JPH11151856A - Reversible thermal recording material and image recording/erasing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reversible thermal recording material which indicates little deformation by laser beams and is capable of formation or erasure of highly contrast highly sensitive recording image and an image recording/erasing method. SOLUTION: A photothermal conversion layer 3, a reversible thermal recording layer 2, and a photothermal conversion layer are laminated in turn on a support 1. Or, A protective layer as the outermost layer, the reversible thermal recording layer, and the photothermal conversion layer are provided, and an air layer is formed between the protective layer and the reversible thermal recording layer or the photothermal conversion layer. Or, by forming the reversible thermal recording layer and the photothermal conversion layer on a foamed polyester film support of 20-50% void ratio, or, in a reversible thermal recording material in which the photothermal conversion layer and the reversible thermal recording layer are formed on one surface of a transparent film, laser beams 5 are emitted from the other surface side of the transparent film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reversible thermosensitive recording material capable of forming or erasing an image by heating, and more particularly to a reversible thermosensitive recording material capable of forming or decoloring an image by irradiating a laser beam. Image recording
It relates to an erasing method.

[0002]

2. Description of the Related Art In recent years, reversible thermosensitive recording materials which can form a temporary image and erase the color of the image when it is no longer needed have attracted attention. A typical example thereof is a reversible thermosensitive recording material using a colorless or light-colored leuco dye and a reversible developer that causes the leuco dye to develop color by heating, and then reheat and decolorize. Are known. Examples of such reversible thermosensitive recording materials include JP-A-6-210954 and JP-A-6-171.
225, JP-A-7-68933, JP-A-7-6893
JP-A-68934 discloses a reversible developer capable of recording and erasing an image with good contrast and capable of maintaining a stable image over time in an environment of daily life.

[0003] However, such a conventional reversible thermosensitive recording material, when repeatedly recording and erasing an image by heating,
In particular, when a thermal head is used, the surface is rubbed while being heated, so that a scratch is generated on the surface of the recording layer. On the other hand, in JP-A-6-34473 and JP-A-8-156410, a protective layer is provided on the surface of such a reversible thermosensitive recording material to reduce scratches on the surface of the recording layer when a thermal head is used. It has been proposed. However, simply providing a protective layer on a conventional reversible thermosensitive recording material may not be sufficient when the number of recording and erasing operations is increased.

[0004] When recording and erasing are repeated by a method in which heat and pressure are applied to the reversible thermosensitive recording layer at the same time as in a thermal head, the reversible thermosensitive recording layer is subjected to temperature and pressure to form a reversible thermochromic composition. There were problems such as elution and destruction of the layer to lower the recording density. As a method of reducing such deterioration due to the thermal head, Japanese Patent Application Laid-Open No. 57-82088 discloses a method of dispersing an organic low-molecular substance such as a higher fatty acid in a resin base material such as a vinyl chloride-vinyl acetate copolymer. A method is disclosed in which, in a reversible thermosensitive recording material, carbon black is contained in a layer adjacent to a recording layer and recording is performed by a laser beam. This enables non-contact printing, but since the carbon black itself is black, the entire image becomes gray and it is difficult to obtain an effective image contrast. JP-A 64-14077 discloses a reversible thermosensitive recording material in which a low-molecular organic material such as a higher fatty acid is dispersed in a resin base material such as a vinyl chloride-vinyl acetate copolymer. Although a method using a dye has been proposed, the contrast of an image is still low because the infrared absorbing dye also absorbs visible light.

[0005]

SUMMARY OF THE INVENTION A reversible thermosensitive recording material capable of recording and erasing an image by heating has a small deformation by a laser beam and has a high contrast and high sensitivity. To provide a recording material and an image recording / erasing method.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted research to solve this problem, and as a result, have reached the invention of the reversible thermosensitive recording material of the present invention. That is, the reversible thermosensitive recording material of the present invention, on a support, a light-to-heat conversion layer containing a light-to-heat conversion material as a main component, usually a colorless or light-colored leuco dye, and heat the leuco dye by heating to reheat the leuco dye. A reversible thermosensitive recording material characterized in that a reversible thermosensitive recording layer containing a reversible color developing agent to be decolorized and a photothermal conversion layer mainly containing a photothermal conversion material are sequentially laminated.

Further, the reversible thermosensitive recording material of the present invention contains, on a support, a colorless or pale-colored leuco dye and a reversible developer which develops the color of the leuco dye by heating and decolorizes it by reheating. A reversible thermosensitive recording layer, a photothermal conversion layer mainly containing a photothermal conversion material, and a reversible thermosensitive recording layer containing a reversible developer.

The reversible thermosensitive recording material of the present invention generally comprises a reversible thermosensitive recording material containing a colorless or pale-colored leuco dye and a reversible color developer which forms the leuco dye by heating and reheats the decolored color. Having a recording layer and a light-to-heat conversion layer containing a light-to-heat conversion material as a main component, forming an air layer between the reversible thermosensitive recording layer and a support located on one side of the light-to-heat conversion layer. And a reversible thermosensitive recording material.

Further, the reversible thermosensitive recording material of the present invention has a protective layer on the outermost layer and usually forms a colorless or pale-colored leuco dye by heating to form the leuco dye, and reheats the leuco dye to erase the color. A reversible heat-sensitive recording layer containing a color developer and a light-to-heat conversion layer containing a light-to-heat conversion material as main components. It is a reversible thermosensitive recording material characterized by forming an air layer.

Further, the reversible thermosensitive recording material of the present invention contains a colorless or pale-colored leuco dye and a reversible color developer which develops the leuco dye by heating and decolorizes the reheated dye by heating. A reversible thermosensitive recording layer and a light-to-heat conversion layer containing a light-to-heat conversion material as main components.
A reversible thermosensitive recording material characterized by being a foamed polyester film of 0 to 50%.

Further, the image recording / erasing method according to the present invention comprises:
On one surface of the transparent film, a light-to-heat conversion layer containing a light-to-heat conversion material as a main component, a colorless or light-colored leuco dye, and a reversible color developer that develops the leuco dye by heating and deheats the color by reheating the leuco dye. Using the above-mentioned reversible thermosensitive recording material provided with a reversible thermosensitive recording layer, and recording or erasing an image by heat generated by irradiating a laser beam from the other side of the transparent film.・ This is the erasing method.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a reversible thermosensitive recording material utilizing a reaction between an electron donating dye precursor such as a leuco compound and a reversible developer, a photothermal conversion material having a photothermal conversion material as a main component is used as a support. It has been found that by sequentially laminating a layer, a reversible thermosensitive recording layer, and a light-to-heat conversion layer, it is possible to form or erase a recorded image with high contrast and high sensitivity.

Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a sectional view showing a reversible thermosensitive recording material according to a first embodiment of the present invention. Here, the principle of an image recording or erasing method is shown. Reference numeral 1 denotes a support made of a polyethylene terephthalate sheet, paper, or the like. The light-to-heat conversion layer 3, the reversible thermosensitive recording layer 2, and the light-to-heat conversion layer 3 are sequentially laminated on the upper surface. A laser light 5 is irradiated from a laser light source 4, the light is focused on the photothermal conversion layer 3 by a lens 6, and the focused portion is caused to generate heat. Do.

For recording or erasing on such a reversible thermosensitive recording layer, it is preferable to heat the reversible thermosensitive recording layer so as to have a uniform temperature distribution. When heating by light irradiation with a laser or the like, if the irradiation time is extremely short, only a part of the reversible thermosensitive recording layer may be heated. In addition, even if the light irradiation is sufficient, when the temperature gradient in the recording layer is severe and the temperature distribution is uneven, it becomes difficult to control the temperature. Insufficient density can be obtained or erasure is insufficient.

Thus, it is important that the temperature of the reversible thermosensitive recording layer is controlled within a certain temperature range. In order for the heat generated in the light-to-heat conversion layer to be transmitted to the reversible thermosensitive recording layer by light irradiation so that the recording portion falls within the temperature range of color development or erasure, the recording layer must be in contact with one light-to-heat conversion layer. In some configurations, heat is transferred from one side only,
The temperature distribution is large and it is difficult to heat uniformly even after long-time light irradiation. In the reversible thermosensitive recording material of the present invention, since there are light-to-heat conversion layers on both sides of the recording layer, part of the incident light is absorbed by the upper light-to-heat conversion layer, and part of the remaining light is part of the lower light-to-heat conversion layer. Is absorbed by. The incident light reflected there is again absorbed by the upper light-to-heat conversion layer. Therefore, since heat is transmitted from both light-to-heat conversion layers provided on both sides of the recording layer, a uniform temperature distribution is easily obtained, and recording can be performed with lower energy irradiation than when a light-to-heat conversion layer is provided on one side. High-sensitivity, high-contrast recording with little unevenness in color density. When erasing a recorded image, it is even more important to maintain the inside of the reversible thermosensitive recording layer in a constant temperature range, and by maintaining the reversible thermosensitive recording layer in the erasing temperature range, good image erasing becomes possible. Become. The ratio of light absorption between the upper light-to-heat conversion layer and the lower light-to-heat conversion layer needs to be determined in consideration of the configuration of the entire recording material, the thermophysical properties of the material used, and the temperature distribution determined by the light irradiation conditions.

As a method for controlling the temperature in the reversible thermosensitive recording layer within a certain range, a reversible thermosensitive recording layer on a support, a photothermal conversion layer mainly containing a photothermal conversion material, a reversible thermosensitive recording layer, It is also effective to sequentially stack the layers. It has been found that this makes it possible to form or erase a recorded image with high contrast and high sensitivity. FIG. 2 is a sectional view showing a reversible thermosensitive recording material according to a second embodiment of the present invention. 1
Is a support made of polyethylene terephthalate sheet, paper or the like. On the upper surface thereof, a reversible thermosensitive recording layer 2, a light-to-heat conversion layer 3, and a reversible thermosensitive recording layer 2 are sequentially laminated. A laser light 5 is irradiated from a laser light source 4, the light is focused on the photothermal conversion layer 3 by a lens 6, and the focused portion is caused to generate heat. Do. In the reversible thermosensitive recording material having such a layer structure, the heat generated in the photothermal conversion layer by light irradiation is transmitted to the reversible thermosensitive recording layer in both the vertical direction, so that the heat does not escape to the base film and the like, so that the photothermal conversion The heat generated in the layer can be fully utilized. This makes it possible to obtain a high contrast between the recorded image and the image with low energy.

As a method for controlling the temperature in the reversible thermosensitive recording layer to be within a certain range, the thermoreversible recording layer includes a reversible thermosensitive recording layer and a light-to-heat conversion layer. It is also effective to form an air layer between the support and the support located on one side. This allows for high contrast,
It has been found that a high-sensitivity recorded image can be formed or erased.

FIG. 3 is a sectional view showing a reversible thermosensitive recording material according to a third embodiment of the present invention. Reference numeral 1 denotes a support made of a polyethylene terephthalate sheet, paper, or the like. An air layer 7, a support portion 8, a light-to-heat conversion layer 3, and a reversible thermosensitive recording layer 2 are sequentially stacked on the upper surface. Then, a laser beam is irradiated from a laser light source, and the laser beam is condensed on the photothermal conversion layer 3 by a lens. In the reversible thermosensitive recording material having such a layer structure, since the air layer acts as a heat insulating layer, heat generated in the light-to-heat conversion layer by light irradiation is transmitted to the reversible thermosensitive recording layer in the upward direction with high efficiency. Heat hardly escapes to the body and the like, and the heat generated in the light-to-heat conversion layer can be sufficiently utilized. This makes it possible to obtain a high contrast between the recorded image and the image with low energy.

As a method for controlling the temperature in the reversible thermosensitive recording layer within a certain range, a protective layer is provided on the outermost layer, and a reversible thermosensitive recording layer and a light-to-heat conversion layer are provided on the support side. It is also effective to form an air layer between any one of the reversible thermosensitive recording layer and the light-to-heat conversion layer and the protective layer. It has been found that this makes it possible to form or erase a recorded image with high contrast and high sensitivity.

FIG. 4 is a sectional view showing a reversible thermosensitive recording material according to a fourth embodiment of the present invention. Reference numeral 1 denotes a support made of a polyethylene terephthalate sheet, paper, or the like. A reversible thermosensitive recording layer 2, a light-to-heat conversion layer 3, an air layer 7, a support portion 8, and a protective layer 9 are sequentially stacked on the upper surface. Then, a laser beam is irradiated from a laser light source, and the laser beam is condensed on the photothermal conversion layer 3 by a lens. In the reversible thermosensitive recording material having such a layer structure, since the air layer acts as a heat insulating layer, heat generated in the photothermal conversion layer by light irradiation is transmitted to the reversible thermosensitive recording layer in the direction of the support with high efficiency. Heat hardly escapes to the protective layer and the like, and the heat generated in the light-to-heat conversion layer can be sufficiently utilized. This makes it possible to obtain a high contrast between the recorded image and the image with low energy. Further, recording or erasing by a contact method such as a thermal head can be made difficult, which is effective in preventing falsification of recording.

As a method for controlling the temperature in the reversible thermosensitive recording layer within a certain range, a foamed polyester film having a reversible thermosensitive recording layer and a light-to-heat conversion layer and having a porosity of 20 to 50% as a support is used. It is also effective to use. It has been found that this makes it possible to form or erase a recorded image with high contrast and high sensitivity.

FIG. 5 is a sectional view showing a reversible thermosensitive recording material according to a fifth embodiment of the present invention. 1 has a porosity of 20 to
The support is a 50% foamed polyester sheet, and a light-to-heat conversion layer 3, a reversible thermosensitive recording layer 2, and a protective layer 9 are sequentially laminated on the support. Then, a laser beam is irradiated from a laser light source, and the laser beam is condensed on the photothermal conversion layer 3 by a lens. In the reversible thermosensitive recording material having such a layer structure, the heat generated in the light-to-heat conversion layer by light irradiation is transmitted to the reversible thermosensitive recording layer with high efficiency because the foamed polyester film serving as the support acts as a heat insulating layer. The heat loss is small, and the heat generated in the light-to-heat conversion layer can be sufficiently utilized. This makes it possible to obtain a high contrast between the recorded image and the image with low energy. When the porosity of the foamed polyester film used is less than 20%, the heat insulating property is insufficient, and when the porosity is more than 50%, the strength of the film is insufficient.

As a method for recording and erasing an image, a reversible thermosensitive recording method is provided in which a transparent film is provided with a photothermal conversion layer mainly composed of a photothermal conversion material and a reversible thermosensitive recording layer containing a reversible developer. It has been found that, when a material is used to record or erase an image by heat generated by irradiating a laser beam from the other side of the transparent film, clear recording can be obtained even when used repeatedly over a long period of time. FIG. 6 is a sectional view showing a reversible thermosensitive recording material according to a sixth embodiment of the present invention. 1 is a transparent film support made of a polyethylene terephthalate sheet or the like. The light-to-heat conversion layer 3, the reversible thermosensitive recording layer 2, and the light-to-heat conversion layer 3 are sequentially laminated on the upper surface. A laser beam 5 from a laser light source 4 is radiated from the support side, and the laser beam is condensed on the light-to-heat conversion layer 3 by a lens 6, and the condensed portion is heated. Alternatively, erasure is performed.

In general, the light-to-heat conversion material may be colored. In a layer configuration in which the light-to-heat conversion layer is disposed on the upper surface of the reversible heat-sensitive recording layer, the recording of the reversible heat-sensitive recording layer is performed by coloring. Occasionally, the contrast of the recorded image is reduced, which makes it difficult to read the image. Further, in the layer configuration in which the reversible thermosensitive recording layer is opaque and is disposed above the light-to-heat conversion layer, the irradiated light is concealed by the reversible thermosensitive recording layer and does not sufficiently transmit to the light-to-heat conversion layer, and the recorded image is In some cases, the reading of an image becomes difficult. In such a case, in order to improve the contrast of the recorded image, it is preferable that the light-to-heat conversion layer is below the reversible thermosensitive recording layer, or that the reversible thermosensitive recording layer has transparency. Even in such a case, the recording sensitivity tends to decrease, the temperature distribution becomes uneven, and the reversible thermosensitive recording layer is easily damaged. In order to solve such problems, it is preferable to use an image recording / erasing method in which a transparent film is used as a support, and light such as laser light is irradiated through the support from the transparent film side without the reversible thermosensitive recording layer.

When a transparent film is used for the support of the reversible thermosensitive recording material, the thickness is 500 μm.
The thickness is preferably 200 μm or less, and more preferably a thickness enough to withstand processing such as coating. As such a transparent film, a film having good heat resistance such as PET, polyetherimide, polyetheretherketone, polysulfone, polyphenylenesulfide, polyarylate, polyethersulfone, polycarbonate, polyethylenenaphthalate, and polyimide is preferable. The same applies when the support is not transparent, glass,
Plastic sheets, paper, etc. are used. As the plastic sheets, PET, polysulfone, polyimide,
Examples include polycarbonate and PBT. The thickness is preferably about 2 μm to 1 mm, and 4 to 500 μm
m is more preferred.

The light-to-heat conversion layer absorbs light such as a laser beam and converts it into heat, and the adjacent heat-sensitive recording layer is colored by the generated heat to record or erase. A dye or the like having a large absorption coefficient with the laser beam to be used is mixed with a resin or the like and used. For example, photothermal conversion materials suitable for semiconductor lasers are 780-830n.
Polymethine dyes such as cyanine and pyrylium dyes, phthalocyanine dyes such as copper phthalocyanine, naphthalocyanine dyes, dithiol metal complex dyes, and the like, which have a structure having an absorption coefficient of 10 ⁴ or more at the wavelength of m Near infrared absorbing dyes such as phenylmethane dyes, aminium dyes, and diimmonium dyes can be used.

These absorbing dyes may be used in combination with a resin and may be any as long as they can be retained, and examples thereof include the following. As the thermoplastic resin, ethylene-
PVC copolymer resin, ethylene-vinyl acetate, ethylene-vinyl acetate-vinyl chloride graft polymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, chlorinated polypropylene resin, chlorinated polyethylene resin, vinyl acetate, phenoxy resin, Butadiene resin, petroleum resin, fluorine resin, polyamide resin, polyimide resin, polyamideimide resin, polyarylate resin, polyetherimide, polyetheretherketone, polyethylene, polyethylene oxide, polycarbonate, polycarbonate polystyrene, polysulfone, polyparamethylstyrene, poly Allylamine, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl ether, polyvinyl butyral,
Examples include polyvinyl acetal, polyvinyl formal, polyphenylene ether, polypropylene, polymethylpentene, methacrylic resin, acrylic resin, and various polyol resins.

Examples of the thermosetting resin include epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, furan resin, polyimide, polyurethane, maleic resin, melamine resin, and urea. There are resins and the like.

Each of these resins may be copolymerized, or two or more of them may be used in combination. The ratio of the light-to-heat conversion material to the resin is preferably 95: 5 to 5:95, and 90: 1.
0 to 10:90 is more preferable. Further, a functional group such as a hydroxyl group or a carboxyl group may be provided to these resins as necessary, and the resin may be crosslinked by heat, ultraviolet rays, or electron beams using a crosslinking agent. In the case of crosslinking by ultraviolet rays, a photopolymerization initiator is required.

Specific examples of the crosslinking agent include isocyanates and the following acrylate monomers. Hexanediol diacrylate (HDDA), neopentyl glycol diacrylate (NPGDA), diethylene glycol diacrylate (DEGDA), tripropylene glycol diacrylate (TPGDA), polyethylene glycol diacrylate (PEG400D)
A), neopentyl glycol hydroxypivalate (HPNDA), diacrylate of neopentyl glycol adipate, diacrylate of ε-caprolactan adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) )
-5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclodecane dimethylol diacrylate, ε-caprolactone adduct of tricyclodecane dimethylol diacrylate, digrindyl ether of 1,6-hexanediol Diacrylate, trimethylolpropane triacrylate (TMPT
A), propionic acid / dipentaerythritol triacrylate, hydroxypivalaldehyde-modified dimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaacrylate of propionic acid / dipentaerythritol, dipentaerythritol hexaacrylate (DPHA), dipenta Ε-caprolactone adduct of erythritol hexaacrylate (DPCA-20, 30, 60), diacrylate of propylene oxide adduct of neopentyl glycol, diacrylate of ethylene oxide adduct of neopentyl glycol hydroxypivalate, polypropylene of trimethylolpropane Triacrylate of oxide adduct, triacrylate of higher fatty acid ester of pentaerythritol Pentaacrylate of 1,3-dioxanepentanol, hexaacrylate of ε-caprolactone adduct of dipentaerythritol, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, ε-caprolactone addition of tricyclodecane dimethylol Diacrylate.

The light source of the light irradiating device is not particularly limited as long as it emits light and is absorbed by the light-to-heat conversion layer to generate heat. Further, a semiconductor laser is particularly preferably used because of its small size.

The leuco dye of the reversible thermosensitive recording layer in the present invention is typically represented by those used for pressure-sensitive recording paper or thermosensitive recording paper, but is not particularly limited. Specific examples include the following, but the present invention is not limited thereto.

(1) Triphenylmethane compounds 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide,

(2) Fluoran compounds 3-diethylamino-6-methylfluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3
-Diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6
-Methyl-7- (m-trifluoromethylanilino) fluoran, 3-diethylamino-6-methyl-7- (o
-Chloroanilino) fluoran, 3-diethylamino-
6-methyl-7- (p-chloroanilino) fluoran,
3-diethylamino-6-methyl-7- (o-fluoroanilino) fluoran, 3-diethylamino-6-methyl-7-n-octylanilinofluoran, 3-diethylamino-6-methyl-7-n-octyl Aminofluoran, 3-diethylamino-6-methyl-7-benzylanilinofluoran, 3-diethylamino-6-methyl-7-dibenzylanilinofluoran, 3-diethylamino-6-chloro-7-methylfluoran , 3-diethylamino-6-chloro-7-anilinofluoran, 3-
Diethylamino-6-chloro-7-p-methylanilinofluoran, 3-diethylamino-6-ethoxyethyl-7-anilinofluoran, 3-diethylamino-7-
Methylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7- (m-trifluoromethylanilino) fluoran, 3-diethylamino-
7- (o-chloroanilino) fluoran, 3-diethylamino-7- (p-chloroanilino) fluoran, 3-
Diethylamino-7- (o-fluoroanilino) fluoran, 3-diethylamino-benzo [a] fluoran,
3-diethylamino-benzo [c] fluoran, 3-dibutylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3-dibutylamino-6-methyl-7- (o-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluoran, 3-dibutylamino-6-methyl-7- (o
-Fluoroanilino) fluoran, 3-dibutylamino-6-methyl-7- (m-trifluoromethylanilino) fluoran, 3-dibutylamino-6-methyl-chlorofluoran, 3-dibutylamino-6-ethoxy Ethyl-7-anilinofluoran, 3-dibutylamino-
6-chloro-7-anilinofluoran, 3-dibutylamino-6-methyl-p-methylanilinofluoran, 3
-Dibutylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-fluoroanilino) fluoran, 3-n-dipentylamino-6-methyl-7-aminofluoran, 3-n- Dipentylamino-6-chloro-7-aminofluoran, 3-n-dipentylamino-7- (p-chloroanilino) fluoran,
3-n-dipentylamino-7- (m-trifluoromethylanilino) fluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-methyl-N
-Propylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-cyclohexylamino)
-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-xylamino) -6-methyl-7- (p-chloroanilino) fluoran, 3- (N-ethyl-p-toluidino) -6 -Methyl-7-anilinofluoran,
3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-
Isoamylamino) -6-chloro-7-anilinofluoran, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran, 3-
(N-ethyl-N-isobutylamino) -6-methyl-
7-anilinofluoran, 3- (N-ethyl-N-ethoxypropylamino) -6-methyl-7-anilinofluoran, 3-cyclohexylamino-6-chlorofluoran, 2- (4-oxahexyl ) -3-Dimethylamino-6-methyl-7-anilinofluoran, 2- (4-
Oxahexyl) -3-diethylamino-6-methyl-
7-anilinofluoran, 2- (4-oxahexyl)
-3-Dipropylamino-6-methyl-7-anilinofluoran, 2-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-methoxy-
6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-chloro-3-methyl-6-p- (p
-Phenylaminophenyl) aminoanilinofluoran, 2-chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-nitro-6-p-
(P-diethylaminophenyl) aminoanilinofluoran, 2-amino-6-p- (p-diethylaminophenyl) aminoanilinofluoran, 2-diethylamino-6-p- (p-diethylaminophenyl) aminoanilinofur Oran, 2-phenyl-6-methyl-6-p-
(P-phenylaminophenyl) aminoanilinofluoran, 2-benzyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-hydroxy-
6-p- (p-phenylaminophenyl) aminoanilinofluoran, 3-methyl-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 3-diethylamino-6-p- (p-diethylamino Phenyl) aminoanilinofluoran, 3-diethylamino-6-p
-(P-dibutylaminophenyl) aminoanilinofluoran, 2,4-dimethyl-6-[(4-dimethylamino) anilino] -fluoran

(3) Fluorene compounds 3,6,6'-tris (dimethylamino) spiro [fluorene-9,3'-phthalide], 3,6,6'-tris (diethylamino) spiro [fluorene-9, 3'-phthalide]

(4) Divinyl compound 3,3-bis- [2- (p-dimethylaminophenyl)
-2- (p-methoxyphenyl) ethenyl] -4,5
6,7-tetrabromophthalide, 3,3-bis- [2-
(P-dimethylaminophenyl) -2- (p-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide, 3,3-bis- [1,1-bis (4-pyrrolidinophenyl) ) Ethylene-2-yl] -4,5,6,7
-Tetrabromophthalide, 3,3-bis- [1- (4-
Methoxyphenyl) -1- (4-pyrrolidinophenyl)
Ethylene-2-yl] -4,5,6,7-tetrabromophthalide

(5) Other compounds 3- (4-diethylamino-2-ethoxyphenyl)-
3- (1-ethyl-2-methylindol-3-yl)
-4-azaphthalide, 3- (4-diethylamino-2-
Ethoxyphenyl) -3- (1-octyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4
-Cyclohexylamino-2-methoxyphenyl) -3
-(1-ethyl-2-methylindol-3-yl)-
4-azaphthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3,6-bis (diethylamino) fluoran-γ- (3′-nitro)
Anilinolactam, 3,6-bis (diethylamino) fluoran-γ- (4′-nitro) anilinolactam,
1,1-bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2,
2-dinitrileethane, 1,1-bis- [2 ′, 2 ′,
2 ″, 2 ″ -tetrakis- (p-dimethylaminophenyl) -ethenyl] -2-β-naphthoylethane, 1,1
-Bis- [2 ′, 2 ′, 2 ″, 2 ″ -tetrakis- (p
-Dimethylaminophenyl) -ethenyl] -2,2-diacetylethane, bis- [2,2,2 ', 2'-tetrakis- (p-dimethylaminophenyl) -ethenyl]-
Methylmalonic acid dimethyl ester, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole- 3- (yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2
-Phenylindol-3-yl) phthalide, 3,3-
Bis (1,2-dimethylindol-3-yl) -5
Dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylamino Phthalide, 3,3-bis (2
-Phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-
(4,4'-bis (dimethylaminophenyl) benzhydryl benzyl ether, N-chlorophenylleucouramine, N-2,4,5 -Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, such as trichlorophenyl leuco auramine,
3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3'-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 3-propyl Spirobenzopyran and the like.

The above usually colorless to pale leuco dyes may be used alone or in combination of two or more.

The reversible color developer used in the reversible thermosensitive recording layer of the present invention includes, for example, those represented by the following general formula 1, but is not limited thereto. The compound is not particularly limited as long as it is a compound capable of causing a significant change in color tone.
An electron-accepting compound represented by the following general formula 1 is preferably used, including a reversible developer composed of a phenolic compound proposed in JP-A-954.

[0040]

Embedded image

In the formula, n represents 1, 2 or 3. m is 0,
Represents 1 or 2. Q represents an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. The ring represented by A is an aromatic ring. X is a divalent group bonded to the aromatic ring represented by A via a nitrogen atom, a divalent group containing two or more heteroatoms, a nitrogen atom, and an aromatic ring represented by A and having 1 carbon atom. It represents a divalent group bonded by the above hydrocarbon group, or a divalent group containing an unsaturated bond or an aromatic ring. R represents an aliphatic hydrocarbon group. The total number of the atoms included in X and R excluding the hydrogen atoms and the atoms constituting the aromatic ring is 8 or more. Specific examples of the substituent represented by Q include a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, t-pentyl group, 2-ethylhexyl group, cyclohexyl group, aliphatic hydrocarbon group such as allyl group, methoxy group, ethoxy group, n- Propyloxy group,
Examples include an alkoxy group such as i-propyloxy group, n-butyloxy group and n-octyloxy group, and a halogen atom such as fluorine, chlorine, bromine and iodine.

Examples of the divalent group in which X is bonded to the aromatic ring represented by A via a nitrogen atom include -NHCO-,-
NH-, -NHCONH-, -NHCONHNH-,-
N = CH -, - N = N -, - NHSO 2 -, - NHCO
_{(P-C 6 H 4)} NHCO -, - NHCO (p-C 6 H 4)
NHCONH -, - NHCO (p- C 6 H 4) NHCOC
ONH -, - NHCO (p- C 6 H 4) CONH -, - N
_{HCO (p-C 6 H 4} ) CONHNHCO -, - NHCO
_{(P-C 6 H 4)} OCONH -, - NHCO (p-C
_{6 H 4) NHCOO -, -} NHCOCH 2 (m-C 6 H 4)
_{NHCO -, - NHCOCH 2 (p} -C 6 H 4) NHCO
_{-, - NHCOCH 2 (p-} C 6 H 4) NHCONH-,
_{-NHCOCH 2 (p-C 6 H} 4) NHCOCONH-,
_{-NHCOCH 2 (p-C 6 H} 4) CONH -, - NHC
_{OCH 2 (p-C 6 H} 4) CONHNHCO -, - NHC
_{OCH 2 (p-C 6 H} 4) CONHNHCONH -, - N
HCOCH ₂ (p-C ₆ H ₄ ) CONNHNHCOO-,-
_{NHCOCH 2 (p-C 6 H} 4) OCONH -, - NHC
_{OCH 2 (p-C 6 H} 4) NHCOO -, - NHCOCH 2
_{CH 2 (p-C 6 H} 4) NHCO -, - NHCOCH 2 CH
_{2 (p-C 6 H 4} ) NHCONH -, - NHCOCH 2 CH
_{2 (m-C 6 H 4} ) NHCOO -, - NHCOCH 2 CH 2
_{(P-C 6 H 4)} NHCOCONH -, - NHCOCH 2
_{CH 2 (p-C 6 H} 4) CONH -, - NHCOCH 2 CH
_{2 (p-C 6 H 4} ) CONHNHCO -, - NHCOCH 2
_{CH 2 (p-C 6 H} 4) CONHNHCONH- the like. When a hydrogen atom is bonded to the nitrogen atom, the hydrogen atom may be substituted with an aliphatic hydrocarbon group such as a methyl group or a cyclohexyl group. Among these, a urea bond is more preferable in terms of decoloring property and image density. Interestingly, when X is -CONH-, -COO-, -S-
Either the decoloring property or the image density becomes unsatisfactory.

Examples of the divalent group containing two or more hetero atoms as X include -SO ₂ NH-, -SS-, -CON
HNH -, - CONHNHCO -, - CONHCH 2 C
O -, - CONHNHCOO -, - CONHCH 2 CO
O -, - CONHNHCONH -, - CONHCH 2 C
ONH-, -CONHNHCONHNH-, -CONH
_{CH 2 CONHNH -, - CH 2} NHCONH -, - CH
₂ CH ₂ NHCONH-, -CH ₂ CH ₂ CH ₂ NHCON
_{H -, - CH 2 CH 2} CH 2 NHCONH -, - SCH 2 C
_{ONH -, - SCH 2 CH 2} CONH -, - S (CH 2) 5
_{CONH -, - S (CH 2} ) 10 CONH -, - S (p-
_{C 6 H 4) CONH -,} - SCH 2 NHCO -, - SCH 2
_{CH 2 NHCO -, - S (} CH 2) 6 NHCO -, - S
_{(P-C 6 H 4)} NHCO -, - SCH 2 NHCONH
_{-, - SCH 2 CH 2 NHCONH} -, - S (CH 2) 6 N
HCONH -, - S (p- C 6 H 4) NHCONH -, -
_{S (CH 2) 1 0 NHCONH} -, - SCH 2 CH 2 NHC
_{OO -, - S (CH 2} ) 6 NHCOO -, - S (p-C 6
_{H 4) NHCOO -, - S} (CH 2) 6 OCONH -, -
_{S (p-C 6 H 4} ) OCONH -, - S (CH 2) 11 OC
_{ONH -, - SCH 2 CH 2} CONH -, - S (CH 2) 5
_{CONH -, - SCH 2 CH 2} NHCO (p-C 6 H 4)
_{-, - SCH 2 CONHNHCO -,} - SCH 2 CH 2 C
_{ONHNHCO -, - S (CH 2} ) 6 CONHNHCO
_{-, - S (CH 2)} 6 CONHNHCO (p-C 6 H 4)
_{-, - S (CH 2)} 10 CONHNHCO -, - S (p-
C ₆ H ₄ ) CONHNHCO-, -SCH ₂ (p-C
_{6 H 4) CONHNHCO -, -} SCH 2 CH 2 NHCOC
_{ONH -, - SCH 2 CH 2} CH 2 NHCOCONH-,
_{-S (CH 2) 11 NHCOCONH -} , - S (p-C 6 H
_{4) NHCOCONH -, - SCH 2} CONHCONH
_{-, - SCH 2 CH 2 CONHCONH} -, - S (p-C
_{6 H 4) CONHCONH -, -} SCH 2 CH 2 NHCON
HCO -, - S (p- C 6 H 4) NHCONHCO -, -
_{SCH 2 CH 2 CONHNHCONH -, -} S (CH 2)
_{10 CONHNHCONH -, - SCH 2 CH} 2 NHNHC
ONH -, - S (p- C 6 H 4) NHNHCONH -, -
_{SCH 2 CH 2 NHCONHNH -, -} S (p-C 6 H 4)
NHCONHNH -, - SCH ₂ CONHCONHNH
_{-, - SCH 2 CH 2 CONHCONHNH} -, - S (C
_{H 2) 10 CONHCONHNH -, -} S (p-C 6 H 4)
CONHNHCONH -, - S (p- C 6 H 4) CONH
CONHNH -, - SCH ₂ CONHCONHNHCO
_{-, - SCH 2 CH 2 CONHCONHNHCO} -, - S
(CH ₂ ) ₁₀ CONHCONHNHCO-, -S (p-
C ₆ H ₄ ) CONHNHCONHCO-, -S (p-C _{6
H 4) CONHCONHNHCO -, - SCH} 2 CONH
_{(CH 2) NHCO -, -} SCH 2 CH 2 CONH (C
_{H 2) NHCO -, - S} (p-C 6 H 4) CONH (C
_{H 2) NHCO -, - S} (CH 2) 10 CONH (CH 2)
_{NHCO -, - SCH 2 CON (} CH 2) NHCONH
_{-, - SCH 2 CH 2 CON} (CH 2) NHCONH-,
—S (CH ₂ ) ₁₀ CONHCONH (CH ₂ ) NHCO
-, - S (p-C 6 H 4) CONH (CH 2) NHCO
_{-, - SCH 2 CH 2 NHCONH} (CH 2) NHCO
_{-, - SCH 2 CH 2 NHCOCH} 2 CONH -, - S
_{(P-C 6 H 4)} NHCONH (CH 2) NHCO -, -
_{S (p-C 6 H 4} ) NHCOCH 2 CONH- , and the like. Specific examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom, a silicon atom, a selenium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a tin atom.

X represents an unsaturated bond or an aromatic ring
Examples of the valent group include -CH = CH-, -CH = N-,
—SO ₂ —, a phenylene group, a group containing a carbon-carbon triple bond, and the like, a group obtained by combining them, and further, on one or both sides thereof, —NHCO
-, -NH-, -NHCONH-, -NHCSNH-,
-N = CH -, - N = N -, - NHSO 2 -, - SO 2 N
A group in which one or two or more linking groups such as H and -S-S- are combined is exemplified. In this case, as a connecting group, other than -CONH-, -O-, -S-, -COO-, -O
Divalent groups such as CO—, —OCOO, —CO—, and —SO ₂ — are also included. X comprises a nitrogen atom, examples of the divalent group linked by an aromatic ring and one or more hydrocarbon group carbon atoms represented by _{A, -CH 2 CONH -, - CH} 2 CH 2
_{CONH -, - CH 2 NHCO -} , - CH 2 CH 2 NHC
_{O -, - CH 2 CH 2} CH 2 NHCO -, - CH 2 CH 2 N
_{HCOO -, - (CH 2)} 6 NHCOO -, - (p-C 6
_{H 4) NHCOO -, - CH} 2 CH 2 OCONH -, -
_{(CH 2) 11 OCONH -,} - (p-C 6 H 4) OCON
_{H -, - CH 2 CH 2} CONHCO -, - (CH 2) 5 CO
_{NHCO -, - CH 2 CH 2} CONHCO (p-C 6 H 4)
_{-, - CH 2 CONHNHCO -,} - CH 2 CH 2 CON
_{HNHCO -, - (CH 2)} 5 CONHNHCO -, -
_{(CH 2) 5 CONHNHCO (p} -C 6 H 4) -, - (C
_{H 2) 10 CONHNHCO -, -} (p-C 6 H 4) CON
_{HNHCO -, - CH 2 (p} -C 6 H 4) CONHNHC
_{O -, - CH 2 CH 2} NHCOCONH -, - CH 2 CH 2
_{CH 2 NHCOCONH -, - (CH} 2) 10 NHCOCO
NH -, - (p-C 6 H 4) NHCOCONH -, - CH
_{2 CONHCONH -, - CH 2 CH} 2 CONHCONH
_{-, - (p-C 6} H 4) CONHCONH -, - CH 2 C
_{H 2 NHCONHCO -, - (p} -C 6 H 4) NHCON
_{HCO -, - CH 2 CH 2} NHCONHNH -, - (p-
_{C 6 H 4) NHCONHNH -,} - CH 2 CH 2 NHNHC
ONH -, - (p-C 6 H 4) NHNHCONH -, - C
_{H 2 CONHNHCONH -, - CH 2} CH 2 CONHN
_{HCONH -, - (CH 2)} 10 CONHNHCONH
_{-, - (p-C 6} H 4) NHNHCO -, - CH 2 CON
_{HCH 2 NHCO -, - CH 2} CH 2 CONHCH 2 NHC
_{O -, - (CH 2)} 10 CONHCH 2 NHCO -, - (p
—C ₆ H ₄ ) CONHCH ₂ NHCO—, —CH ₂ CONH
_{CH 2 NHCONH -, - CH 2} CH 2 CONHCH 2 NH
_{CONH -, - (CH 2)} 10 CONHCH 2 NHCONH
_{-, - (p-C 6} H 4) CONHCH 2 NHCONH-,
_{-CH 2 CH 2 NHCONHCH 2 NHCO -} , - (p-
_{C 6 H 4) NHCONHCH 2 NHCO} -, - CH 2 CH 2
_{NHCOCH 2 CONH -, - (p} -C 6 H 4) NHCO
CH ₂ CONH— and the like.

As the aliphatic hydrocarbon group represented by R,
Hexyl, octyl, nonyl, cyclohexyl, decyl, undecyl, dodecyl, cyclododecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, 16-methylheptadecyl, octadecyl, 9-octadecenyl group, nonadecyl group, eicosyl group, henicosyl group,
Examples include a docosyl group, a tricosyl group, a tetracosyl group, a 2-norbornyl group, a 7,7-dimethylnorbornyl group, a 1-adamantyl group, a cholesteryl group, and a 5-phenylpentyl group. These may be branched, may be polycyclic, and may contain an unsaturated bond. However, it is necessary for the decoloring property that the total number of atoms excluding the atoms constituting the aromatic ring and the hydrogen atom among the atoms included in X and R is 8 or more, particularly 14 or more.

Next, specific examples of the reversible developer preferably used in the present invention will be described, but the present invention is not limited thereto.

4'-hydroxyheptaneanilide, 4 '
-Hydroxy-3-methyloctaneanilide, 4'-hydroxynonadecaneanilide, 3'-hydroxynonadecaneanilide, 4'-hydroxy-10-octadeceneanilide, 15-cyclohexyl-4'-hydroxypentadecaneanilide, 4'- Hydroxy-5-tetradeceneanilide, 3'-cyclohexyl-4'-hydroxyheptadecaneanilide, 3'-allyl-4'-hydroxypentadecaneanilide, 3'-chloro-4'-hydroxyoctadecaneanilide, 3'-hydroxydodecane Anilide, 2 ', 4'-dihydroxyheptadecane anilide,

4'-hydroxy-4-hexylbenzanilide, 4'-hydroxy-4-octadecylbenzanilide, 4'-hydroxy-4-pentadecylaminocarbonylbenzanilide, 4'-hydroxy-4-hexylcarbonylaminobenz Anilide, 4'-hydroxy-4- (heptylthio) benzanilide, 4'-hydroxy-4-octadecyloxybenzanilide, 4 '
-Hydroxy-4-dodecylsulfonylbenzanilide, 4'-hydroxy-4-nonylsulfonyloxybenzanilide, 4'-hydroxy-4-dodecyloxysulfonylbenzanilide, 4'-hydroxy-4-pentadecylaminosulfonylbenzanilide, 4'-hydroxy-4- (N-heptadecylideneamino) benzanilide,

4'-hydroxy-3,4-dioctyloxybenzanilide, 4'-hydroxy-3-octyl-4- (octylthio) benzanilide, 4'-hydroxy-3- (heptadecylthio) -5-pentadecyloxybenz Anilide, 4'-hydroxy-3-heptadecylcarbonylamino-5-dodecylbenzanilide,
4'-hydroxy-3-octadecylaminocarbonyl-5-tetradecylaminocarbonylbenzanilide,
4'-hydroxy-3-octadecylsulfonylamino-5-octadecyloxybenzanilide, 4'-hydroxy-3-heptadecyloxysulfonyl-5-tetradecyloxysulfonylbenzanilide, 4'-hydroxy-3,5-bis ( N-docosylideneamino) benzanilide;

4'-hydroxy-4-octadecylcarbonylaminobenzanilide, 4'-hydroxy-3-
Octadecylcarbonylamino-5-octadecyloxybenzanilide, 3'-allyl-4'-hydroxy-
4-pentadecylbenzanilide, 4'-hydroxy-
3'-methyl-4-nonyloxybenzanilide, 4 '
-Hydroxy-3'-propyl-4-nonadecylcarbonyloxybenzanilide, 3'-butyl-4'-hydroxy-4-octadecyloxycarbonylbenzanilide, 3'-hydroxy-4-pentadecylcarbonyloxybenzanilide, '-Hydroxy-4-nonadecylsulfonylbenzanilide, 3', 4 ', 5'-trihydroxy-4-tetracosylaminosulfonylbenzanilide, 3', 5'-dihydroxy-4-pentacosylaminocarbonylbenz Anilide, 3'-hydroxy-4- (N-dodecylideneamino) benzanilide,
N- [4- (3-hydroxyphenylaminocarbonyl) benzylidene] pentadecylamine;

N-cyclohexyl-4-hydroxybenzhydrazide, N-cyclohexylmethyl-4-hydroxybenzhydrazide, N-cyclohexyl-4-hydroxybenzamide, N-cyclohexylmethyl-4-
Hydroxybenzamide, N-methyl-N-octadecyl-4-hydroxybenzamide, N- (3-methylhexyl) -4-hydroxybenzamide, N-octadecyl-4-hydroxybenzhydrazide, N- (8-octadecenyl) -4- Hydroxybenzamide,

4-hydroxy-4'-dodecylbenzanilide, N-methyl-4-hydroxy-4'-octadecylbenzanilide, 4-hydroxy-4'-octadecyloxybenzanilide, 4-hydroxy-4'-
(Octadecylthio) benzanilide, 4-hydroxy-4'-hexadecylcarbonylbenzanilide, 4-
Hydroxy-4'-heptadecyloxycarbonyloxybenzanilide, 4-hydroxy-4'-dodecyloxycarbonylbenzanilide, 4-hydroxy-4 '
-Heptadecylcarbonyloxybenzanilide, 4-
Hydroxy-4'-cyclohexylaminobenzanilide, 4-hydroxy-4'-octadecylaminobenzanilide,

4-hydroxy-4'-heptadecylcarbonylaminobenzanilide, 4-hydroxy-4'-
Octadecylaminocarbonylbenzanilide, 4-hydroxy-4'-dodecylsulfonylbenzanilide, 4-hydroxy-4'-octadecyloxysulfonylbenzanilide, 4-hydroxy-4'-dodecylsulfonyloxybenzanilide, N-4-hydroxybenzoyl -N'-octadecylidene-1,4-phenylenediamine, N-4- (4-hydroxyphenylcarbonylamino) benzylidenedecylamine, 4-
Hydroxy-4'-tetradecyloxycarbonylaminobenzanilide, 4-hydroxy-4'-octadecylureylenebenzanilide,

3-hydroxy-4'-dodecyloxybenzanilide, N-methyl-4-hydroxy-3'-octadecyloxybenzanilide, 3-hydroxy-
4'-tetradecylbenzanilide, N-methyl-3-
Hydroxy-4'-octadecylbenzanilide, N-
Dodecyl-4-hydroxy-3-methylbenzamide,
3-methoxy-4-hydroxy-4'-octadecyloxybenzanilide, 3-chloro-4-hydroxy-
4'-octadecylbenzanilide, N-octadecyl-4-hydroxy-2,5-dimethylbenzamide, 4
-Hydroxy-4'-octadecyloxy-3'-chlorobenzanilide, 4-hydroxy-3 ', 4'-didecyloxybenzanilide, 4-hydroxy-3'-octadecylamino-4'-octadecyloxybenzanilide, 4-hydroxy-2'-chloro-3 ', 5'-
Didecyloxybenzanilide, 4-hydroxy-
3 ', 4'-dioctadecyloxybenzanilide, 4
-Hydroxy-4'-octyl-3'-methylbenzanilide, 3-hydroxy-4-methyl-4'-tetradecylbenzanilide, N-methyl-4-hydroxy-
3'-octadecylbenzanilide,

4- (N-octadecylsulfonylamino) phenol, 4- (N-methyl-N-octadecylsulfonylamino) phenol, 4- (N-3-methylhexylsulfonylamino) phenol, 4'-hydroxy-4-phenol Cyclohexylbenzenesulfonanilide,
4'-hydroxy-4-octadecyloxybenzenesulfonanilide, 4'-hydroxy-4- (dodecylthio) benzenesulfonanilide, 4'-hydroxy-4
-Hexylcarbonylbenzenesulfonanilide, 4 '
-Hydroxy-4- (8-heptadecenyl) carbonylbenzenesulfonanilide, 4'-hydroxy-4-octyloxycarbonyloxybenzenesulfonanilide, 4'-hydroxy-4-dodecylcarbonyloxybenzenesulfonanilide, 4'-hydroxy-4 -Octadecylaminobenzenesulfoneanilide,

4'-hydroxy-4-heptadecylcarbonylaminobenzenesulfonanilide, 4'-hydroxy-4-dodecylaminocarbonylbenzenesulfonanilide, 4'-hydroxy-4-dodecylsulfonylbenzenesulfonanilide, 4'-hydroxy- 4-octadecyloxysulfonylbenzenesulfonanilide, 4'-hydroxy-4-dodecylsulfonyloxybenzenesulfonanilide, N-dodecylidene-4-
(4-hydroxyphenyl) aminosulfonylaniline, N-4- (4-hydroxyphenylaminosulfonyl) benzylideneoctadecylamine, 4'-hydroxy-4-octyloxycarbonylaminobenzenesulfonanilide, 4'-hydroxy-4-octadecyloxy Carbonylaminobenzenesulfonanilide, 4 '
-Hydroxy-4-octadecylureylenebenzenesulfonanilide,

N-methyl-4'-hydroxy-3-octadecyloxybenzenesulfonanilide, 3'-hydroxy-4-dodecylbenzenesulfonanilide, 3-
Methyl-4- (N-dodecylsulfonamino) phenol, 3'-methoxy-4'-hydroxy-4-octadecyloxybenzenesulfonanilide, 3'-chloro-
4'-hydroxy-4-octadecylbenzenesulfonanilide, 4'-hydroxy-2,5-dimethyl-4-
Octadecylbenzenesulfonanilide, 3-methyl-
4- (N-octadecylsulfonamino) phenol,
4'-hydroxy-3,4-dioctadecyloxybenzenesulfoneanilide,

1- (4-hydroxyphenyldithio) octadecane, 1- (4-hydroxyphenyldithio)-
9-octadecene, 1- (2-fluoro-4-hydroxyphenyldithio) octadecane, 1- (2-ethoxy-4-hydroxyphenyldithio) octadecane, 1-
(3-chloro-4-hydroxyphenyldithio) octadecane,

4'-hydroxy-4-tetradecyldiphenyl sulfide, 4'-hydroxy-4-octadecyldiphenyl sulfide, 4'-hydroxy-4-octadecylcarbonylaminodiphenyl sulfide, 4 '
-Hydroxy-4-octadecyloxydiphenyl sulfide, 4'-hydroxy-4-octadecyloxysulfonyldiphenyl sulfide, 4'-hydroxy-4
-Octadecylsulfonylaminodiphenyl sulfide,

4'-hydroxy-3,4-didecyloxydiphenyl sulfide, 4'-hydroxy-3,4-
Dioctadecyloxydiphenyl sulfide, 4- (1
5-cyclohexylpentadecyl) -4'-hydroxydiphenyl sulfide, 4'-hydroxy-4- (5-
Tetradecenyl) diphenyl sulfide,

3'-chloro-4'-hydroxy-4-octadecyldiphenyl sulfide, 3'-hydroxy-
4-dodecyldiphenyl sulfide, 3'-hydroxy-4-octadecyldiphenyl sulfide, 3'-hydroxy-4-dodecyloxycarbonyldiphenyl sulfide,

N- (4-hydroxyphenyl) -N'-
Hexylurea, N- (4-hydroxyphenyl) -N '
-Dodecyl urea, N- (4-hydroxyphenyl)-
N'-hexadecyl urea, N- (4-hydroxyphenyl) -N'-octadecyl urea, N- (4-hydroxyphenyl) -N'-icosyl urea, N- (4-hydroxyphenyl) -N'-cyclododecyl Urea, N- (4
-Hydroxyphenyl) -N'-docosylurea, N-
(4-hydroxyphenyl) -N'-cholesteryl urea, N- (4-hydroxyphenyl) -N '-(2-heptyloctyl) urea, N- (4-hydroxyphenyl) -N'-(9-octadecenyl) urea,

N- (3-allyl-4-hydroxyphenyl) -N'-octadecylurea, N- (2-hydroxyphenyl) -N'-octylurea, N- (3-hydroxyphenyl) -N'-octadecyl Urea, N- (3,4
-Dihydroxyphenyl) -N'-octadecylurea,
N- (3,4,5-trihydroxyphenyl) -N'-
Trichosyl urea, N- (4-hydroxyphenyl)-
N '-(4-tetradecylphenyl) urea, N- (4-
(Hydroxyphenyl) -N′-hexadecylthiourea,
N- (4-hydroxyphenyl) -N'-octadecylthiourea;

4-undecanoylamino-1- (4-hydroxyphenylaminocarbonyl) benzene, 4-octadecanoylamino-1- (4-hydroxyphenylaminocarbonyl) benzene, 4- (octadecylaminocarbonyl) amino- 1- (4-hydroxyphenylaminocarbonyl) benzene, 4-octadecylamino-1- (4-hydroxyphenylamino) carbonylmethylbenzene, N-octadecyl-N′-p- (4-hydroxyphenylcarbamoyl) phenyl oxamide,
4- (octadecylaminocarbonyl) amino-1-
(4-hydroxyphenylcarbamoyl) methylbenzene, 4- (octadecylamino) carbonyl-1- (4
-Hydroxyphenylcarbamoyl) methylbenzene,
N-octadecanoyl-N'-p- (p-hydroxyphenylcarbamoylmethyl) benzoylhydrazine, N
-Dodecanoyl-N'-p- [2- (p-hydroxyphenylcarbamoyl) ethyl] benzoylhydrazine,

N- (4-hydroxyphenylmethyl)-
N'-n-tetradecyl urea, N- (4-hydroxyphenylmethyl) -N'-n-octadecyl urea, N-
[2- (4-hydroxyphenyl) ethyl] -N'-n
-Tetradecyl urea, N- [2- (4-hydroxyphenyl) ethyl] -N'-n-octadecyl urea, N-
[3- (4-hydroxyphenyl) propyl] -N'-
n-dodecyl urea, N- [3- (4-hydroxyphenyl) propyl] -N'-n-octadecyl urea, N-
[6- (4-hydroxyphenyl) hexyl] -N'-
n-dodecyl urea, N- [2- (3-hydroxyphenyl) ethyl] -N'-n-octadecyl urea, N- [2
-(3,4-dihydroxyphenyl) ethyl] -N'-
n-octadecyl urea,

Nn-octadecyl- (4-hydroxyphenyl) acetamide, Nn-dodecyl-3- (4
-Hydroxyphenyl) propanamide, Nn-octadecyl-3- (4-hydroxyphenyl) propanamide, N- (4-hydroxyphenylmethyl) octadecanamide, N- [2- (4-hydroxyphenyl) ethyl] octadecane Amide, N- [3- (4-hydroxyphenyl) propyl] octadecanamide, N- [3
-(3-hydroxyphenyl) propyl] octadecanamide, N- [3- (3,4-dihydroxyphenyl)
Propyl] octadecaneamide,

N- (4-hydroxybenzoyl) -N '
-N-octanoylhydrazine, N- (4-hydroxybenzoyl) -N'-n-tetradecanoylhydrazine, N- (4-hydroxybenzoyl) -N'-n-octadecanoylhydrazine, N- (2, 4-dihydroxybenzoyl) -N'-n-octanoylhydrazine,
N- (2,4-dihydroxybenzoyl) -N'-n-
Octadecanoylhydrazine, N- (4-hydroxybenzoyl) -N'-n-tetradecylaminocarbonylhydrazine, N- (4-hydroxybenzoyl) -N '
-N-octadecylaminocarbonylhydrazine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecylaminocarbonylhydrazine, N- (2,4-
Dihydroxybenzoyl) -N'-n-octadecylaminocarbonylhydrazine, N- (4-hydroxybenzoyl) -N'-n-octyloxycarbonylhydrazine, N- (4-hydroxybenzoyl) -N'-n-
Dodecyloxycarbonylhydrazine, N- (2,4-
Dihydroxybenzoyl) -N'-n-tetradecyloxycarbonylhydrazine, N- (2,4-dihydroxybenzoyl) -N'-n-octadecyloxycarbonylhydrazine, N- (4-hydroxybenzoyl)-
N'-n-tetradecylhydrazinocarbonylhydrazine, N- (4-hydroxybenzoyl) -N'-n-octadecylhydrazinocarbonylhydrazine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecylhydrazinocarbonylhydrazine, N- (2
4-dihydroxybenzoyl) -N'-n-octadecylhydrazinocarbonylhydrazine;

N- (4-hydroxybenzoyl) -N '
-N-octanoylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-tetradecanoylmethylenediamine, N- (4-hydroxybenzoyl)-
N'-n-octadecanoyl methylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecanoylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N'-n-octadecanoylmethylenediamine, N- (4-hydroxybenzoyl) −
N'-n-octylaminocarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-dodecylaminocarbonylmethylenediamine, N- (4-
(Hydroxybenzoyl) -N'-n-tetradecylaminocarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-octadecylaminocarbonylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N'- n-octadecylaminocarbonylmethylenediamine, N- (4-hydroxybenzoyl)-
N'-n-tetradecyloxycarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-
Octadecyloxycarbonylmethylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecyloxycarbonylmethylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-octadecyloxycarbonylmethylenediamine, N- (4
-Hydroxybenzoyl) -N'-n-octylhydrazinocarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-dodecylhydrazinocarbonylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N '-N-tetradecylhydrazinocarbonylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N'-n-octadecylhydrazinocarbonylmethylenediamine,

Nn-octadecyl-2- (p-hydroxyphenylthio) acetamide, Nn-octadecyl-3- (p-hydroxyphenylthio) propanamide, Nn-decyl-11- (p-hydroxy Phenylthio) undecaneamide, N- (pn-octylphenyl) -6- (p-hydroxyphenylthio) hexanamide, Nn-octadecyl-p- (p-hydroxyphenylthio) benzamide, N- [2 -(P-hydroxyphenylthio) ethyl] -n-octadecanamide, N- [p- (p-hydroxyphenylthio) phenyl] -n-octadecanamide, N- (p-hydroxyphenylthio) methyl-N'- n-octadecyl urea,
N- [2- (p-hydroxyphenylthio) ethyl]-
N'-n-tetradecyl urea, N- [2- (p-hydroxyphenylthio) ethyl] -N'-n-octadecyl urea, N- [2- (3,4-dihydroxyphenylthio) ethyl] -N ' -N-octadecyl urea, N- [p
-(P-hydroxyphenylthio) phenyl] -N'-
n-octadecyl urea, N- [10- (p-hydroxyphenylthio) decyl] -N'-n-decyl urea, N-
[2- (p-hydroxyphenylthio) ethyl] -n-octadecylcarbamate, N- [p- (p-hydroxyphenylthio) phenyl] -n-dodecylcarbamate, Nn-octadecylcarbamic acid- [2 − (P−
Hydroxyphenylthio) ethyl], N- [3- (p-
(Hydroxyphenylthio) propionyl] -NN-octadecanoylamine, N- [2- (p-hydroxyphenylthio) aceto] -N'-n-octadecanohydrazide, N- [3- (p-hydroxy Phenylthio) propiono] -N'-n-octadecanohydrazide, N-
[3- (3,4-dihydroxyphenylthio) propiono] -N'-n-octadecanohydrazide, N- [6-
(P-Hydroxyphenylthio) hexano] -N'-n
-Tetradecanohydrazide, N- [6- (p-hydroxyphenylthio) hexano] -N'-n-octadecanohydrazide, N- [6- (p-hydroxyphenylthio) hexano] -N '-( p-n-octylbenzo) hydrazide, N- [11- (p-hydroxyphenylthio) undecano-N'-n-decanohydrazide, N-
[11- (p-hydroxyphenylthio) undecano-
N'-n-tetradecanohydrazide, N- [11- (p
-Hydroxyphenylthio) undecano-N'-n-octadecanohydrazide, N- [11- (p-hydroxyphenylthio) undecano-N '-(6-phenyl) hexanohydrazide, N- [11- (3 , 4,5-Trihydroxyphenylthio) undecano] -N'-n-octadecanohydrazide, N- [p- (p-hydroxyphenylthio) benzo] -N'-n-octadecanohydrazide, N- [P- (p-hydroxyphenylthiomethyl)
Benzo] -N'-n-octadecanohydrazide, N-
[3- (p-hydroxyphenylthio) propyl] -N
'-N-octadecyloxamide, N- [3- (3,4
-Dihydroxyphenylthio) propyl] -N'-n-
Octadecyl oxamide, N- [11- (p-hydroxyphenylthio) undecyl] -N'-n-decyl oxamide, N- [p- (p-hydroxyphenylthio) phenyl] -N'-n-octadecyl oxamide, N-
[2- (p-hydroxyphenylthio) acetyl] -N
'-N-octadecyl urea, N- [3- (p-hydroxyphenylthio) propionyl] -N'-n-octadecyl urea, N- [2- (p-hydroxyphenylthio)
Ethyl] -N'-n-octadecanoyl urea, N- [p
-(P-hydroxyphenylthio) phenyl] -N'-
n-octadecanoyl urea, 3- [3- (p-hydroxyphenylthio) propionyl] -n-octadecylcarbazate, 4- [2- (p-hydroxyphenylthio) ethyl] -1-n-octadecyl semicarbazide,
1- [2- (p-hydroxyphenylthio) ethyl]-
4-n-octadecyl semicarbazide, 1- [p- (p
-Hydroxyphenylthio) phenyl] -4-n-tetradecylsemicarbazide, 1- [3- (p-hydroxyphenylthio) propionyl] -4-n-octadecylsemicarbazide, 1- [p- (p-hydroxyphenylthio) Benzoyl] -4-n-octadecyl semicarbazide, 4- [2- (p-hydroxyphenylthio) ethyl] -1-n-tetradecanoyl semicarbazide, 4-
[P- (p-hydroxyphenylthio) phenyl] -1
-N-octadecanoyl semicarbazide, 1- [2-
(P-Hydroxyphenylthio) acetamide] -1-
n-octadecanoylaminomethane, 1- [11- (p
-Hydroxyphenylthio) undecaneamide] -N '
-N-decanoylaminomethane, 1- [p- (p-hydroxyphenylthio) benzamide] -1-n-octadecanoylaminomethane, 1- [3- (p-hydroxyphenylthio) propanamide] -1 -(N'-n-octadecylureido) methane, 1- [11- (p-hydroxyphenylthio) undecaneamide] -N '-(N
'-N-decylureido) methane, 1- {N'-[2-
(P-Hydroxyphenylthio) ethyl] ureido｝-
1-n-octadecanoylaminomethane, N- [2-
(P-hydroxyphenylthio) ethyl] -N'-n-
Octadecylmalonamide,

N- [2- (p-hydroxyphenyl) ethyl] -n-octadecylcarbamate, Nn-octadecylcarbamate- [2- (p-hydroxyphenyl) ethyl], N- [3- (p -Hydroxyphenyl)
Propionyl] -Nn-octadecanoylamine, N
-[6- (p-hydroxyphenyl) hexanoyl]-
Nn-octadecanoylamine, N- [3- (p-hydroxyphenyl) propionyl] -N- (pn-octylbenzoyl) amine, N- [2- (p-hydroxyphenyl) aceto] -N '-N-dodecanohydrazide, N- [2- (p-hydroxyphenyl) aceto]-
N'-n-octadecanohydrazide, N- [3- (p-
Hydroxyphenyl) propiono] -N'-n-octadecanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N'-n-docosanohydrazide, N
-[6- (p-hydroxyphenyl) hexano] -N '
-N-tetradecanohydrazide, N- [6- (p-hydroxyphenyl) hexano] -N'-n-octadecanohydrazide, N- [6- (p-hydroxyphenyl) hexano] -N '-( pn-octylbenzo) hydrazide, N- [11- (p-hydroxyphenyl) undecano-N'-n-decanohydrazide, N- [11- (p-
(Hydroxyphenyl) undecano-N′-n-octadecanohydrazide, N- (p-hydroxybenzo) -N ′
-N-octadecanohydrazide, N- [p- (p-hydroxyphenyl) benzo] -N'-n-octadecanohydrazide, N- [p- (p-hydroxyphenylmethyl) benzo] -N'- n-octadecanohydrazide, N
-[3- (p-hydroxyphenyl) propyl] -N '
-N-octadecyloxamide, N- [3- (3,4-
Dihydroxyphenyl) propyl] -N'-n-octadecyl oxamide, N- [p- (p-hydroxyphenyl) phenyl] -N'-n-octadecyl oxamide,
N- [2- (p-hydroxyphenyl) acetyl] -N
'-N-octadecyl urea, N- [2- (p-hydroxyphenyl) ethyl] -N'-n-octadecyl urea,
N- [3- (p-hydroxyphenyl) propionyl]
-N'-n-octadecyl urea, N- [p- (p-hydroxyphenyl) benzoyl] -N'-n-octadecyl urea, N- [2- (p-hydroxyphenyl) ethyl] -N'-n- Octadecanoyl urea, 4- [2-
(P-hydroxyphenyl) ethyl] -1-n-octadecylsemicarbazide, 1- [2- (p-hydroxyphenyl) ethyl] -4-n-tetradecylsemicarbazide, 1- [2- (p-hydroxyphenyl) ethyl ]-
4-n-octadecyl semicarbazide, 1- [2- (p
-Hydroxyphenyl) acetyl] -4-n-tetradecylsemicarbazide, 1- [3- (p-hydroxyphenyl) propionyl] -4-n-octadecylsemicarbazide, 1- [11- (p-hydroxyphenyl) undecanoyl]- 4-n-decyl semicarbazide, 4-
[2- (p-hydroxyphenyl) ethyl] -1-n-
Octadedecanoyl semicarbazide, 4- [p- (p-
[Hydroxyphenyl) phenyl] -1-n-octadecanoyl semicarbazide, 1- [2- (p-hydroxyphenyl) acetamido] -1-n-octadecanoylaminomethane, 1- [3- (p-hydroxyphenyl) Propanamide] -1-n-octadecanoylaminomethane, 1- [2- (p-hydroxyphenyl) acetamido] -1- (3-n-octadecylureido) methane,
1- [3- (p-hydroxyphenyl) propanamide] -1- (3-n-octadecylureido) methane,
1- [11- (p-hydroxyphenyl) undecanamido] -1- (3-n-decylureido) methane, 1-
{3- [2- (p-hydroxyphenyl) ethyl] ureide} -1-n-octadecanoylaminomethane, N-
[2- (p-hydroxyphenyl) ethyl] -N'-n
-Octadecylmalonamide,

4-n-octadecylaminophenol,
4- (1-octadecynyl) phenol, 4- (1,3
-Octadecadinyl) phenol and the like.

These may be used alone or as a mixture of two or more kinds. Usually, 5 to 5000% by weight, preferably 10 to 3% by weight, based on the colorless to pale leuco dye.
000% by weight.

The resin of the reversible thermosensitive recording layer may be provided with a functional group, if necessary, similarly to the resin of the light-to-heat conversion layer, and may be crosslinked by heat, ultraviolet rays, electron beams or the like. The same thing can be used for a crosslinking agent, a photopolymerization initiator and the like.

The reversible thermosensitive recording material of the present invention repeatedly records and erases an image by heating by light irradiation.
In order to prevent the deterioration of the reversible thermosensitive recording material, it is possible to provide a protective layer (heat-resistant layer). It is also possible. Examples of a material for forming such a protective layer include a water-soluble polymer, latex, and a polymerizable compound. For example, polyurethane resin, polyester resin, epoxy resin, melamine resin, polyvinyl alcohol, nitrocellulose, methacrylate, acrylate oligomer, acrylate oligomer and the like can be mentioned. If necessary, epoxy compounds, urea derivatives, crosslinking agents such as vinyl compounds, phosphoric acid,
A sulfonic acid-based, polyamide-based, amine-based curing agent or the like can be added. Alternatively, a protective layer can be formed on the reversible thermosensitive recording material by means of laminating, etc. in a state of a transparent film such as polyethylene or polyethylene terephthalate in advance. In this case, if necessary, the protective layer or the intermediate layer may be composed of two or three or more layers.

The reversible thermosensitive recording layer, light-to-heat conversion layer, protective layer or intermediate layer includes diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, and hydroxide. Aluminum, pigments such as urea-formalin resin, etc., in addition to zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearic amide, wax such as caster wax, A dispersant such as sodium dioctyl sulfosuccinate, a surfactant, a fluorescent dye, and the like can also be contained.

A heat-fusible substance can be contained in the reversible thermosensitive recording layer as an additive for adjusting the color development sensitivity and the decoloring temperature of the reversible thermosensitive recording layer. 60 ° C-20
Those having a melting point of 0 ° C. are preferred, and
Those having a melting point of 0 ° C. are preferred. A sensitizer used in general thermosensitive recording paper can also be used. For example, waxes such as N-hydroxymethyl stearamide, stearamide, palmitamide, etc.
Naphthol derivatives such as 2-benzyloxynaphthalene,
Biphenyl derivatives such as p-benzylbiphenyl and 4-allyloxybiphenyl, 1,2-bis (3-methylphenoxy) ethane, 2,2'-bis (4-methoxyphenoxy) diethyl ether, bis (4-methoxyphenyl) Polyether compounds such as ethers, and carbonic acid or oxalic acid diester derivatives such as diphenyl carbonate, dibenzyl oxalate, bis (p-methylbenzyl) oxalate, and the like can be added in combination, but are not limited thereto. is not.

The structure of the reversible thermosensitive recording material of the present invention is such that the reversible thermosensitive recording layer, another layer, the surface on which the reversible thermosensitive recording layer is provided or the surface on the opposite side are electrically and magnetically. Alternatively, a material capable of optically recording information may be included. Further, a back coat layer may be provided on the surface opposite to the surface on which the reversible thermosensitive recording layer is provided for the purpose of preventing curling and electrification, and may be subjected to an adhesive process or the like.

The method of forming each layer constituting the reversible thermosensitive recording material of the present invention on a support is not particularly limited, and it can be formed by a conventional method. For example, a smearing device such as an air knife coater, a blade coater, a bar coater, a curtain coater, and a gravure coater, and various printing machines using a method such as lithographic, letterpress, intaglio, flexo, gravure, screen, and hot melt can be used. In addition to the usual drying process, UV irradiation and
Each layer can be held by EB irradiation. By these methods, smearing and printing can be performed one layer at a time or simultaneously at multiple layers.

In the reversible thermosensitive recording material of the present invention, rapid cooling following heating may be required to form a color-recorded image. Should be late. For example, it is also possible to develop a color development state by heating by light irradiation and then rapidly cooling by pressing a low-temperature metal block or the like. In addition, when light irradiation such as laser light is performed and heating is performed for an extremely short time, cooling is performed immediately after the completion of heating, so that a colored state can be maintained. On the other hand, besides the heat from the light-to-heat conversion layer, relatively appropriate heat sources (radiant heat from a light source such as a thermal head, a heat roll, a heat stamp, high-frequency heating, an electric heater, and a tungsten lamp or a halogen lamp, hot air, etc.) When heated for a long time, not only the recording layer but also the support is heated, so even if the heat source is removed, the cooling speed is slow, so it can be erased in a decolored state and combined with an appropriate heat source May be recorded or erased.

[0080]

The present invention will be described in more detail with reference to the following examples.

(A) Preparation of coating solution for reversible thermosensitive recording layer 20 parts of 3-di-n-butylamino-6-methyl-7-anilinofluoran as a leuco dye and N- [3 -(P-hydroxyphenyl) propiono]
100 parts of -N'-n-octadecanohydrazide, and a vinyl chloride-vinyl acetate copolymer resin 80 as a binder resin
Parts (VAGH, manufactured by Union Carbide Co., Ltd.) and 600 parts of toluene as a solvent, and mix with a ball mill.
The mixture was pulverized for an hour to prepare a reversible thermosensitive recording layer coating solution.

(B) Preparation of Coating Solution for Light-to-Heat Conversion Layer Titanyl phthalocyanine was used as a light-to-heat conversion material in 100 parts.
Part, polyester resin as resin (trade name Byron 20)
0, manufactured by Toyobo Co., Ltd.) 100 parts, isocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) 2 as a crosslinking agent
Parts, and 500 parts of toluene as a solvent were mixed to prepare a photothermal conversion layer coating solution. (C) Preparation of protective layer coating solution Aronix M8030 (manufactured by Toa Gosei Chemical Industry) 90
Parts, N-vinyl-2-pyrrolidone 5 parts, Irgacure 500 (manufactured by Nippon Ciba Geigy) 5 parts, Mizukasil P-5
27 (manufactured by Mizusawa Chemical Co., Ltd.) was added, and the mixture was sufficiently stirred to prepare an ultraviolet-curable protective layer coating liquid.

The coating solution of the photothermal conversion layer prepared in Example 1 (B) was dried to about 1 μm,
About 5 μm after drying the reversible heat-sensitive coating solution prepared in (A),
The light-heat conversion layer coating solution prepared in (B) is laminated on a 188 μm white polyethylene terephthalate (PET) sheet so as to have a thickness of about 1 μm after drying, and is aged at 60 ° C. for 48 hours to have a light-heat conversion layer. A reversible thermosensitive recording material was obtained.

Example 2 The photothermal conversion material of the coating solution for photothermal conversion layer prepared in (B) was a near infrared absorbing dye (trade name: CY-9, manufactured by Nippon Kayaku Co., Ltd.).
The procedure was the same as in Example 1 except that the parts were changed to parts, to obtain a reversible thermosensitive recording material having a light-to-heat conversion layer.

Example 3 After drying the reversible thermosensitive recording layer coating solution prepared in (A),
about 2 μm after drying the photothermal conversion layer coating solution prepared in (B).
The reversible thermosensitive recording layer coating solution prepared in (A) was dried and laminated on a 188 μm white polyethylene terephthalate (PET) sheet to a thickness of about 2 μm after drying, and aged at 60 ° C. for 48 hours. A reversible thermosensitive recording material having a conversion layer was obtained.

Example 4 After drying the reversible thermosensitive recording layer coating solution prepared in (A),
about 2 μm after drying the photothermal conversion layer coating solution prepared in (B).
It is laminated on a transparent polyethylene terephthalate (PET) sheet having a thickness of 25 μm so that the thickness becomes 48 μm.
Time aging was performed. This transparent polyethylene terephthalate sheet is used as a protective layer, and 40
Support part provided with a window part of mm × 30 mm, 200 μm
A thick white polyethylene terephthalate sheet was sequentially bonded with a polyester adhesive to obtain a reversible thermosensitive recording material integrated.

Example 5 After drying the reversible thermosensitive recording layer coating solution prepared in (A),
about 2 μm after drying the photothermal conversion layer coating solution prepared in (B).
It was laminated on a 188 μm white polyethylene terephthalate (PET) sheet to a thickness of μm. Next, a reversible thermosensitive recording material obtained by integrating a transparent polyethylene terephthalate sheet having a thickness of 25 μm as a protective layer by sequentially bonding a polyester-based adhesive to a support portion having a 40 mm × 30 mm window provided on the upper surface of the light-to-heat conversion layer. Obtained.

Example 6 After drying the coating solution for the reversible thermosensitive recording layer prepared in (A),
about 2 μm after drying the photothermal conversion layer coating solution prepared in (B).
The protective layer coating solution prepared in (C) was dried and laminated on a 188 μm foamed polyethylene terephthalate sheet (titania dispersion, porosity: 40%) to a thickness of 3 μm after drying.
Aging was performed in a 0 ° C. environment for 48 hours to obtain a reversible thermosensitive recording material having a light-to-heat conversion layer.

The coating solution of the photothermal conversion layer prepared in Example 7 (B) was dried to about 2 μm,
After drying the reversible thermosensitive recording layer coating solution prepared in (A),
2 μm after drying the photothermal conversion layer coating solution prepared in (B).
m and laminated on a 75 μm transparent polyethylene terephthalate (PET) sheet, and aged at 60 ° C. for 48 hours to obtain a reversible thermosensitive recording material having a light-to-heat conversion layer.

The coating solution of the photothermal conversion layer prepared in Example 8 (B) was dried to about 2 μm,
After drying the reversible thermosensitive recording layer coating solution prepared in (A),
about 2 μm after drying the photothermal conversion layer coating solution prepared in (B).
It is laminated on a 75 μm transparent polyethylene terephthalate (PET) sheet to a thickness of
After time aging, a reversible thermosensitive recording material having a light-to-heat conversion layer was obtained.

Comparative Example 1 The photothermal conversion layer coating solution prepared in (B) was dried to about 1 μm,
The reversible heat-sensitive coating solution prepared in (A) is laminated on a 188 μm white polyethylene terephthalate (PET) sheet so as to have a thickness of about 5 μm after drying, and is aged at 60 ° C. for 48 hours to have a light-to-heat conversion layer. A reversible thermosensitive recording material was obtained.

Comparative Example 2 The reversible heat-sensitive coating solution prepared in (A) was dried to about 5 μm,
The light-heat conversion layer coating solution prepared in (B) is laminated on a 188 μm white polyethylene terephthalate (PET) sheet so as to have a thickness of about 1 μm after drying, and is aged at 60 ° C. for 48 hours to have a light-heat conversion layer. A reversible thermosensitive recording material was obtained.

Comparative Example 3 The photothermal conversion layer coating solution prepared in (B) was dried to about 2 μm,
After drying the reversible thermosensitive recording layer coating solution prepared in (A),
The protective layer coating solution prepared in (C) was dried and laminated on a 188 μm foamed polyethylene terephthalate sheet (titania dispersion, porosity: 15%) so as to have a thickness of 3 μm after drying.
Aging was performed in a 0 ° C. environment for 48 hours to obtain a reversible thermosensitive recording material having a light-to-heat conversion layer.

Comparative Example 4 The coating solution of the photothermal conversion layer prepared in (B) was dried to about 2 μm,
After drying the reversible thermosensitive recording layer coating solution prepared in (A),
The protective layer coating solution prepared in (C) was dried and laminated on a 100 μm foamed polyethylene terephthalate sheet (titania dispersion, porosity: 60%) to a thickness of 3 μm after drying.
Aging was performed in a 0 ° C. environment for 48 hours to obtain a reversible thermosensitive recording material having a light-to-heat conversion layer.

The following evaluation test was performed on the reversible thermosensitive recording material produced as described above. Test method Using the reversible thermosensitive recording materials obtained in Examples and Comparative Examples, a laser recording device (830 nm) having a variable irradiation light power was irradiated with a laser beam (830 nm) with a spot diameter of 100 μmφ and a feed rate of 4
The recording was performed at 0 mm / sec and an irradiation light intensity of 50 to 200 mW.
Was used as the recording density. Further, after the obtained color recording image portion was irradiated with a laser beam at 20 to 100 mW to erase the color, the density was measured in the same manner to obtain the erased density. After the printing and decoloring were repeated 100 times, the recording surface was observed and evaluated according to the following criteria. Example 7,
No. 8 was irradiated with laser light from the transparent film side without the reversible thermosensitive recording layer. ：: There is no unevenness in both the recorded state and the erased state, and the state is good. X: Streaked density unevenness during recording and color development remaining upon erasure.

[0096]

[Table 1]

From Table 1, Examples 1, 2, and 8 in which the photothermal conversion recording layer, the reversible thermosensitive recording layer, and the photothermal conversion layer were sequentially laminated, the reversible thermosensitive recording layer, the photothermal conversion layer, and the reversible thermosensitive recording layer were sequentially formed. In each of Example 3 in which the layers were laminated, Examples 4 and 5 in which the air layer was laminated, and Example 6 in which foamed PET was used as the support, recording and erasing were good, and a saturated recording density was obtained with an irradiation light power of 100 mW or less. I was able to do it. It was possible to repeat this. In Examples 7 and 8, laser irradiation was performed from the transparent film side, and recording and erasing were possible. In Comparative Examples 1 and 3 in which a light-to-heat conversion layer and a reversible thermosensitive recording layer were stacked, and in Comparative Example 2 in which a reversible thermosensitive recording layer and a light-to-heat conversion layer were stacked, recording and erasing were possible, but the saturation density was not obtained. An irradiation light power of 150 mW or more was required, the saturation density was low, and erasing could not be performed sufficiently. In Comparative Example 4, when the recording and erasing were repeated, the support was destroyed, and the contrast between recording and erasing could not be maintained. Thereby, a clear difference is recognized between the example and the comparative example, and it is confirmed that the present invention has a great effect.

[0098]

According to the present invention, a reversible thermosensitive recording material characterized in that a photothermal conversion layer mainly composed of a photothermal conversion material, a reversible thermosensitive recording layer, and a photothermal conversion layer are sequentially laminated on a support, or a reversible thermosensitive recording material, By sequentially laminating a thermosensitive recording layer, a photothermal conversion layer, and a reversible thermosensitive recording layer, or having a reversible thermosensitive recording layer and a photothermal conversion layer, one of the reversible thermosensitive recording layer and the photothermal conversion layer By forming an air layer between the support and the outermost layer, or having a protective layer on the outermost layer, having a reversible thermosensitive recording layer and a light-to-heat conversion layer, the reversible thermosensitive recording layer and the By forming an air layer between any one of the light-to-heat conversion layers and the protective layer, or by having a reversible thermosensitive recording layer and a light-to-heat conversion layer on a foamed polyester film support having a porosity of 20 to 50%. ,
Alternatively, in a reversible thermosensitive recording material in which a light-to-heat conversion layer and a reversible thermosensitive recording layer are provided on one side of a transparent film, image recording / irradiation with laser light from the other side of the transparent film.
According to the erasing method, it can be used as a reversible thermosensitive recording material capable of forming or erasing a high-contrast, high-sensitivity recorded image with little deformation by a laser beam and an image recording / erasing method.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a reversible thermosensitive recording material according to a first embodiment of the present invention.

FIG. 2 is a sectional view showing a reversible thermosensitive recording material according to a second embodiment of the present invention.

FIG. 3 is a sectional view showing a reversible thermosensitive recording material according to a third embodiment of the present invention.

FIG. 4 is a sectional view showing a reversible thermosensitive recording material according to a fourth embodiment of the present invention.

FIG. 5 is a sectional view showing a reversible thermosensitive recording material according to a fifth embodiment of the present invention.

FIG. 6 is a sectional view showing a reversible thermosensitive recording material according to a sixth embodiment of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support 2 reversible thermosensitive recording layer 3 light-to-heat conversion layer 4 laser light source 5 laser light 6 lens 7 air layer 8 support section 9 protective layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B41M 5/18 108

Claims (6)

[Claims] 1. A reversible color developing method in which a light-to-heat conversion layer containing a light-to-heat conversion material as a main component, a colorless or light-colored leuco dye, and the leuco dye are colored by heating and then reheated to decolor the support. A reversible thermosensitive recording material characterized by sequentially laminating a reversible thermosensitive recording layer containing an agent and a photothermal conversion layer mainly comprising a photothermal conversion material. 2. A reversible thermosensitive recording layer containing a colorless or pale-colored leuco dye and a reversible developer for recoloring the leuco dye by heating and reheating the dye, and a photothermal conversion. A reversible thermosensitive recording material, comprising: a light-to-heat conversion layer mainly composed of a material; and a reversible thermosensitive recording layer. 3. A reversible thermosensitive recording layer containing a colorless or pale-colored leuco dye, a reversible developer which develops the leuco dye by heating and reheats and decolorizes the leuco dye, and a light-to-heat conversion material as main components. Reversible thermosensitive recording characterized in that an air layer is formed between the reversible thermosensitive recording layer and a support located on either side of the light-to-heat conversion layer. material. 4. A reversible thermosensitive recording having a protective layer on the outermost layer and containing a colorless or pale-colored leuco dye and a reversible developer which develops the color of the leuco dye by heating and decolorizes it by reheating. And a light-to-heat conversion layer containing a light-to-heat conversion material as a main component, and an air layer is formed between one of the reversible thermosensitive recording layer and the light-to-heat conversion layer and the protective layer. Reversible thermosensitive recording material. 5. A reversible thermosensitive recording layer and a light-to-heat conversion material containing a colorless or pale-colored leuco dye and a reversible developer for heating to re-decolor the leuco dye on a support. A reversible thermosensitive recording material, comprising: a light-to-heat conversion layer containing, as a main component, a foamed polyester film having a porosity of 20 to 50%. 6. A reversible method in which a light-to-heat conversion layer containing a light-to-heat conversion material as a main component, a colorless or light-colored leuco dye, and the leuco dye are colored by heating and reheated to decolorize the transparent film. An image is recorded by heat generated by irradiating a laser beam from the other side of the transparent film using the reversible thermosensitive recording material according to claim 1 provided with a reversible thermosensitive recording layer containing a color developer. Alternatively, an image recording / erasing method characterized by erasing.