gravure coating. Next, on the side of the colored layer, 3 g / m of the "decolorizing layer coating liquid" having the following composition was applied through the primer layer 16.
^Two coatings were applied to form an erasable layer 6. Then, the same primer layer 17 as described above and 4 g / m ² of the thermosensitive coloring layer 3 of the "thermosensitive coloring layer coating solution 2" which develops a red-orange color having the following composition of the low energy coloring type, and the above for the thermal printing thin film layer are used. A primer layer 18 similar to the above was provided by gravure coating. Then, the thermal printing thin film layer 4 was formed by providing tin with a thickness of 500 Å by a vacuum deposition method. Further, a protective layer 5 similar to that of Example 1 was provided by gravure coating via a primer layer 19 made of a vinyl chloride / vinyl acetate copolymer varnish containing a carbonyl group, and the multicolor thermosensitive recording medium of Example 2 was provided. Formed a card. "Decoloring layer coating liquid" 4,4-dithiodimorpholine 10 parts Polyvinyl alcohol 10 parts Water 30 parts "Thermal coloring layer coating liquid 2" -Dispersion A 3-Diethylamino-7-chlorofluorane 10 parts Polyvinyl alcohol ( 10% aqueous solution) 10 parts Water 30 parts Dispersion B Bisphenol A 10 parts Polyvinyl alcohol (10% aqueous solution) 10 parts Water 30 parts Dispersion A / dispersion B = 1/5.

When an image is provided on the multicolor recording medium,
As shown in FIG. 10, in the low energy printing unit 10, when the printing energy of 1.0 mJ / dot is applied to the thermal head to destroy the thermal printing thin film layer 4 and form the destructive printing thin film layer 41 to be a transparent portion. At the same time, an image was printed by the printing coloring layer 33 by coloring the thermosensitive coloring layer 3. At this time, the print coloring layer 33 becomes a color mixture with the print magnetic recording layer 27 bordered by the destructive print thin film layer 41. Next, a high-energy printing portion 20 is provided to break the heat-sensitive printing thin-film layer 4 to form a transparent break-printing thin-film layer 41, and at the same time, the heat-sensitive color-developing layer 3 is colored by the decoloring layer 6. A printed magnetic recording layer 27 formed by only the portion of the destroyed destructive printing thin film layer 41 which is erased by the activated active decoloring layer 61 to become the transparent decolorized coloring layer 34.
Was printed. That is, an image formed by "color mixing of the print coloring layer 33 and the print magnetic recording layer 27" and the destructive print thin film layer 41.
The image of the "printed magnetic recording layer 27" formed on the transparent portion of 2 is clearly formed in two colors. Then, when magnetic recording was performed on this multicolor thermosensitive recording medium with a magnetic head, a recording density of 420 FRPI (flux rev
ersal per inch), the reproduction output is 5.9 in the printing section.
V, 6.3 V in the non-printing portion, and the influence of the printing on the reduction in the output of the reproduction output was 6%, which was within the range of no practical problem.

The materials and forming methods of the base sheet, the coloring layer, the heat-sensitive printing thin film layer, the decolorizing layer, the heat-sensitive coloring layer and the protective layer, which are the specific constituents, will be described below.

The base sheet of the present invention is formed by stretching a thermoplastic resin such as polyamide, cellulose triacetate, cellulose diacetate, polystyrene, polypropylene, polyester, polyimide, polycarbonate, saponified ethylene / vinyl acetate copolymer, or polyvinyl chloride. Alternatively, a non-stretched sheet, a metal such as copper or aluminum, a paper, a resin-impregnated paper, a synthetic paper or the like can be used as a single layer or a laminated sheet. And its thickness depends on the material processing method,
It is 0.03 to 2 mm, though it depends on the rigidity and the physical properties required depending on the application. Then, if necessary, coloring is performed with an inorganic or organic pigment or dye. A preferred material is a stretched polyester sheet of 0.05 to 0.4 mm or a heat-resistant synthetic paper excellent in print coating suitability. Further, a magnetic recording portion for recording information, an IC memory, and an optical memory can be provided in a part of the base sheet. The magnetic recording portion may be directly formed on the base material sheet to further form the multicolor thermosensitive recording medium of the present invention.

The coloring layer has a desired hue by mixing ordinary inorganic or organic pigments as a single substance or in an appropriate mixture, and a fibrin derivative such as ethyl cellulose, a rosin derivative, an acrylic resin, a polyester resin and a wax, a plasticizer, a stabilizer. There are those which use a resin varnish containing additives such as the above as a binder, and those which use an ionizing radiation curable resin composed of an acrylic resin, its oligomer and a monomer. The pattern layer may be formed of a solvent-drying ink or a reaction-curing ink for ordinary lithographic printing plates, intaglio plates including gravure plates, stencil plates, letterpress printing plates, or roll printing, depending on the printing method. You can The colored layer can be formed on the entire surface or a part of the substrate by a usual coating method such as roll coating or air knife coating in addition to the above printing method.

The heat-sensitive printing thin film layer is formed by vacuum deposition, sputtering or plating of a metal such as tellurium, tin, indium, bismuth, lead or zinc or an alloy thereof, or a compound of a metal having a low melting point such as tellurium carbide. And the like. The thickness of the heat-sensitive printing thin film layer may be a thickness that completely shields the colored layer from 100 to 20.
It is 00Å, preferably 500 to 1000Å.

The thermosensitive coloring layer comprises a conventionally known colorless or light-colored leuco dye having a lactone ring, a lactam ring, a spiropyran ring or the like as a coloring main agent, and a coloring aid for reacting with the leuco dye to develop a color when heated. Agent and color former,
Polyvinyl alcohol, methoxy cellulose, methyl cellulose, sodium polyacrylate, sodium alginate,
Roll coating, air knife coating, etc. with a coating solution using an aqueous solution of a natural or synthetic polymer such as starch or casein or an aqueous dispersion of vinyl chloride / vinyl acetate copolymer or styrene / butadiene / acrylic resin latex as a binder. It can be formed by a coating method. The coating amount is 0.5 to 10 g / m ² , preferably ^{2 to 5} g / m ² , depending on the desired color density.
²

The erasing layer for erasing the chromogenic layer composed of the above-mentioned materials is a conventionally used erasing agent such as higher aliphatic alcohol, polyether, polyethylene glycol derivative, acetamide, stearyl amide, A nitrogen-containing organic compound such as phthalonitrile is dissolved or dispersed in the binder used for the above-mentioned color forming agent, and is applied by the same method to form. The coating amount is, depending on the coating amount of the thermosensitive coloring layer, 0.5 to 10 g / m ² , preferably ² to 5 g / m ² .

The protective layer is provided in order to prevent physical damage such as rubbing or chemical contamination such as oil on the various coating layers or the formed images. If necessary, a varnish of a thermoplastic resin mainly composed of an acrylic type, a urethane type, a polyester type, or a vinyl chloride / vinyl acetate copolymer is added with a lubricant such as wax or silicone resin or an antistatic agent. Further, those having a functional group, such as polyurethane, polyester and polyether resins, which are cured by polyisocyanate, heat such as aminoalkyd, resin-modified drying oil, or oxidative curable varnish,
Ionizing radiation curable resin is used. The coating method can be an ordinary method depending on the shape curing method of the base sheet or the resin varnish, and the coating amount is 1 to 10 g.
/ M ² , preferably ² to 5 g / m ² . Magnetic recording layer is γ-Fe ₂ O ₃ , Co deposited γ-Fe ₂ O ₃ , Fe ₃ O ₄ , CrO ₂ , Fe, Fe
-Ro, Fe-Co, Co-Cr, Co-Cr, Co-Ni, Mn-Al, Ba ferrite and other conventionally known magnetic fine particles are dispersed in a suitable ink vehicle to obtain a gravure coat, roll coat, knife coat, etc. It can be formed by a conventionally known method. Alternatively, a metal or alloy such as Fe-Co, Co-Cr, or Co-Ni, or an oxide thereof may be used to form the base sheet by a vacuum deposition method, a sputtering method, a plating method, or the like. The thickness of the magnetic recording layer formed by coating is 1
-100 μm, preferably 5-20 μm. The thickness of the magnetic recording layer formed by a vacuum deposition method, a sputtering method, a plating method or the like is 100 to 10000Å, preferably 5
00 to 1000 °. Vehicles in which γ-Fe ₂ O _{3 and the} like are dispersed are polyvinyl butyral, vinyl chloride / vinyl acetate copolymers, polyurethanes, polyesters, cellulose derivatives, acrylic resins, styrene / maleic acid copolymers, and the like. Then, rubber such as nitrile rubber and urethane elastomer is added as needed. If necessary, additives such as surfactants, waxes and silicone oils, and carbon and other pigments may be added to the above vehicle in which the magnetic fine particles are dispersed.

When forming each of the above layers, it is preferable to provide a primer layer, if necessary, for the purpose of more firmly and stabilizing the adhesion between the layers. The primer layer is selected from varnishes such as polyester / isocyanate, polyether / isocyanate, vinyl chloride / vinyl acetate copolymer acrylic resin, etc., which are used as adhesives, depending on the characteristics of each layer. The coating amount may be the minimum necessary without a coating application part, and 0.1 to ² g / m ² is provided by roll coating or gravure coating.

[0023]

[Effect] Since each invention of the present application is configured as described above, the following effects can be obtained. As described above, the first aspect of the present invention comprises a colored layer, a thermosensitive coloring layer that develops color in high-energy printing, a low-energy destruction thermosensitive printing thin-film layer, and a protective layer. It Therefore, in the low energy printing,
In high-energy printing, an image is clearly formed by "color mixture of a printing coloring layer and a printing coloring layer". Also,
A second aspect of the present invention is a "color mixture of a print coloring layer and a print coloring layer" in a low energy printing portion by using a coloring layer, a low energy coloring layer and a high energy erasing layer in combination.
By using the decolorizing layer together with the image by the above, and by using the decolorizing layer together, the image by the "printing coloring layer" can be clearly formed without edging by other colors. Since the thermosensitive coloring layer is provided as a single layer, different colors do not occur due to the temperature difference, and an image in which hues are clearly separated can be formed. Since different printing methods of the thermosensitive coloring layer, the thermosensitive printing thin film layer, the coloring layer, and the erasing layer are used, a clear image can be formed on the card without affecting mutual coloring in the printing process. . In addition, the layer thickness for expressing multiple colors can be made thin, and magnetic reading becomes easy even when laminated on a magnetic card or the like.

[Brief description of drawings]

FIG. 1 is a schematic view showing a cross section of a layer structure of a multicolor thermosensitive recording medium.

FIG. 2 is a schematic view showing a cross section of an image formed by printing from the multicolor thermosensitive recording medium of FIG.

FIG. 3 is a schematic view showing a cross section of a layer structure using an erasing layer of a multicolor thermosensitive recording medium.

FIG. 4 is a schematic diagram showing a cross section of an image formed by printing from the multicolor thermosensitive recording medium of FIG.

FIG. 5 is a schematic view showing a cross section of another layer structure of the multicolor thermosensitive recording medium.

FIG. 6 is a schematic view showing a cross section of an image formed by printing from the multicolor thermosensitive recording medium of FIG.

FIG. 7 is a schematic view showing a cross section of the constitution of the multicolor thermosensitive recording medium of the example.

FIG. 8 is a schematic view showing a cross section of an image formed by printing from the multicolor thermosensitive recording medium of FIG.

FIG. 9 is a schematic view showing a cross section of the configuration of a multicolor thermosensitive recording medium of another example.

FIG. 10 is a schematic view showing a cross section of an image formed by printing from the multicolor thermosensitive recording medium of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Color layer 21 Design layer 23 Print coloring layer 24 Print pattern layer 26 Magnetic recording layer 27 Print magnetic recording layer 3 Thermosensitive coloring layer 33 Printing coloring layer 34 Decoloring coloring layer 4 Thermal printing thin film layer 41 Destruction printing thin film layer 5 Protective layer 6 Decoloring layer 61 Active decoloring layer 10 Low energy printing part 20 High energy printing part 16, 17, 18, 19 Primer layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location 7416-2H B41M 5/26 S 7416-2H X 7416-2H 102

Claims (4)

[Claims] 1. A card provided with a multi-color printed image, in which a colored layer, a thermosensitive coloring layer, a thermosensitive printing thin film layer, and a protective layer are sequentially laminated on one surface of a substrate sheet. Characteristic multicolor thermal recording medium. 2. The card according to claim 1, wherein a coloring layer, a decoloring layer that acts with higher energy than the thermosensitive coloring layer, a thermosensitive coloring layer, a thermosensitive printing thin film layer, and a protective layer are provided on one surface of the substrate sheet. A multicolor heat-sensitive recording medium, characterized in that it is laminated in order. 3. In the card provided with the multicolor printing,
The multicolor thermosensitive recording medium according to claim 1 or 2, wherein a magnetic recording layer is provided on at least one surface of the substrate sheet. 4. A card provided with the multicolor printing,
The multicolor thermosensitive recording medium according to claim 1, 2 or 3, wherein a pattern layer and a coloring layer or a pattern layer are provided on one surface of the substrate sheet.