JPH0930122A - Multicolor thermal recording medium - Google Patents

Abstract

(57) [Abstract] [Purpose] In a card provided with a multicolored printed image, due to a change in printing energy, there is no edging due to a color difference due to a temperature difference around the printed part, and a multicolored printed image can be easily and Provided is a multicolor thermosensitive recording medium which can be clearly formed. [Structure] A colored layer 2, a heat-sensitive printing thin film layer 4, a heat-sensitive coloring layer 3 which operates with lower energy than the heat-sensitive printing thin film layer 4, and a protective layer 5 are sequentially laminated on one surface of a substrate sheet 1.

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 heat-sensitive coloring layer, a pattern layer and a coloring layer on a base sheet, and an image is printed on a portion of the heat-destructed thin film of a heat-sensitive printing thin film that has been destroyed by heating, or a part of the colored image is printed. The present invention relates to a multicolor heat-sensitive recording medium which enables clear multicolor printing by erasing the color.

[0002]

2. Description of the Related Art Conventionally, as a method of 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 is used. It is known to laminate a basic material layer and a thermosensitive coloring layer.

[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. An object of the present invention is to provide a multicolor thermosensitive recording medium such as a card which can easily and clearly obtain a multicolor printed image without edging around the printing portion due to a change in printing energy in multicolor printing. It is what Further, when the thermosensitive recording medium is provided on the magnetic recording layer of a card having a magnetic recording layer, the problem that the layer thickness becomes thick due to the multicolor and the magnetic reading becomes difficult is solved.

[0004]

A card provided with multicolor printing according to the present invention has a colored layer, a heat-sensitive printing thin film layer, and a heat-sensitive coloring that works at lower energy than the heat-sensitive printing thin film layer on one surface of a substrate sheet. A multicolor thermosensitive recording medium in which a layer and a protective layer are sequentially laminated. The second invention is, on one surface of the base material sheet, a colored layer, a heat-sensitive printing thin film layer, a decoloring layer that operates at higher energy than the heat-sensitive color developing layer, and a heat-sensitive film that operates at lower energy than the heat-sensitive printing thin film layer. It is a multicolor thermosensitive recording medium in which a color forming layer and a protective layer are sequentially laminated. A third aspect of the invention is the same as the first and second aspects of the invention, in which a magnetic recording layer is provided on at least one surface of the substrate sheet of the multicolor thermosensitive recording medium. Further, a fourth invention is, in the card provided with the multicolored prints of the first, second and third inventions, wherein a pattern layer and a coloring layer or a pattern layer is provided on one surface of the base sheet. It is a multicolor thermal recording medium.

As shown in FIG. 1, the multicolor thermosensitive recording medium of the present invention operates on one side of the substrate sheet 1 with a colored layer 2, a thermosensitive printing thin film layer 4, and a lower energy than the thermosensitive printing thin film layer 4. The thermosensitive coloring layer 3 and the protective layer 5 are laminated in this order.

When a printed image is provided on the multicolor thermosensitive recording medium, as shown in FIG. 2, in the low energy printing section 10, the thermosensitive coloring layer 3 forms the printing coloring layer 33, and the thermosensitive printing is made of metal. Since the thin film layer 4 exists as a concealing layer, an image is formed only by the "printing and coloring layer 33". In the high-energy printing section 20, the thermosensitive coloring layer 3 forms the printing coloring layer 33, and at the same time, the thermosensitive printing thin film layer 4 is destroyed by the same image as the printing coloring layer 33 to be a transparent destructive printing thin film layer 41. Thus, a multicolored image is formed by the "color mixture of the print coloring layer 23 and the print coloring layer 33" bordered by the destructive print thin film layer 41. That is, the base sheet 1 is provided with a print coloring layer 33 formed of a thermosensitive coloring layer.
In addition, a multicolor image is clearly printed by the color mixture of the print coloring layer 23 and the print coloring layer 33.

The second invention, as shown in FIG. 3, is a decoloring layer which acts on the one surface of the substrate sheet 1 at a higher energy than the coloring layer 2, the thermosensitive printing thin film layer 4 and the thermosensitive coloring layer 3. 6,
The heat-sensitive printing thin film layer 4 is composed of a heat-sensitive coloring layer 3 which operates at lower energy and a protective layer 5. The magnetic recording layer 26 of the third invention and / or the pattern layer 21 of the fourth invention are formed on the base sheet 1. The pattern layer 21 can be provided together with the coloring layer 2, or can be formed only by the pattern layer. Further, the magnetic recording layer 26 can also have a function as a coloring layer.

When an image is provided on the multicolor recording medium,
As shown in FIG. 4, in the low-energy printing portion 10, the thermosensitive coloring layer 3 forms a printing coloring layer 33, and the thermosensitive printing thin film layer 4 made of metal exists as a concealing layer. ] Image is formed. Further, in the high-energy printing portion 20, the print coloring layer 33 composed of the thermosensitive coloring layer 3 is erased by the active erasing layer 61 in which the erasing layer 6 is activated to become the transparent erasing coloring layer 34. At the same time, the thermal printing thin film layer 4 is destroyed to become a transparent destructive printing thin film layer 41, and the "printing coloring layer 23" bordered by the destructive printing thin film layer 41 is formed. That is, an image is clearly printed on the base sheet 1 by the print coloring layer 33 formed of the thermosensitive coloring layer and the print coloring layer 23 framed by the destructive print thin film layer 41.

[0009]

As described above, the present invention comprises a colored layer, a heat-sensitive printing thin film layer, and if necessary, a decoloring layer and a heat-sensitive coloring layer. Therefore, in low energy printing, the "thermosensitive coloring layer" consisting of only the thermosensitive coloring layer, in high energy printing
"Mixing of color between print coloring layer and print coloring layer" or by using together with decoloring layer, the image formed by "printing coloring layer" bordered by the destructive printing thin film layer is clearly formed without edging due to other hues. it can. Since the thermosensitive coloring layer is provided as a single layer, there is no difference in hue due to the temperature difference, and the effect of printing an image in which the hue is clearly separated is exerted. And
Since different printing methods of the thermosensitive coloring layer, the thermosensitive printing thin film layer, the coloring layer, and the erasing layer are used, mutual coloring is not affected in the printing step, and a vivid image is formed. Also, the layer thickness for expressing multiple colors can be reduced,
Even if it is laminated on a magnetic card or the like, the magnetic reading ability is maintained. Further, by using a picture layer in combination, it is possible to provide a thermosensitive recording medium having a more varied image.

[0010]

Embodiments of the present invention will now be described in more detail with reference to the drawings. (Example 1) As shown in FIG. 5, a primer layer 16 (acrylic varnish) was applied by gravure printing 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, hereinafter, the coating amount in the present specification is described as solid content), black colored layer 2
And a primer layer 17 for the heat-sensitive printing thin film layer 4 made of acrylic varnish. Then, tin was provided on the colored layer 2 side by a vacuum vapor deposition method to a thickness of 500 Å to form a thermal printing thin film layer 4. Further, a primer layer 18 made of vinyl chloride / vinyl acetate copolymer varnish is provided, and 3 g / m ^{2 of} the “thermosensitive color developing layer coating liquid” that develops the following reddish orange color is applied to react the thermosensitive color developing layer 3 and the two liquid reaction. Type of linear polyester
A varnish consisting of isocyanate, an antistatic agent and a lubricant was provided as the protective layer 5 by the 2 g / m ² gravure coating method to form a card provided with the multicolor heat-sensitive recording medium of Example 1. "Thermal coloring layer coating liquid" -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 Mixture of dispersion A / dispersion B = 1/5.

When printing an image on the multicolor recording medium, as shown in FIG. 6, in the low-energy printing section 10, a printing of 0.5 mJ / dot is applied to the thermal head, and the thermal coloring layer 3 is applied. Was developed to form a reddish orange image by the "printing coloring layer 33". At this time, the heat-sensitive printing thin film layer 4 is not destroyed and therefore keeps the concealing property, and the colored image of the card is only the "printing coloring layer 33". Next, in the high-energy printing unit 20, the thermal head has 1.2 mJ /
Applying the dot applied energy, the thermal printing thin film layer 4
To form a transparent printed thin film layer 41, and the colored layer 2 is used as a printed colored layer 23, and the printed coloring layer 3 is formed.
An image mixed with 3 was printed. That is, on the base sheet 1, an image obtained by mixing the black color layer 23 formed by the transparent layer of the destructive print thin film layer 41 with the black color layer 23 and the color layer 33, and a red color of the color layer 33 alone. The image of can be printed clearly.

Example 2 As shown in FIG. 7, a black magnetic recording layer 2 also serving as a coloring layer 2 on one surface of a biaxially stretched polyester sheet having a thickness of 188 μm as a base sheet 1.
The coating amount of 6 was 30 g / m ² , and the polyester primer layer 17 for the thermal printing thin film layer 4 was provided. Next, tin was provided on the side of the magnetic recording layer 26 by a vacuum evaporation method to a thickness of 500 Å to form the thermal printing thin film layer 4. Furthermore, a primer layer 18 is provided, and the following "erasing layer coating liquid" is added at 3 g / m ²
The decoloring layer 6 was formed by coating. Further, a thermosensitive coloring layer 3 that develops a reddish orange color similar to that of Example 1 and a protective layer 5 are provided by gravure coating via a primer layer 19 to form a card provided with the multicolor thermosensitive recording medium of Example 2. did. "Decoloring layer coating liquid" 4,4-dithiodimorpholine 10 parts Polyvinyl alcohol 10 parts Water 30 parts

When an image is provided on the multicolor recording medium,
As shown in FIG. 8, in the low-energy printing unit 10, printing energy of 0.5 mJ / dot is applied to the thermal head to cause the thermosensitive coloring layer 3 to develop color, and the “printing coloring layer 3
3 ”to form a reddish orange image. At this time, since the thermal printing thin film layer 4 is not destroyed, the concealing property is maintained and the colored image of the card is only the "printing coloring layer 33". Next, in the high-energy printing unit 20, the thermal head is
A printing color forming layer 3 is formed by applying a printing energy of J / dot to form a destroyed printing thin film layer 41 which is made transparent by breaking the thermal printing thin film layer 4 and which is colored by the thermosensitive coloring layer 3.
3 is a monochromatic "printing magnetic layer" which is decolored by the active decoloring layer 61 which is the decoloring layer 6 activated to become the decoloring coloring layer 34, and as a result, is bordered only by the transparent destructive printing thin film layer 41. The recording layer 27 ″ could be provided. That is, a two-color image of the red-orange image formed by the print coloring layer 33 and the magnetic recording layer 27 formed on the transparent portion of the destructive print thin film layer 41 is clearly formed on the card. Magnetic recording was performed on this multicolor thermosensitive recording medium with a magnetic head, and a recording density of 420 FRPI (flux reversal per inc) was obtained.
In h), the reproduction output is 5.9 V in the printing part and 6.3 V in the non-printing part, and the effect of the reproduction output on the magnetic recording layer due to printing is 6%, which is practically no problem. It was in the range.

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 a stretched 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,
0.03 depending on the physical properties required for rigidity and application
~ 2 mm. Then, if necessary, coloring is performed with an inorganic or organic pigment or dye. A preferred material is a stretched polyester sheet of 0.08 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. Other,
If desired, the magnetic recording layer may be colored. In addition, the pattern layer, depending on the printing method, is formed by a solvent-drying ink or a reaction-curing ink for ordinary planographic printing, intaglio including gravure printing, stencil printing, letterpress printing or roll-up printing. You can The colored layer can also be formed by a usual coating method such as roll coating or air knife coating in addition to the above printing method.

For the heat-sensitive printing thin film layer, 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 is vacuum-deposited, sputtered or plated. 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 heat-sensitive color-forming layer is a conventionally known colorless or light-colored leuco dye having a lactone ring, a lactam ring, a spiropyran ring or the like, and a color-forming aid that reacts with the leuco dye to form 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 depends on the desired concentration of the thermosensitive color developing layer, but is 0.5 to 10 g / m ² , preferably 2 to
It is 5 g / m ² .

The color erasing layer for erasing the color forming layer composed of the above-mentioned materials is a conventionally used color erasing agent such as higher aliphatic alcohol, polyether, polyethylene glycol derivative, acetamide, stearyl amide. And a nitrogen-containing organic compound such as phthalonitrile are dissolved or dispersed in the binder used for the above-mentioned color-developing agent by a similar method to form a coating solution. The coating amount is 0.5 to 10 g / m ² , though it depends on the amount of the thermosensitive coloring layer.
It is preferably ² to 5 g / m ² .

The protective layer is provided in order to prevent physical damage such as friction and 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 application method can be an ordinary method according to the shape curing method of the base sheet or the resin varnish, and the application amount is 0.5 to 1
0 g / m ^2, preferably from 2-5 g / m ^2.

The magnetic recording layer is γ-Fe ₂ O ₃ , Co-deposited γ-Fe ₂ O ₃ ,
Fe ₃ O ₄ , CrO ₂ , Fe, Fe-Cr, Fe-Co, Co-Cr, Co-Ni, M
A dispersion in which conventionally known magnetic fine particles such as n-Al and Ba ferrite are dispersed in an appropriate ink vehicle can be formed by a conventionally known method such as gravure coating, roll coating and knife coating. Fe-Co, Co-Cr, Co
It is also possible to form a base material sheet by using a metal or alloy such as -Ni or an oxide thereof, 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 to 100 μm, preferably 5 to 20.
μm. The thickness of the magnetic recording layer formed by vacuum deposition, sputtering, plating or the like is 100-100.
It is 00Å, preferably 500 to 1000Å. γ-Fe ₂
Vehicles that disperse O ₃ etc. are polyvinyl butyral,
Examples thereof include vinyl chloride / vinyl acetate copolymer, polyurethane, polyester, cellulose derivative, acrylic resin, styrene / maleic acid copolymer. 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. It is composed of a coloring layer, a thermosensitive printing thin film layer, and if necessary, a decoloring layer and a thermosensitive coloring layer. Therefore, when printing with low energy, the "thermosensitive coloring layer" consisting of only the thermosensitive coloring layer is used.
"Mixing of color between print coloring layer and print coloring layer" or by using an erasable layer as described in the second invention, an image formed by "print coloring layer" is clearly formed without edging by other colors. Produces the effect of Since the thermosensitive color-developing layer is provided as a single layer, there is no rimming of the image and the hues can be clearly separated. Further, since different printing methods of the thermosensitive coloring layer, the thermosensitive printing thin film layer, the coloring layer, and the decoloring layer are used, a clear image can be formed without mutual mutual coloring in the printing process. In addition, since each color is expressed, the thickness of each layer can be made thin, and even if it is laminated on a magnetic card or the like, magnetic reading can be easily performed. Further, by using it together with the picture layer, it is possible to provide a heat-sensitive recording medium having various images.

[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 the constitution of the multicolor thermosensitive recording medium of the example.

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 structure of a multicolor thermosensitive recording medium of another 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.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Coloring layer 21 Picture layer 23 Printed coloring layer 26 Magnetic recording layer 27 Printed 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

Claims (4)

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