JP2002187359A - Multicolor heat-sensitive recording medium, its manufacturing method and method for printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multicolor heat-sensitive recording medium capable of preventing a profile-like color mixing between a plurality of heat-sensitive color developing layers and which may not use a heat-sensitive color developing layer for requiring a high application heat energy. SOLUTION: The multicolor heat-sensitive recording medium comprises a first heat-sensitive color developing layer 4 formed on a base 2, a disabled region 5 formed on a part of the layer 4 to disable or dull its color developing function, and a second heat-sensitive color developing layer 6 formed to cover the region 5 wider than the region 5 to color develop in a color different from that of the layer 4. Thus, when the layer 6 is heated, the layer 4 is not color developed in the region 5 but printed by a color only by a monochromatic color developing of the layer 6, and both the layers 4 and 6 are together color developed in color in mixed color developing to be printed on a laminated part except the region 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multicolor heat-sensitive recording medium having a plurality of heat-sensitive layers having different colors, a method for producing the same, and a method for printing.

[0002]

2. Description of the Related Art In order to obtain a heat-sensitive foam that can be identified in multiple colors on a single heat-sensitive recording medium, a method of printing information in different colors on a heat-sensitive paper by offset printing or the like and providing a plurality of types is generally used. is there. Here, the thermal foam refers to, for example, a label or the like having an area where a printing frame is previously formed by printing or the like in an area where printing is performed on a thermosensitive recording medium with a predetermined thermosensitive color. Taking the form for Takkyubin (registered trademark) as an example, it is formed of two types of heat-sensitive forms printed with original payment and cash on delivery with characters of different colors. When this thermal recording paper is used, it is necessary to change the thermal foam according to the customer.

Further, there is a multicolor heat-sensitive recording medium for realizing a plurality of heat-sensitive foams. A multicolor heat-sensitive recording medium is disclosed in, for example, JP-A-57-178791, and the like.
At least two different colors at different color temperatures
This is a recording material in which two heat-sensitive coloring layers are formed on a base material such as paper, and usually has a high-temperature coloring layer as a lower layer and a low-temperature coloring layer as an upper layer. In general, a thermal head is used as a means for applying heat energy in order to form a color on these coloring layers. When printing and recording using such a recording medium, images of different colors can be obtained by applying different thermal energies. For example, when a relatively low heat energy is applied, the color develops blue, and when a relatively high heat energy is applied, the color develops black.

In this type of multicolor heat-sensitive recording medium, when a low heat energy is applied, there is no problem with a heat-sensitive coloring layer that forms a color with low heat energy. However, when a coloring layer that forms a color with high heat energy is formed, for example, There is a problem in that the temperature of the edge of the print pattern becomes low, and at that time, the heat-sensitive coloring layer that develops with low energy develops color, thereby causing color mixing. The reason for this is that the temperature around the heated dots of the thermal head when high thermal energy is applied is low, so the contour becomes low, and the heat-sensitive coloring layer that develops color with low applied thermal energy develops color. is there.

[0005] Obtaining a plurality of thermal recording foams from the above-described conventional multicolor thermal recording medium is problematic in that color mixing is unavoidable and necessitates a difference between high-temperature and low-temperature thermal coloring materials. The only option was to lower the color sensitivity on the high temperature side.

[0006] In addition, the means for attaching thermosensitive recording media having different color tones on one base material is troublesome and costly. As described above, the method using a two-color thermal recording medium is as follows.
In order to avoid the problem of color mixing of a plurality of heat-sensitive coloring layers and to avoid color mixing, it is necessary to increase the difference in color formation start temperature. Therefore, it is necessary to form a color with low sensitivity, so that high sensitivity is required, that is, high heat energy is required to form a color. It is with. Further, an application time is required to apply high thermal energy, and the printing speed must be reduced. Further, it is required to control the thermal history to prevent color mixing as much as possible, which complicates the system and increases the cost.

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention
In order to solve the above-described problems, it is possible to prevent color mixing of contours between a plurality of heat-sensitive coloring layers, and to eliminate the need for using a heat-sensitive coloring layer requiring high applied heat energy. It is another object of the present invention to provide a recording medium and a printing method thereof, and further provide a manufacturing method capable of manufacturing a multicolor thermosensitive recording medium by a simple manufacturing process.

[0008]

According to the first aspect of the present invention,
A base material, a first thermosensitive coloring layer formed on the base material, a disabled area in which the coloring function of a part of the first thermosensitive coloring layer is disabled or blunted; And a second heat-sensitive coloring layer that is formed so as to cover the disabled area over a wider area than the disabled area and that emits a color different from the first heat-sensitive coloring layer. This is a multicolor heat-sensitive recording medium.

Therefore, when the second thermosensitive coloring layer is heated,
In the disabled area, the first thermosensitive layer can be printed with only the single color of the second thermosensitive coloring layer without coloring, and the first thermosensitive coloring layer and the second thermosensitive coloring layer can be printed in the layered portion other than the disabled area. Printing can be performed in a color by mixed color development due to both the heat-sensitive coloring layer and the heat-sensitive coloring layer. In other words, by positively utilizing the mixed color development of the first and second thermosensitive coloring layers to print, the entire printed portion becomes mixed color, and only the outline portion becomes mixed color. High quality printing without color mixture is possible.

According to a second aspect of the present invention, in the multicolor heat-sensitive recording medium according to the first aspect, the first thermosensitive coloring layer develops a color when the laminated second thermosensitive coloring layer is colored. It is characterized by being formed in.

Therefore, in the laminated portion of the first thermosensitive coloring layer and the second thermosensitive coloring layer, it is ensured that the first thermosensitive coloring layer always develops the color when the second thermosensitive coloring layer is colored. I can do it. At this time, it is possible to prevent the first thermosensitive coloring layer from being colored by the disabling action of the disabling area.

The invention described in claim 3 is the first or second invention.
In the multicolor heat-sensitive recording medium described above, when the coloring temperature of the first thermosensitive coloring layer is α and the coloring temperature of the second thermosensitive coloring layer is β, each thermosensitive coloring layer satisfies the relationship α ≦ β. Is formed.

Therefore, when the color temperature α of the first heat-sensitive coloring layer and the color temperature β of the second heat-sensitive color layer satisfy the relationship of α ≦ β, the color difference between the first heat-sensitive color layer and the second heat-sensitive color layer is satisfied. In the laminated body portion, when the second heat-sensitive coloring layer is colored, the first heat-sensitive coloring layer can also be positively used for color mixing, which can always be colored, and contour-shaped color mixing can also be reliably prevented.
At the same time, multi-color development according to the purpose can be performed by applying the same energy, and high-quality, high-speed multi-color printing can be performed with simple printing control.

According to a fourth aspect of the present invention, a base material, a first thermosensitive coloring layer formed on the base material, and the first thermosensitive coloring layer formed on the first thermosensitive coloring layer are different from each other. A multicolor heat-sensitive recording medium, comprising: a second thermosensitive coloring layer that develops a color; and a disabled area in which the coloring function of a part of the second thermosensitive coloring layer is disabled or blunted.

Therefore, when the second thermosensitive coloring layer is heated,
In the disabled region, the second thermosensitive layer can be printed with only the color of the first thermosensitive coloring layer without coloring, and in the laminate portion other than the disabled region, the first thermosensitive coloring layer and the second thermosensitive layer can be printed. It is possible to print in a color by mixed color development due to both the color forming layer and the color forming layer. In other words, by positively utilizing the mixed color development of the first and second thermosensitive coloring layers to print, the entire printed portion becomes mixed color, and only the outline portion becomes mixed color. High quality printing without color mixture is possible.

[0016] The invention according to claim 5 provides the invention according to claims 1 to 4.
In the multicolor heat-sensitive recording medium according to any one of the above, a plurality of the first heat-sensitive coloring layer and the second heat-sensitive coloring layer are formed in different regions on the base material, The color of at least one of the second thermosensitive coloring layers is different from each other.

Accordingly, in realizing the invention according to any one of the first to fourth aspects, it is possible to perform printing with more various colors.

[0018] The invention according to claim 6 is the invention according to claims 1 to 3.
In the multicolor heat-sensitive recording medium according to any one of the above, the first heat-sensitive coloring layer has a region where the second heat-sensitive coloring layer is not laminated.

Therefore, in realizing the invention according to any one of the first to third aspects, it is possible to perform printing in which only the first heat-sensitive color forming layer is added with a single color, thereby further diversifying. it can.

[0020] The invention according to claim 7 is that the first surface is provided on one surface of the base material.
Forming a heat-sensitive coloring layer, forming a disabled area for disabling or dulling the color-forming function of a part of the first heat-sensitive coloring layer, and forming a color different from the first heat-sensitive coloring layer. Forming a second thermosensitive coloring layer so as to cover the disabled area on the first thermosensitive coloring layer over a wider area than the disabled area using a thermosensitive coloring material. This is a method for producing a multicolor heat-sensitive recording medium.

Therefore, the multicolor heat-sensitive recording medium according to the present invention can be manufactured by a simple manufacturing process.

[0022] The invention according to claim 8 is a step of forming a disabled region for disabling or dulling the coloring function of a part of the first thermosensitive coloring layer formed on one surface of the base material, A second heat-sensitive coloring layer is formed using a heat-sensitive coloring material that develops a color different from that of the first heat-sensitive coloring layer so as to cover the disabled area on the first heat-sensitive coloring layer over a wider area than the disabled area. And a process for producing a multicolor thermosensitive recording medium.

Accordingly, the first thermosensitive coloring layer is formed basically by using a commercially available thermosensitive recording paper on which the first thermosensitive coloring layer is originally formed. The process can be omitted, and the manufacturing process can be further simplified.

According to a ninth aspect of the present invention, the first substrate is provided on one surface of the substrate.
A step of forming a thermosensitive coloring layer, a step of forming a second thermosensitive coloring layer on the first thermosensitive coloring layer, and a disabling region for disabling or dulling a part of the coloring function of the second thermosensitive coloring layer. Forming a multicolor thermosensitive recording medium.

Therefore, the multicolor heat-sensitive recording medium according to the present invention can be manufactured by a simple manufacturing process.

According to a tenth aspect of the present invention, there is provided a method for forming a second heat-sensitive coloring layer on a first heat-sensitive coloring layer formed on one surface of a substrate, and a coloring function of a part of the second heat-sensitive coloring layer. Forming a disabling region for disabling or dulling the heat-sensitive recording medium.

Therefore, the first heat-sensitive coloring layer is formed basically by using a commercially available heat-sensitive recording paper on which the first heat-sensitive coloring layer is originally formed. The process can be omitted, and the manufacturing process can be further simplified.

The eleventh aspect of the present invention provides the first, second, and third aspects.
6. The multicolor thermosensitive recording medium according to 3 or 5, wherein printing by mixed color development is performed by heating with a heating means in a laminated portion of the first thermosensitive coloring layer and the second thermosensitive coloring layer, and the printing is performed on the disabled area. A printing method using a multicolor heat-sensitive recording medium, characterized in that the second heat-sensitive coloring layer portion is printed by a single color of the second heat-sensitive coloring layer by heating by the heating means.

Therefore, multicolor printing using the multicolor heat-sensitive recording medium according to the first, second, third or fifth aspect can be easily performed by applying the same heating energy.

According to a twelfth aspect of the present invention, there is provided the multicolor thermosensitive recording medium according to the sixth aspect, wherein the first thermosensitive coloring layer and the second thermosensitive coloring layer are mixed and colored by heating by a heating means at a layered portion. Printing is performed, and in the second thermosensitive coloring layer portion on the disabled area, printing is performed by a single color of the second thermosensitive coloring layer by heating by the heating means, and the second thermosensitive coloring layer is printed by the second thermosensitive coloring layer. In a printing method using a multicolor heat-sensitive recording medium, the first heat-sensitive coloring layer is printed by a single color in the area where the heat-sensitive coloring layer is not laminated. is there.

Therefore, multicolor printing using the multicolor heat-sensitive recording medium according to claim 6 can be easily performed by applying the same heating energy.

According to a thirteenth aspect of the present invention, there is provided the multicolor thermosensitive recording medium according to the fourth or fifth aspect, wherein a color is mixed by heating by a heating means in a laminated portion of the first thermosensitive coloring layer and the second thermosensitive coloring layer. The multi-color printing is performed by performing printing by color development, and printing by the single-color development of the first thermo-sensitive coloring layer by heating by the heating means in the disabled area of the second thermo-sensitive coloring layer. This is a printing method using a thermosensitive recording medium.

Therefore, multicolor printing using the multicolor heat-sensitive recording medium according to claim 4 or 5 can be easily performed by applying the same heating energy.

[0034]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [First Embodiment of the Invention] One embodiment of the present invention will be described as a first embodiment of the present invention.
FIG. 1 is a schematic view of a multicolor heat-sensitive recording medium 1a according to a first embodiment of the present invention, and FIG.
(B) is a plan view thereof. This multicolor thermal recording medium 1a
Is a heat-sensitive recording medium capable of partially developing different colors.

As the base material 2, for example, high quality paper is used.
An undercoat layer 3 made of clay, a binder resin, and the like, and a first thermosensitive coloring layer 4 are laminated on one surface of the base material 2. The first thermosensitive coloring layer 4 is partially formed with a disabled area 5 in which at least thermal energy for coloring is disabled or blunted. Further, the first thermosensitive coloring layer 4 is provided on the first thermosensitive coloring layer 4 provided with the disabling region 5, and the second thermosensitive coloring layer which develops a color having a different color tone when colored by applying heat energy. 6 are laminated, and a protective layer 7 is further laminated thereon as required. In this case, the protective layer 7 is provided when the environmental conditions or the like used are severe.

Next, a specific example for producing the above-described multicolor thermal recording medium 1a will be described. First, the first thermosensitive coloring layer 4 is formed on one surface of the substrate 2 on which the undercoat layer 3 is provided, by applying and drying the film to a dry film thickness of 5 μm using a roll coater.

<Formulation of ink for first thermosensitive coloring layer 4> Developer dispersion liquid Developer: 4-hydroxy-4'-isoboropoxydiphenyl sulfone (F-647 manufactured by Chukyo Yushi Co., Ltd.): 3 parts by weight Sensitizer: methylsteroamide (D75 manufactured by Chukyo Yushi Co., Ltd.)
7) 2 parts by weight Lubricant: zinc stearate (Z-7-3 manufactured by Chukyo Yushi Co., Ltd.)
0) 0.3 parts by weight Inorganic pigment: calcium carbonate 2 parts by weight PVA117 2 parts by weight (manufactured by Kuraray Co., Ltd.) Water 33 parts by weight The above-mentioned composition was dispersed with a paint shaker for 3 hours to give a developer dispersion. Obtained.

Leuco Dye A Dispersion Leuco Dye: RED-3 (manufactured by Yamamoto Kasei): 1 part by weight PVA117 (10% solution): 2 parts by weight Water: 3 parts by weight Obtained.

Leuco Dye B Dispersion Leuco Dye: 3,6-dimethoxyhumeolan: 1 part by weight PVA117 (10% solution): 2 parts by weight Water: 3 parts by weight is dispersed by a sand mill to obtain a dispersion of the leuco dye liquid B. Obtained.

Leuco Dye C Dispersion Leuco Dye ... CLV ... 1 part by weight (Y-CV manufactured by Chukyo Yushi Co., Ltd.)
L) PVA117 (10% solution) 2 parts by weight Water 3 parts by weight is dispersed with a paint shaker to obtain a leuco dye C dispersion.

Next, an ink was prepared by mixing 1 part by weight of the above-described dispersion of leuco dye A, 1 part by weight of dispersion of leuco dye B, and 1 part by weight of developer dispersion.
The first thermosensitive coloring layer 4 is formed by applying and drying the upper surface of the undercoat layer 3 formed on the first thermosensitive coloring layer.

The first thermosensitive coloring layer 4 thus obtained
, The disabling region 5 is partially formed. The position and shape of the disabled area 5 are determined depending on the use of the multicolor thermal recording medium 1.

Here, the specific formation of the disabled region 5 will be described. First, in the first thermosensitive coloring layer 4, a process for reducing the coloring function in a preset region is performed. The treatment uses 2-methylpiperazine as a disabling agent, prepares the following coating solution, and applies and infiltrates the region set as described above by the flexographic printing method, thereby disabling the disabled region 5. Form.

(Disabling agent ink) Samprene 1B-F370 (manufactured by Sanyo Kasei) 15%
Solution: 80 parts by weight 2-Methylpiperazine (disabling agent): 20 parts by weight Next, the barrier layer 8 is formed as necessary. This barrier layer 8 is formed to prevent the disabling agent from diffusing into the second thermosensitive coloring layer 6. The barrier layer 8 is formed by applying a 1: 1 mixed solution of SCX-70 (manufactured by Johnson Polymer) and PVA117 by a roll coater, and then applying and drying it so that the film thickness after drying becomes 2 μm. , Formed by performing a calendar process.

Next, a coating liquid obtained by mixing 1 part by weight of the dispersion of Leuco Dye C and 1 part by weight of the developer was formed into a coating layer by a roll coater, and then dried to a thickness of 5 μm.
The second thermosensitive coloring layer 6 is formed by adjusting the application amount and the like so that

Further, if necessary, the following coating solution is formed by a roll coater so that the dry film thickness becomes 2 μm by the same method as described above, and then dried to form a protective layer 7. Is formed, and finally, a calendering process is performed to obtain a multicolor heat-sensitive recording medium 1a.

(Ink of the protective layer 7) Lubricant: zinc stearate (Z-7-3 manufactured by Chukyo Yushi-Jiyu)
0) 2 parts by weight Calcium carbonate 11.2 parts by weight PVA117 2 parts by weight Water 22 parts by weight is dispersed by a sand mill to obtain a coating liquid.

The multicolor heat-sensitive recording medium thus obtained
1a is that the first heat-sensitive coloring layer 4 and the second heat-sensitive coloring layer 6 are formed by selecting materials having the same applied heat energy for coloring, and each coloring is performed by applying substantially the same heat energy. 1st thermosensitive coloring layer 4 and 2nd thermosensitive coloring layer 6
However, only the disabled area 5 is the first in the disabled area.
Since the heat-sensitive coloring layer 4 does not form a color, the color of the second heat-sensitive coloring layer 6 alone (blue of the color of CLV crystal violet lactone), and other regions of the laminate portion are the first heat-sensitive coloring layer 4 and the second heat-sensitive coloring. It becomes a color mixture with the layer 6 and becomes almost black. In this mixed color development, since the entire heated portion is colored, color mixing does not occur only at the outline portion.

As described above, a portion in which a layered portion composed of the first thermosensitive coloring layer 4 and the second thermosensitive coloring layer 6 is printed in a mixed color and a color in which only the second thermosensitive coloring layer 6 is formed in a single color. Thus, a multicolor heat-sensitive recording medium 1a having a portion to be printed is obtained.

That is, as shown in the plan view of FIG. 1 (b), the first and second thermosensitive coloring layers 4 and 6 can be mixed and colored on the completed multicolor thermosensitive recording medium 1a. A thermosensitive coloring area 11 and a thermosensitive coloring area 12 in which only the second thermosensitive coloring layer 6 can be colored.

As described above, according to the present embodiment, unlike the conventional multi-color thermal recording paper, it is not necessary to apply an extremely different thermal energy to form two colors, and it is possible to set the printing area of an arbitrary predetermined printing area. Different colors can be printed in different areas. Here, assuming that the coloring temperature of the first thermosensitive coloring layer 4 is α and the coloring temperature of the second thermosensitive coloring layer 6 is β, α =
Although a material satisfying the relationship β was used, at least α ≦ β
When the following relationship is satisfied and the upper second thermosensitive coloring layer 6 is colored, the lower first thermosensitive coloring layer 4 only needs to be capable of simultaneously coloring.

Although the present embodiment has been described with reference to the case where a leuco dye is used, the present invention is not limited to the example of the present embodiment, and the first thermosensitive coloring layer 4 and the second thermosensitive coloring layer 6 can be mixed and colored. With respect to the color of the second heat-sensitive coloring layer 6 that forms a single color and the color of the second heat-sensitive coloring layer 6, a heat-sensitive recording material having a desired color can be appropriately selected.

For example, as the blue leuco dye used in the second thermosensitive coloring layer 6, CLV, BLMB (Yamamoto Soda Co., Ltd.), BLUE-63, BLUE-502 (Yamamoto Kasei Co., Ltd.), BLUE-220 ( Yamaoka Chemical Co., Ltd.), BLU
E-3 (manufactured by Hodogaya Chemical Co., Ltd.) or the like can be used.

The leuco dyes used in the first thermosensitive coloring layer 4 include the following.

Leuco Dye A: A red (magenta) dye or the like can be used. For example, PSD-HR, PS
DP (manufactured by Nippon Soda Co., Ltd.), RED-500, RED-5
20, RED-DCF (Hodogaya Chemical Co., Ltd.), RED-3, RED-40, Y-1 (Yamamoto Kasei Co., Ltd.) and the like can be used.

Leuco dye B: As the yellow leuco dye, 3,6-dimethoxyfluoran, 1- (4-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene and the like are used. It is possible.

When the color tone of the second heat-sensitive coloring layer 6 is changed, for example, when a red dye is used, a blue dye is used as the leuco dye A for the first heat-sensitive coloring layer 4. Any of these leuco dyes may be used as long as a desired color tone can be obtained by mixing one type or a plurality of types.

Further, the color representing the color tone when the first heat-sensitive coloring layer 4 and the second heat-sensitive coloring layer 6 are mixed and colored does not need to be black. Leuco dyes used for the color forming layer 4 and the second thermosensitive color forming layer 6 may be selected.

The developer of the present embodiment is 4-hydroxy-
The case where 4'-isopoloxydiphenylsulfone is used has been described, but is not limited thereto, and phenols, phenol metal salts, carboxylic acid metal salts, sulfonic acids, sulfonates, phosphoric acids, metal phosphates are used. And oxides such as acid phosphates, metal salts of acid phosphates, phosphorous acid, metal salts of phosphite and the like.

For example, bisphenol A, 2,4-dihydroxyacetophenone (2,4-HAP), 2,5-
HAP, 2,6-HAP, 3,5-HAP, 2,3,4
-HAP, 2,4-dihydroxybenzophenone (2,
4-HBP), 4,4'-HBP, 2,3,4-HB
P, 2,4,4'-HBP, 2,2 ', 4,4'-HB
P, 2,3-dihydrobenzoic acid, methyl 3,5-dihydrobenzoate, 4,4'-biphenol, 2,3,4
4'-tetrahydroxybenzophenone and the like can be used.

The developer used in the first thermosensitive coloring layer 4 depends on the interaction with the inactivating agent and the like, so that it is necessary to select a developing agent according to the inactivating agent used. The inactivating agent of the present embodiment used 2-methylpiperazine,
Not limited to this, ripened plastic polyethers,
Polyethylene imines, stearyl alcohols, polyethylene glycol and the like can be used as long as they prevent color development of the first thermosensitive coloring layer 4. It is also possible to add a material for improving the erasure storage stability.

By using a combination of a disabling agent and a color developing agent which is inactivated by reacting with the color developer of the first heat-sensitive color forming layer 4 and which does not react with the color developer of the second heat-sensitive color forming layer 6, It is also possible to make 8 unnecessary. Needless to say, the protective layer 7 is unnecessary when the durability is not required.

Further, in the above description, an example in which the first thermosensitive coloring layer 4 is laminated on the base material 2 has been described. However, the thermosensitive coloring layer (first thermosensitive coloring layer) is previously laminated on the base material. A commercially available thermosensitive coloring paper may be used. According to this, the step of laminating and forming the first thermosensitive coloring layer can be omitted.

[Second Embodiment of the Invention] Another embodiment of the present invention will be described as a second embodiment of the present invention.

Embodiment 2 of the present invention has the same structure and structure as Embodiment 1 of the invention, and will be described with reference to FIG. 1. However, the first thermosensitive coloring layer 4 has a black leuco. The difference from the first embodiment is that a dye is used. That is, a black leuco dye is used as the leuco dye A of the first embodiment. Further, no leuco dye B was used. The leuco dye C used in the second thermosensitive coloring layer 6 may be the same as in the first embodiment.

However, the amount of the leuco dye used in the first thermosensitive coloring layer 4 needs to be larger than that of the leuco dye used in the second thermosensitive coloring layer 6 or the coating thickness must be increased (both may be used). . Thus, when the portion other than the disabled region is heated, the second thermosensitive coloring layer 6 is made apparently indistinguishable due to the coloring of the first thermosensitive coloring layer 4.

For example, the leuco dye of the first thermosensitive coloring layer 4 is added to the second part of ODB-2 (manufactured by Yamamoto Kasei Co., Ltd.) at 5 parts by weight.
The leuco dye of the thermosensitive coloring layer 6 is blended so as to be 1 part by weight. The sensitizer and the developer in the developer dispersion need to be changed in accordance with the amount of the leuco dye.

More specifically, <First thermosensitive coloring layer 4> Developer dispersion A Developer: 4-hydroxy-4'-isopoloxydiphenylsulfone (F-647 manufactured by Chukyo Yushi Co., Ltd.) 10 parts by weight Sensitizer: Metelsteroamide (D-7 manufactured by Chukyo Yushi Co., Ltd.)
57) 5 parts by weight Lubricant: zinc stearate (Z7-3 manufactured by Chukyo Yushi Co., Ltd.)
0) 1 part by weight Inorganic pigment: calcium carbonate 2 parts by weight PVA117 3 parts by weight (manufactured by Kuraray Co., Ltd.) Water 50 parts by weight The above composition was dispersed with a paint shaker for 3 hours to obtain a developer dispersion. .

Leuco Dye A Dispersion Leuco Dye: ODB-2 (manufactured by Yamamoto Kasei): 5 parts by weight PVA117 (10% solution): 5 parts by weight Water: 15 parts by weight Obtained.

The above dispersion was mixed at a ratio of 1: 1 and coated and dried with a roll coater to a dry film thickness of 7 μm.

After the first thermosensitive coloring layer 4 was applied, the disabled area 5 was formed by flexographic printing in the same manner as in the first embodiment. Further, similarly to the case of the first embodiment, after the barrier layer 8 is provided, a calendar process is performed, and the second thermosensitive coloring layer 6 is laminated.

<Second heat-sensitive coloring layer 6> Developer dispersion Liquid developer: 4-hydroxy-4'-isopoloxydiphenyl sulfone (F-647 manufactured by Chukyo Yushi Co., Ltd.) 3 parts by weight Sensitizer: methyl Steroamide (D-7 manufactured by Chukyo Yushi Co., Ltd.)
57) 2 parts by weight Lubricant: zinc stearate (Z-7-3 manufactured by Chukyo Yushi Co., Ltd.)
0) 0.3 parts by weight Inorganic pigment: calcium carbonate 2 parts by weight PVA117 2 parts by weight (manufactured by Kuraray Co., Ltd.) Water 33 parts by weight The above-mentioned composition was dispersed with a paint shaker for 3 hours to give a developer dispersion. Obtained.

Leuco Dye C Dispersion Leuco Dye CVL 1 part by weight (Y-CV manufactured by Chukyo Yushi Co., Ltd.)
L) PVA117 (10% solution): 2 parts by weight Water: 3 parts by weight The above dispersion was mixed and applied with a roll coater to form a coating layer, and then dried to form a second thermosensitive coloring layer 6. (The same as in the first embodiment). further,
The multi-color thermosensitive recording medium 1 is completed by forming the protective layer 7 in the same manner as in the first embodiment.

The multicolor thermosensitive recording medium 1b thus obtained has the same effects as in the first embodiment.

As in the case of the first embodiment, the second thermosensitive coloring layer 6 is not limited to blue, and may use a red-based dye or the like.

The evaluations shown in Table 1 were performed with the label printer KP-50 manufactured by Toshiba Tec Corporation in both the first and second embodiments. In addition, the blue color in the print result in Table 1 means the blue color on the disabled area 5.

[0077]

[Table 1]

Third Embodiment Another embodiment of the present invention will be described as a third embodiment of the present invention. FIG.
Is a multicolor thermal recording medium 1 according to Embodiment 3 of the present invention.
2A is a schematic view, FIG. 2A is a sectional view, and FIG. 2B is a plan view thereof. The same members as those in the first and second embodiments of the invention are denoted by the same reference numerals, and detailed description of common technical contents is omitted (the same applies to the following embodiments).

The multicolor heat-sensitive recording medium 1b of the third embodiment
First, another first thermosensitive coloring layer 4b is formed on the undercoat layer 3 formed on the base material 2 in a different region from the first thermosensitive coloring layer 4a. Next, disabling regions 5a and 5b are formed in each of the thermosensitive coloring layers 4a and 4b. Further, a barrier layer 8 and second thermosensitive coloring layers 6a and 6b are formed on these layers.
Are laminated. Thereafter, a multicolor heat-sensitive recording medium 1b on which the protective layer 7 is formed is obtained. That is, the first thermosensitive coloring layer 4
a, 4b and the second thermosensitive coloring layers 6a, 6b are formed in different regions on the base material 2.

According to the multicolor heat-sensitive recording medium 1b having such a structure, the heat-sensitive coloring area 11a can be printed by mixing and coloring of a laminate of the first and second heat-sensitive coloring layers 4a and 6a. In the heat-sensitive coloring area 12a, printing can be performed by single-color coloring of the second heat-sensitive coloring layer 6a. The thermosensitive coloring area 11b can be printed by mixing and coloring a laminate of the first thermosensitive coloring layer 4b and the second thermosensitive coloring layer 6b, and the thermosensitive coloring area 12b can be printed by monochromatic coloring of the second thermosensitive coloring layer 6b. It becomes possible. For example, the first thermosensitive coloring layer 4a uses a leuco dye that develops magenta and yellow. The second thermosensitive coloring layer 6a uses a cyan leuco material. By doing so, the thermosensitive coloring area 11a becomes black, and the thermosensitive coloring area 12a becomes cyan. Also,
A leuco dye in which the first thermosensitive coloring layer 6b develops yellow,
When the same cyan-based leuco material as the second thermosensitive coloring layer 6a is used for the second thermosensitive coloring layer 6b, the thermosensitive coloring area 11b emits green, and the thermosensitive coloring area 12b becomes cyan. Of course, the present invention is not limited to such a combination, and it goes without saying that various colors can be reproduced by changing a part of each of the first and second thermosensitive coloring layers. In particular, the first thermosensitive coloring layers 4a, 4b
And / or different colors of the second thermosensitive coloring layers 6a and 6b, a multicolor thermosensitive recording medium 1b having various coloring configurations is obtained.

[Fourth Embodiment] Another embodiment of the present invention will be described as a fourth embodiment of the present invention. FIG.
Is a multicolor thermal recording medium 1 according to Embodiment 4 of the present invention.
3 (a) is a cross-sectional view, and FIG. 3 (b) is a plan view thereof.

The multicolor heat-sensitive recording medium 1c of the fourth embodiment
First, the first thermosensitive coloring layer 4c on the undercoat layer 3 formed on the base material 2 is formed. Next, a disabled region 5c is formed in the first thermosensitive coloring layer 4c. Further, the barrier layer 8 and the second thermosensitive coloring layer 6c are formed in a part of the first thermosensitive coloring layer 4c. Thereafter, by forming the protective layer 7, the multicolor heat-sensitive recording medium 1c is obtained. That is,
In the above-described embodiment, the second heat-sensitive coloring layer
Although the thermosensitive coloring layer 6 is formed, in the fourth embodiment, the first thermosensitive coloring layer 4 includes a single-layer structure region where the second thermosensitive coloring layer 6 is not laminated.

According to the multicolor heat-sensitive recording medium 1c having such a structure, the heat-sensitive coloring area 11c can be printed by mixing and coloring of a laminate of the first and second heat-sensitive coloring layers 4c and 6c. The heat-sensitive coloring area 12c can be printed by a single color of the second heat-sensitive coloring layer 6c.
The heat-sensitive coloring area 13c including only the heat-sensitive coloring layer 4c can be printed by the single-color coloring of the first heat-sensitive coloring layer 4c.
For example, when the first thermosensitive coloring layer 4c uses a yellow leuco dye and a magenta leuco dye, and the second thermosensitive coloring layer 6c uses a cyan leuco dye, the thermosensitive coloring area 11c is black and the thermosensitive coloring area 12c is cyan. The color and thermosensitive coloring area 13c can obtain red coloring. Of course, it is not limited to such a combination of colors.

[Fifth Embodiment] Another embodiment of the present invention will be described as a fifth embodiment of the present invention. FIG.
Is a multicolor thermal recording medium 1 according to a fifth embodiment of the present invention.
4D is a schematic view, FIG. 4A is a sectional view, and FIG. 4B is a plan view thereof.

The multicolor thermosensitive recording medium 1d of the fifth embodiment
In (1), the first thermosensitive coloring layer 4d is formed on the surface of the base material 2 on which the undercoat layer 3 is formed. Next, the barrier layer 8 is formed on the first thermosensitive coloring layer 4d. Next, a second thermosensitive coloring layer 6 d is formed on the barrier layer 8. Further, a process for disabling or dulling the thermosensitive coloring function is performed on a part of the second thermosensitive coloring layer 6d in the same manner as in the above-described embodiment, and as shown in FIG.
By forming d, a multicolor thermal recording medium 1d is obtained.

Here, in order to cope with the environment in which the multicolor thermosensitive recording medium 1d is used, if necessary, a protective layer 7 is formed to prevent deterioration of the thermosensitive coloring layer due to, for example, humidity. be able to. Further, the barrier layer 8 need not be formed on the entire surface of the first thermosensitive coloring layer 4d, but may be formed at least in a region where the disabled region 5d is formed. This barrier layer 8 is used when a disabling agent or the like penetrates into the first thermosensitive coloring layer 4d when forming the disabled zone 5d, and reduces the thermosensitive coloring function. Therefore, the barrier layer 8 may not necessarily be provided if the thermosensitive coloring function is not reduced. For example, when the inactivating agent selectively has an effect only on the second thermosensitive coloring layer 6d or when the first thermosensitive coloring layer 4d
The barrier layer 8 may be omitted if there is no fear of diffusion into the barrier layer.

The multicolor heat-sensitive recording medium 1 thus formed
4B, which is a plan view of FIG. 4D, the thermosensitive coloring area 11d includes a first thermosensitive coloring layer 4d and a second thermosensitive coloring layer 6d.
d indicates a region corresponding to the laminate, and when printing is performed in the heat-sensitive coloring area 11d, printing is performed by mixing and coloring the heat-sensitive coloring layers 4d and 6d by the applied thermal energy. The thermosensitive coloring area 12d is also formed by the single-color coloring of the first thermosensitive coloring layer 4d because the coloring function of the second thermosensitive coloring layer 6d is disabled when thermal energy is applied for coloring in the same manner. It will be printed.

As described above, the heat-sensitive coloring areas 11d and 12d
Is formed, different colors can be developed. Further, for example, if the same coloring temperature of the thermosensitive coloring material of the first thermosensitive coloring layer 4d and the same coloring temperature of the thermosensitive coloring material of the second thermosensitive coloring layer 6d is selected, all the printing areas of the multicolor thermosensitive recording member 1d are set. Printing with the same applied energy (coloring)
can do. In addition, even if one having a different coloring temperature is selected, it is of course possible to print all printing areas by applying heat energy for coloring the thermosensitive coloring layer having a higher coloring temperature. .

As described above, the coloring temperatures of the first thermosensitive coloring layer 4d and the second thermosensitive coloring layer 6d can be arbitrarily selected.

As described in each of the embodiments, the present invention can provide a multicolor heat-sensitive recording medium capable of recording various colors with a simple structure. In each of the embodiments in which color mixing is actively used, a method in which the second heat-sensitive coloring layer does not seem to be able to confirm color appearance when the first heat-sensitive coloring layer develops color, as described in Embodiment 2, is also realized. If possible, the embodiment is included in the present invention. For example, when the first thermosensitive coloring layer is a black coloring layer and the second thermosensitive coloring layer is a blue coloring layer, the color mixture of black and blue becomes substantially black. This is included in the concept of “color mixture”.

[0091]

According to the first aspect of the present invention, when the second heat-sensitive coloring layer is heated, the first heat-sensitive coloring layer does not develop a color in the disabled area, and the second heat-sensitive coloring layer uses only a single color. In the laminate portion other than the disabled area, printing can be performed in a color by mixed color formation by the first heat-sensitive coloring layer and the second heat-sensitive coloring layer both forming a color. By actively utilizing the mixed color development of the first thermosensitive coloring layer and the second thermosensitive coloring layer for printing, there is no contour-like color mixture in which the entire printed portion becomes mixed color and only the contour portion is mixed. High quality printing is possible.

According to the second aspect of the present invention, in the multicolor thermosensitive recording medium according to the first aspect, the first thermosensitive coloring layer and the second thermosensitive coloring layer are provided.
With respect to the laminated body portion with the heat-sensitive coloring layer, it is possible to positively use the mixed color development in which the first heat-sensitive coloring layer always develops the color when the second heat-sensitive coloring layer is colored. The disabling effect can prevent the first thermosensitive coloring layer from coloring.

According to the third aspect of the present invention, in the multicolor heat-sensitive recording medium according to the first or second aspect, the color forming temperature α of the first heat-sensitive coloring layer and the color forming temperature β of the second heat-sensitive coloring layer are α
By satisfying the relationship of ≦ β, aggressive color mixing in which the first thermosensitive coloring layer always develops the color of the second thermosensitive coloring layer in the layered portion of the first thermosensitive coloring layer and the second thermosensitive coloring layer. It can be used reliably, contour color mixing can be reliably prevented, and at the same time, multi-color development according to the purpose can be performed by applying the same energy. Thus, high-speed multicolor printing can be performed.

According to the fourth aspect of the present invention, when the second heat-sensitive coloring layer is heated, the second heat-sensitive coloring layer does not form a color in the disabled area, and printing is performed in a color based on only the coloring of the first heat-sensitive coloring layer. In addition, the first heat-sensitive coloring layer and the second heat-sensitive coloring layer can be printed in a mixed color due to the simultaneous coloring of the first and second heat-sensitive coloring layers in the layered portion other than the disabled area. The printing is performed by positively utilizing the mixed color development of the layer and the second thermosensitive coloring layer, so that the entire printed portion becomes the mixed color development and only the outline portion is the mixed color. Printing becomes possible.

According to the fifth aspect of the present invention, in order to realize the invention of any one of the first to fourth aspects, printing with a wider variety of colors becomes possible.

According to the sixth aspect of the present invention, in order to realize the invention of any one of the first to third aspects, it becomes possible to perform printing in which a single color of the first thermosensitive coloring layer alone is added. And further diversification can be achieved.

According to the seventh aspect of the present invention, the multicolor heat-sensitive recording medium of the first aspect can be manufactured by a simple manufacturing process.

According to the eighth aspect of the invention, it is basically the same as the seventh aspect of the invention, but in particular, by using a commercially available thermosensitive recording paper in which the first thermosensitive coloring layer is originally formed, The process of forming the first thermosensitive coloring layer can be omitted, and the manufacturing process can be further simplified.

According to the ninth aspect of the present invention, the multicolor heat-sensitive recording medium of the fourth aspect can be manufactured by a simple manufacturing process.

According to the tenth aspect of the present invention, it is basically the same as the ninth aspect of the invention, but in particular, by using a commercially available thermosensitive recording paper in which the first thermosensitive coloring layer is originally formed, The process of forming the first thermosensitive coloring layer can be omitted, and the manufacturing process can be further simplified.

According to the eleventh aspect of the present invention, the multicolor printing using the multicolor thermal recording medium according to the first, second, third or fifth aspect can be easily performed by applying the same heating energy. it can.

According to the twelfth aspect, the sixth aspect is provided.
Multicolor printing using the described multicolor thermosensitive recording medium can be easily performed by applying the same heating energy.

According to the thirteenth aspect, according to the fourth aspect,
Alternatively, multicolor printing using the multicolor heat-sensitive recording medium described in 5 can be easily performed by applying the same heating energy.

[Brief description of the drawings]

FIGS. 1A and 1B schematically show a multicolor heat-sensitive recording medium according to Embodiments 1 and 2 of the present invention, wherein FIG. 1A is a cross-sectional view and FIG.

FIGS. 2A and 2B schematically show a multicolor thermosensitive recording medium according to Embodiment 3 of the present invention, wherein FIG. 2A is a cross-sectional view and FIG.

3A and 3B schematically show a multicolor thermal recording medium according to Embodiment 4 of the present invention, wherein FIG. 3A is a cross-sectional view and FIG. 3B is a plan view thereof.

4A and 4B schematically show a multicolor thermal recording medium according to Embodiment 5 of the present invention, wherein FIG. 4A is a cross-sectional view and FIG. 4B is a plan view thereof.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multicolor thermosensitive recording medium 2 Substrate 4 1st thermosensitive coloring layer 5 Disabled area 6 2nd thermosensitive coloring layer

Claims (13)

[Claims] A first heat-sensitive coloring layer formed on the base material; a disabled area in which a coloring function of a part of the first heat-sensitive coloring layer is disabled or blunted; A second thermosensitive coloring layer formed so as to cover the disabled area on the thermosensitive coloring layer over a wider area than the disabled area, and developing a color different from the first thermosensitive coloring layer. A multicolor heat-sensitive recording medium characterized by the above-mentioned. 2. The multicolor heat-sensitive layer according to claim 1, wherein the first heat-sensitive color-forming layer is formed so as to form a color when the second heat-sensitive color-forming layer is colored. recoding media. 3. When each of the first heat-sensitive coloring layers has a color-forming temperature of α and the second heat-sensitive coloring layer has a color-forming temperature of β, each heat-sensitive coloring layer is formed so as to satisfy the relationship α ≦ β. 3. The multicolor heat-sensitive recording medium according to claim 1, wherein: 4. A base material; a first thermosensitive coloring layer formed on the base material; and a second thermosensitive coloring layer formed on the first thermosensitive coloring layer and having a different color from the first thermosensitive coloring layer. A multicolor heat-sensitive recording medium, comprising: a thermosensitive coloring layer; and a disabled area in which a coloring function of a part of the second thermosensitive coloring layer is disabled or blunted. 5. A plurality of the first thermosensitive coloring layer and the second thermosensitive coloring layer are formed in different regions on the base material, and at least one of the first thermosensitive coloring layers or the second thermosensitive coloring layers. 5. The multicolor heat-sensitive recording medium according to claim 1, wherein one of the colors to be developed is different. 6. The multicolor thermosensitive recording medium according to claim 1, wherein the first thermosensitive coloring layer has a region where the second thermosensitive coloring layer is not laminated. 7. A step of forming a first thermosensitive coloring layer on one surface of a substrate, and a step of forming a disabled area for disabling or dulling a coloring function of a part of the first thermosensitive coloring layer; The second thermosensitive coloring layer is formed by using a thermosensitive coloring material that develops a color different from that of the first thermosensitive coloring layer so as to cover the disabled area on the first thermosensitive coloring layer over a wider area than the disabled area. Forming a multicolor thermal recording medium. 8. A step of forming a disabled region for disabling or dulling a color-forming function of a partial region of the first thermosensitive coloring layer formed on one surface of the base material; Forming a second heat-sensitive coloring layer so as to cover the disabled area on the first heat-sensitive coloring layer over a wider area than the disabled area using a heat-sensitive coloring material that develops a different color. A method for producing a multicolor thermosensitive recording medium, comprising: 9. A step of forming a first thermosensitive coloring layer on one surface of a substrate, a step of forming a second thermosensitive coloring layer on the first thermosensitive coloring layer, and a step of forming a part of the second thermosensitive coloring layer. Forming a disabling region for disabling or dulling the color-forming function. 10. A step of forming a second thermosensitive coloring layer on a first thermosensitive coloring layer formed on one surface of a substrate, and disabling or dulling a coloring function of a part of the second thermosensitive coloring layer. Forming a disabled region. 11. The multi-color thermosensitive recording medium according to claim 1, 2, 3 or 5, wherein a layered portion of said first thermosensitive coloring layer and said second thermosensitive coloring layer is mixed and colored by heating by a heating means. Multicolor heat-sensitive printing, wherein printing is performed, and in the second heat-sensitive coloring layer portion on the disabled area, printing is performed by heating the heating means with a single color of the second heat-sensitive coloring layer. Printing method using a recording medium. 12. The multi-color heat-sensitive recording medium according to claim 6, wherein the first heat-sensitive color-forming layer and the second heat-sensitive color-forming layer are printed by mixed-color printing by heating by a heating means in a laminated portion. In the second thermosensitive coloring layer portion on the disabled area, printing by monochromatic coloring of the second thermosensitive coloring layer is performed by heating by the heating means, and the second thermosensitive coloring layer is printed by the second thermosensitive coloring layer.
A printing method using a multi-color heat-sensitive recording medium, wherein printing is performed by a single color of the first heat-sensitive color forming layer by heating by the heating means in an area where the heat-sensitive color forming layer is not laminated. 13. The multi-color thermosensitive recording medium according to claim 4, wherein printing by mixed color development is performed by heating with a heating means in a laminated portion of the first thermosensitive coloring layer and the second thermosensitive coloring layer. A multicolor heat-sensitive recording medium characterized in that printing is performed in a monochromatic color of the first heat-sensitive coloring layer by heating by the heating means in the disabled area of the second heat-sensitive coloring layer. Printing method.