JPH09254548A - Reversible thermal recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reversible thermal recording material utilizing the reaction of a color former such as a fluorane compd. and a coupler allowing the color former to generate a reversible hue change by heating, having good image contrast, capable of forming and erasing an image, reduced in damage even if repeatedly used in color development and color erasure and having high water resistance. SOLUTION: This reversible thermal recording material is constituted by providing a reversible thermal recording layer containing a usually colorless or light-colored electron donating dye precursor and a reversible coupler allowing the dye precursor to develop a color by heating and erasing the color by reheating the developed color dye precursor on at least the single surface of a support. In this case, a thermal reaction type aq. polyurethane resin is added to the reversible thermal recording layer. This polyurethane resin can be added to the protective layer provided on the upper surface of the thermal recording layer or to the anchor layer provided between the support and the reversible thermal recording layer or to both layers. It is also pref. to use the thermal reaction type aq. polyurethane resin together with polyamines or polyols. It is also pref. to thermally treat the reversible thermal recording material.

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 and erasing an image by heating. The reversible thermosensitive recording material is less damaged by repeated use of coloring and decoloring, and has strong water resistance. A heat recording material is provided.

[0002]

2. Description of the Related Art A thermosensitive recording material generally comprises a support having thereon a thermosensitive recording layer mainly composed of an electron-donating, usually colorless or pale-colored dye precursor and an electron-accepting developer. By heating with a thermal head, a hot pen, a laser beam, or the like, the dye precursor and the developer react instantaneously to obtain a recorded image. Japanese Patent Publication No. 43-4160, Japanese Patent Publication No. Sho 4
It is disclosed in JP-A-5-14039.

In general, such a heat-sensitive recording material cannot erase the portion of the image once formed and return to the state before the image is formed. Therefore, when further information is recorded, the image is not recorded. There was no choice but to add to the formation part. For this reason, when the area of the heat-sensitive recording portion is limited, there has been a problem that the recordable information is limited and all necessary information cannot be recorded.

In recent years, a reversible thermosensitive recording material has been devised which can be repeatedly used for image formation and image erasure in order to deal with such a problem. For example, JP-A-54-11937.
7, JP-A-63-39377, JP-A-63
No. 41186 discloses a heat-sensitive recording material composed of a resin base material and organic low-molecules dispersed in the resin base material. However, since this method reversibly changes the transparency of the heat-sensitive recording material by heat energy, the contrast between the image-formed area and the image-unformed area is insufficient.

Further, in the methods described in JP-A-50-81157 and JP-A-50-105555, since the image to be formed changes according to the ambient temperature, the image forming state and the erasing state. The holding temperatures are different, and these two states cannot be held for an arbitrary period at room temperature.

Further, in Japanese Patent Laid-Open No. 59-120492, the hysteresis characteristic of the color-developing component is utilized to keep the recording material in the hysteresis temperature range, thereby forming an image.
Although a method of maintaining the erased state is described, this method requires a heating source and a cooling source for image formation and erasure, and the temperature range in which the image formation state and the erased state can be maintained is limited to the hysteresis temperature region. However, it is still insufficient for use in the temperature environment of daily life.

On the other hand, JP-A-2-188293, JP-A-2-188294, and International Publication No. WO90 /
No. 11898 describes a reversible thermosensitive recording medium composed of a leuco dye and a color-developing and decoloring agent for coloring and decoloring the leuco dye by heating. The color-developing agent is an amphoteric compound having an acidic group for coloring the leuco dye and a basic group for decolorizing the colored leuco dye, and has a coloring effect by an acidic group or a decolorizing effect by a basic group by controlling thermal energy. One is preferentially generated to perform color development and decoloration. However, in this method, it is impossible to completely switch the color development reaction and the color removal reaction only by controlling the thermal energy, and since both reactions occur at a certain ratio at the same time, sufficient color development density cannot be obtained, and the color removal Can not be done completely. Therefore, sufficient image contrast cannot be obtained. Also,
Since the decoloring action of the basic group also acts on the color development part at room temperature,
The phenomenon that the density of the color-developed portion decreases with time cannot be avoided.

Further, JP-A-5-124360 discloses a reversible thermosensitive recording medium which develops and decolorizes a leuco dye by heating, and an organic phosphoric acid compound and α-hydroxy aliphatic compound as an electron-accepting compound. Specific phenol compounds such as carboxylic acids, fatty acid dicarboxylic acids, and alkylthiophenols having an aliphatic group having 12 or more carbon atoms, alkyloxyphenols, alkylcarbamoylphenols, and gallic acid alkylesters are exemplified. However, even with this recording medium, the two problems of low color density or incomplete decolorization cannot be solved at the same time, and the temporal stability of the image is not satisfactory in practice.

As described above, the conventional technique has good image contrast, enables formation and erasing of an image, and has no practical change in color density even when color development and decoloration are repeated many times. No thermosensitive recording material was known.

The present applicant has found a novel reversible color developer capable of forming and erasing an image with good contrast and maintaining a stable image over time in an environment of daily life. It was previously proposed in Japanese Patent Application No. 4-347032. However, in the reversible thermosensitive recording material obtained by this method, if coloring and erasing are repeated at the same location, the recording layer deteriorates and the printing density decreases, and the water resistance of the recording layer is insufficient. However, there is a problem that the recording layer swells or peels off when it is immersed in water for a long time. In contrast,
Japanese Patent Application Laid-Open No. 6-8626 proposes a curing reaction product of polyvinyl butyral and an isocyanate compound in the protective layer, but when the number of repetitions increases, there are problems such as print density reduction and insufficient water resistance. Still there.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a reversible thermosensitive recording material which is capable of forming an image and erasing the image, has little damage by repeated use of coloring and decoloring, and has high water resistance. To provide.

[0012]

Means for Solving the Problems The present inventor has conducted a study to solve this problem. As a result, at least one surface of the support is usually provided with a colorless or pale-color electron-donating dye precursor,
Use of a heat-reactive water-based urethane resin in a reversible thermosensitive recording material provided with a reversible thermosensitive recording layer containing a reversible developer that causes the dye precursor to develop a color by heating and reheats the dye to decolorize it. This has solved this problem.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present applicant has developed a novel reversible color developing device capable of forming and erasing an image with good contrast and maintaining a stable image over time in an environment of daily life. An agent has been found and previously proposed in JP-A-6-210954. However, the reversible thermosensitive recording material obtained by this method has a problem that the reversible color developer has a relatively long-chain aliphatic hydrocarbon group or the adhesion of the reversible thermosensitive recording layer is low. have. For example, when color development and decoloration are repeated at the same location, the thermal head is repeatedly exposed to pressure and a heat source, so that the protective layer is easily peeled off, or the reversible thermosensitive recording layer is likely to flow out. . There is also a problem that the water resistance of the recording layer is insufficient, especially when the recording layer is immersed in water for a long time, the recording layer swells or peels off.

To solve these problems, the present inventor has studied the electron-donating dye precursor, the reversible developer and the adhesives thereof. As a result, the use of the heat-reactive water-based polyurethane resin for the reversible thermosensitive recording material. As a result, the present invention succeeded in obtaining a reversible heat-sensitive recording material having good repetitive durability without impairing the color developability and having sufficient water resistance. A heat-reactive water-based polyurethane resin is an aqueous solution or dispersion of a heat-reactive urethane resin, which is also called a block-type urethane resin. It has two or more blocked isocyanate groups in one molecule, and an isocyanate group is generated by heating. However, since it is cured by crosslinking, it is generally used as a coating material, a crosslinking agent, and a fiber processing agent. It is presumed that these heat-reactive water-based polyurethane resins cross-link in the layers to which they are added and contribute greatly to the repeated durability of the reversible thermosensitive recording material.

Such a heat-reactive water-based polyurethane resin is a compound having two or more blocked isocyanate groups in one molecule, and specific examples include the following. Tolylene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, trimethylol propane and tolylene diisocyanate reaction product, trimethylol propane and diphenylmethane diisocyanate reaction product, trimethylol propane and naphthalene diisocyanate reaction product, trimethylol propane and xylylene diisocyanate Reaction product, reaction product of trimethylolpropane and hexamethylene diisocyanate, reaction product of trimethylolpropane and tolidine diisocyanate, reaction product of isocyanuric acid and tolylene diisocyanate, reaction product of isocyanuric acid and diphenylmethane diisocyanate, reaction of isocyanuric acid and naphthalene diisocyanate Reaction product of isocyanuric acid and hexamethylene diisocyanate The ends of the free isocyanate groups of the reaction product of isocyanuric acid and xylylene diisocyanate include those blocked.

Examples of the blocking agent include phenols such as phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, p-tert-octylphenol, thymol, p-naphthol, p-nitrophenol and p-chlorophenol. Blocking agent, methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol,
Alcohol-based blocking agents such as phenyl cellosolve, furfuryl alcohol, cyclohexanol, etc., active methylene-based blocking agents such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, mercaptans such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan A system blocker, an acid amide blocker such as acetanilide, acetanizide, acetic acid amide, and benzamide can be used.

Further, succinimide, maleic imide,
imide or amide blocking agents such as ε-caprolactam, diphenylamine, phenylnaphthylamine,
Amine-based blocking agents such as aniline and carbazole, imidazole-based blocking agents such as imidazole and 2-ethylimidazole, urea-based blocking agents such as urea, thiourea and ethyleneurea, phenyl N-phenylcarbamate, 2-oxazolidone Such as carbamate-based blocking agents, imine-based blocking agents such as ethyleneimine, oxime-based blocking agents such as formaldoxime, acetoaldoxime, methylethylketoxime, cyclohexanoneoxime, sodium bisulfite, potassium bisulfite, etc. A sulfite-based blocking agent or the like can be used.

Blocking of the isocyanate group for preparing the heat-reactive water-based urethane resin is carried out by, for example, adding a catalyst to the compound having an isocyanate group and a blocking agent in an inert solvent at room temperature to 160 ° C. It is obtained by reacting at a temperature of. For example, the heat-reactive water-based urethane resin of the present invention can be obtained by dissolving or dispersing the heat-reactive urethane resin thus prepared in water. For dispersion in water, a dispersant can be used if necessary.

Generally, the temperature at which an isocyanate group is generated from a block isocyanate group largely depends on the type of blocking agent. When sodium bisulfite is used as the blocking agent, the temperature at which the isocyanate group is generated is as low as about 50 ° C., which is particularly preferable. Since the resulting heat-reactive urethane resin is highly hydrophilic, it can be dissolved or dispersed in water. It is easy and particularly preferable.

These heat-reactive water-based polyurethane resins can be used in the reversible thermosensitive recording layer, or can be used as an anchor in a protective layer provided with a protective layer on the upper surface or between the support and the reversible thermosensitive recording layer. It can be used in an anchor layer provided with a layer, or can be used in combination with each layer without any problem.

When the above heat-reactive water-based polyurethane resin is used, it is preferable to have a binder having a group which reacts with the isocyanate group dissociated by the blocking agent in the layer, such as a hydroxyl group, an amino group, an amide group or an imino group. An aqueous binder having a group and the like can be mentioned. Specific examples thereof include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide / acrylic acid ester. / Methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, ethylene /
Water-soluble polymers such as alkali salts of maleic anhydride copolymer, polyvinyl acetate, polyurethane, polyacrylic acid ester, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, Examples thereof include latex such as ethylene / vinyl acetate copolymer, but are not limited thereto.

It is also preferable to use such a heat-reactive water-based polyurethane resin in combination with polyamines or polyols. Examples of such polyamines include aliphatic or aromatic amines containing two or more amino groups. Specifically, for example, hexamethylenediamine,
1,10-diaminodecane, 1,12-diaminododecane, 4,4′-diaminodiphenylmethane, 4,4′-
Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether and the like can be mentioned. Further, as the polyols, polyether-based polyols, polyester-based polyols and the like can be used, and specifically, for example, polypropylene glycol, polytetramethylene glycol, a condensation polymer of adipic acid and a polyhydric alcohol, ε-caprolactam and a polyhydric alcohol. Examples thereof include ring-opening polymerization products of alcohol.
By the combined use of polyamines or polyols,
The reason why one layer of water resistance, repeated durability, and interlayer adhesion is obtained is that the isocyanate group generated by the blocking agent dissociating from the blocked isocyanate group is due to the presence of highly reactive polyamines or polyols.
It is presumed that this may be because the production of the polymer compound is promoted more.

The amount of the heat-reactive water-based polyurethane resin used is about 0.2 to 3.0 equivalents, preferably 0.8 to 2 equivalents, of the blocked isocyanate group to 1 equivalent of the reactive group. preferable. In the present invention, the crosslinking reaction is carried out in the recording layer, but the reaction temperature is 50 ° C or higher, preferably 100 ° C or higher and the reaction temperature or lower, and the reaction time is 0.1
It may be done in about 100 hours. Needless to say, a long reaction time is required when the reaction temperature is low, and a short time is required when the reaction temperature is high. Although the present invention does not require a catalyst, the addition of Lewis base, phosphines, etc. is effective in shortening the curing time.

The electron-donating dye precursor used in the present invention is typified by those generally used for pressure-sensitive recording paper and heat-sensitive recording paper, but is not particularly limited.
Specific examples include the following,
The present invention is not limited to this. (1) Triarylmethane compound 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- ( p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5 -Dimethylaminophthalide, 3-p
-Dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like,

(2) Diphenylmethane compound 4,4'-bis (dimethylaminophenyl) benzhydryl benzyl ether, N-chlorophenyl leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, etc.

(3) Xanthene compound Rhodamine B anilinolactam, Rhodamine B p-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3- Diethylamino-7-phenylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7- (3,4-dichloroanilino) fluorane, 3 -Diethylamino-7
-(2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3- (N
-Ethyl) tolylamino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-ethyl) tolylamino-6-methyl-7-phenethylfluoran, 3-diethylamino-7- (4-nitroanilino) fluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-
(N-Methyl) propylamino-6-methyl-7-anilinofluorane, 3- (N-ethyl) isoamylamino-6-methyl-7-anilinofluorane, 3- (N-methyl) cyclohexylamino- 6-methyl-7-anilinofluorane, 3- (N-ethyl) tetrahydrofurylamino-6-methyl-7-anilinofluorane and the like,

(4) Thiazine-based compound benzoyl leuco methylene blue, p-nitrobenzoyl leuco methylene blue, etc.

(5) Spiro compounds 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3'-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3 -Methoxybenzo) spiropyran, 3-propylspirobenzopyran and the like.

The above usually colorless to light-colored electron-donating dye precursors may be used alone or in combination of two or more.

The reversible color developer used in the present invention includes, for example, those represented by the general formula 1, but is not limited thereto, and a reversible change in color tone is caused to the dye precursor by heating. The compound is not particularly limited as long as it is a compound capable of generating, but the following compounds including a reversible color developing agent composed of a phenolic compound proposed by JP-A-6-210954 by the present applicant in view of image contrast, durability against repetition, etc. The electron-accepting compound represented by 1 is preferably used.

[0031]

Embedded image

In Formula 2, n represents 1, 2 or 3. m represents 0, 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 hetero atoms, a nitrogen atom-containing aromatic ring represented by A, 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 thereof include alkoxy groups such as i-propyloxy group, n-butyloxy group and n-octyloxy group, and halogen atoms 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. Of these, the 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 in which X is two or more heteroatoms 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) 10 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) 1 0 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, in addition to the linking group, -CONH-, -O-, -S-, -COO-, -O.
Divalent groups such as CO—, —OCOO, —CO—, and —SO ₂ — are also included.

Examples of the divalent group in which X contains a nitrogen atom and is bonded to the aromatic ring represented by A by a hydrocarbon group having 1 or more carbon atoms include -CH ₂ CONH- and -CH ₂ CH ₂ CO
_{NH -, - CH 2 NHCO -} , - CH 2 CH 2 NHCO
_{-, - CH 2 CH 2 CH} 2 NHCO -, - CH 2 CH 2 NH
_{COO -, - (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 thereof include docosyl group, tricosyl group, tetracosyl group, 2-norbornyl group, 7,7-dimethylnorbornyl group, 1-adamantyl group, cholesteryl group and 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 the atoms included in X and R excluding the hydrogen atom and the atoms constituting the aromatic ring 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'-hydroxyoctadecananilide, 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 ′
-Heptadecyl carbonyloxybenzanilide, 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- 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-dioctadecyloxybenzenesulfonanilide,

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-tetradecyl diphenyl sulfide, 4'-hydroxy-4-octadecyl diphenyl sulfide, 4'-hydroxy-4-octadecyl carbonylaminodiphenyl sulfide, 4 '
-Hydroxy-4-octadecyloxydiphenyl sulfide, 4'-hydroxy-4-octadecyloxysulfonyl diphenyl 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'-
Tricosyl 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) octadecane amide, 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] octadecanamide,

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 '-( pn-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] carbazic acid-n-octadecyl, 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) undecanamido] -N '-(N
'-N-decylureido) methane, 1- {N'-[2-
(P-Hydroxyphenylthio) ethyl] ureido｝-
1-n-octadecanoylaminomethane, N- [2-
(P-hydroxyphenylthio) ethyl] -N'-n-
Octadecyl malonamide,

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]-
N-n-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-tetradecyl semicarbazide, 1- [3- (p-hydroxyphenyl) propionyl] -4-n-octadecyl semicarbazide, 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) acetamide] -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 in admixture of two or more, and usually 5 to 5000% by weight, preferably 10 to 3000% by weight, based on the colorless or light-colored electron-donating dye precursor. Used.

A heat-fusible substance may be contained in the reversible thermosensitive recording layer as an additive for controlling the color developing sensitivity and the decoloring temperature of the reversible thermosensitive recording layer. 60 ° C
Those having a melting point of ~ 200 ° C are preferable, and especially 80 ° C.
Those having a melting point of -180 ° C are preferred. A sensitizer used in general thermosensitive recording paper can also be used. For example, waxes such as N-hydroxymethylstearic acid amide, stearic acid amide and palmitic acid amide, naphthol derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as p-benzylbiphenyl and 4-allyloxybiphenyl, 1,2. -Bis (3-
Polyether compounds such as methylphenoxy) ethane, 2,2'-bis (4-methoxyphenoxy) diethyl ether, bis (4-methoxyphenyl) ether, diphenyl carbonate, dibenzyl oxalate, bis (p-methylbenzyl) oxalate Carbonic acid or oxalic acid diester derivatives such as esters can be added in combination, but are not limited thereto.

The reversible thermosensitive recording material of the present invention repeatedly writes and erases an image by heating,
In order to prevent the deterioration of the reversible thermosensitive recording layer, it is also possible to provide a known protective layer, and a protective layer containing a heat-reactive aqueous polyurethane resin provided on the reversible thermosensitive recording layer as an intermediate layer, Furthermore, a known protective layer can be provided. 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, a crosslinking agent such as an epoxy compound, a urea derivative, or a vinyl compound, and a curing agent such as a phosphoric acid type, a sulfonic acid type, a polyamide type, and an amine type can be added.
Alternatively, a protective layer can be formed on a reversible thermosensitive recording material by means of laminating or the like 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.

For the reversible thermosensitive recording layer, protective layer or intermediate layer, diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide,
Pigments such as zinc oxide, silicon oxide, aluminum hydroxide, and urea-formalin resin, in addition, zinc stearate,
Higher fatty acid metal salts such as calcium stearate, waxes such as paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearic acid amide, caster wax, etc .; dispersants such as sodium dioctyl sulfosuccinate; further, surfactants, fluorescent dyes, etc. Can also be contained.

As the support used in the reversible thermosensitive recording material of the present invention, paper, coated paper, various non-woven fabrics, woven cloth, synthetic resin film, synthetic resin laminated paper, synthetic paper, metal foil, glass, or the like, or A composite sheet in which these are combined can be arbitrarily used according to the purpose, and may be transparent, translucent or opaque, but is not limited thereto. The thickness of the support is
The range is not particularly limited as long as it can withstand repeated use, but is 20 to 1300 μm, preferably 40 to 1000 μm.
m.

The structure of the reversible thermosensitive recording material of the present invention is such that the reversible thermosensitive recording layer, the other layer, the surface provided with the reversible thermosensitive recording layer, or the surface on the opposite side is electrically or 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 further 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 the 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, and a carten coater, a planographic printing plate, a relief printing plate,
It is possible to use various printing machines using intaglio, flexo, gravure, screen, hot melt and the like. Furthermore, in addition to the usual drying process, each layer can be held by UV irradiation / 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 after heating is required to form a color recorded image, and the cooling rate after heating is required to erase the recorded image. It's good if it's late. For example, after heating by an appropriate method, by rapidly cooling by pressing a low-temperature metal block or the like, a colored state can be developed. In addition, when a thermal head, a laser beam or the like is used for heating for an extremely short period of time, it is cooled immediately after the heating is completed, so that the coloring state can be maintained. On the other hand, when heated with an appropriate heat source (thermal head, laser light, heat roll, heat stamp, high frequency heating, radiant heat from a light source such as a tungsten lamp or halogen lamp, hot air, etc.) for a relatively long time, recording Since not only the layer but also the support and the like are heated, even if the heat source is removed, the cooling speed is slow and the state is decolorized. Therefore, even if the same heating temperature and / or the same heat source is used, the colored state and the decolored state can be arbitrarily expressed by controlling the cooling rate.

[0072]

The present invention will be described in more detail with reference to the following examples. Example 1 (A) Preparation of reversible heat-sensitive coating liquid 40 parts of 3-di-n-butylamino-6-methyl-7-anilinofluorane, which is a dye precursor, together with 90 parts of 2.5% polyvinyl alcohol aqueous solution. It was crushed for 24 hours with a ball mill to obtain a dye precursor dispersion liquid. Next, 100 parts of N- [3- (p-hydroxyphenyl) propiono] -N'-n-octadecanohydrazide as a reversible developer was pulverized and dispersed in a ball mill for 24 hours together with 400 parts of a 2.5% aqueous polyvinyl alcohol solution to disperse. A liquid was obtained. After mixing the above two dispersions, 200 parts of an acrylic emulsion (manufactured by Siden Chemical Co., Sibinol EK-44, solid content: 40%) as a binder, and elastron BN04 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a heat-reactive water-based polyurethane resin) Minute 3
(3%) 30 parts and 400 parts of water were added and mixed well to prepare a reversible thermosensitive coating liquid.

(B) Coating of reversible thermosensitive recording material The reversible thermosensitive coating solution prepared in (A) was coated on a polyethylene terephthalate (PET) sheet so that the solid coating amount was 4 g / m ² . After drying, it was treated with a super calendar to obtain a coated sheet B.

(C) Coating of protective layer On the coating layer of the coating sheet B obtained in (B), Aronix M
8030 (Toagosei Chemical Industry Co., Ltd.) 90 parts, N-vinyl-
5 parts of 2-pyrrolidone, 5 parts of Irgacure 500 (manufactured by Nippon Ciba Geigy) and 5 parts of Mizukasil P-527 (manufactured by Mizusawa Chemical) were added, and the UV-curable resin sufficiently stirred was added to 1.0 part.
g / m ^2, and cured with an ultraviolet irradiation device (Rapid Cure, manufactured by Ushio Inc.) to obtain a reversible thermosensitive recording material having a protective layer. Further, the obtained reversible thermosensitive recording material was heat-treated at 120 ° C. for 1 hour.

Example 2 In the preparation of the reversible heat-sensitive coating liquid (A) of Example 1, the heat-reactive water-based polyurethane resin was changed to 25 parts of Elastron BN08 (Daiichi Kogyo Seiyaku Co., solid content 40%). Except for this, the procedure was the same as in Example 1.

Example 3 In the preparation of the (A) reversible heat-sensitive coating liquid of Example 1, the heat-reactive water-based polyurethane resin was changed to 40 parts of Elastron BN69 (Daiichi Kogyo Seiyaku, solid content 40%). Except for this, the procedure was the same as in Example 1.

Examples 4 to 6 In the preparation of the reversible heat-sensitive coating liquid (A) of Example 1, 4,4'-diaminodiphenylmethane (Example 4) and 4,4'-diaminodiphenylsulfone ( Example 5) was the same as Example 1 except that 10 parts of each of 4,4′-diaminodiphenyl ether (Example 6) were used in combination.

Example 7 The procedure of Example 1 was repeated, except that the coating of the reversible thermosensitive recording material (B) of Example 1 was changed as follows. (B) Coating of reversible thermosensitive recording material Acrylic emulsion (Sibinol EK, manufactured by Seiden Chemical Co., Ltd.) was applied to polyethylene terephthalate (PET) sheet.
-35, solid content 40%) 25 parts, heat-reactive water-based polyurethane resin 3 parts elastron BN04 (Daiichi Kogyo Seiyaku Co., solid content 33%) 5 parts Mizukasil P-527 (manufactured by Mizusawa Chemical Co., Ltd.), water 10 parts And the solid coating amount is 1 g / m
^It was coated so that it would be ² and used as an anchor layer. next,
The reversible heat-sensitive coating liquid prepared in (A) was coated on the anchor layer so that the solid coating amount was 4 g / m ² , dried and then treated with a super calendar to obtain a coated sheet B.

Example 8 Example 8 was performed in the same manner as in Example 1 except that the coating of the protective layer (C) in Example 1 was changed as follows. (C) Coating of protective layer On the coating layer of the coating sheet B obtained in (B), 25 parts of acrylic emulsion (Cybinol EK-55 manufactured by Saiden Chemical Co., solid content 40%), heat-reactive water-based polyurethane resin As elastron BN04 (Daiichi Kogyo Seiyaku, solid content 3
3%) 3 parts and water 35 parts are mixed to give a solid coating amount of 1 g / m ²
Was applied to form an intermediate layer. Next, 90 parts of Aronix M8030 (manufactured by Toagosei Chemical Industry Co., Ltd.), 5 parts of N-vinyl-2-pyrrolidone, 5 parts of Irgacure 500 (manufactured by Ciba Geigy), and 5 parts of Mizukasil P-527 (manufactured by Mizusawa Chemical Co., Ltd.) were added and sufficiently stirred. UV curable resin
After coating so as to be 0 g / m ² , curing was performed with an ultraviolet irradiation device (Rapid Cure, manufactured by Ushio Inc.)
A reversible thermosensitive recording material having an intermediate layer and a protective layer was obtained.
Further, the obtained reversible thermosensitive recording material was heat-treated at 120 ° C. for 1 hour.

Example 9 In the coating of the protective layer (C) of Example 1, heat treatment was carried out 5 times.
The same procedure as in Example 1 was repeated except that the temperature was changed to 0 ° C. for 72 hours.

Comparative Example 1 The procedure of Example 1 was repeated except that the heat-reactive water-based polyurethane resin was not used in the preparation of the reversible heat-sensitive coating liquid (A) of Example 1.

Comparative Example 2 In the preparation of the reversible heat-sensitive coating liquid (A) of Example 7 and the coating of the reversible heat-sensitive recording material (B), the heat-reactive water-based polyurethane resin was not used, except that Same as Example 7.

Comparative Example 3 Example 8 was repeated except that the heat-reactive water-based polyurethane resin was not used in the preparation of the reversible heat-sensitive coating liquid of Example 8 and the coating of the protective layer (C). Same as.

Comparative Example 4 In the coating of the protective layer (C) of Example 1, the heat treatment was carried out 4 times.
The same procedure as in Example 1 was repeated except that the temperature was changed to 0 ° C. for 24 hours.

The following evaluation tests were carried out on the reversible thermosensitive recording materials prepared as described above. Test method The reversible thermosensitive recording materials obtained in the examples and comparative examples were applied with an application pulse of 2.0 milliseconds for a thermal facsimile printing tester TH-PMD manufactured by Okura Electric Co. with a print head KJT-256-8MGF1 manufactured by Kyocera. Printed under the condition of a voltage of 25 V, and the obtained color image is a densitometer Macbeth RD918
Was measured as a color density. The obtained colored image portion was heated at 120 ° C. for 1 second using a heat stamp to erase the color, and then the density was measured in the same manner to obtain the erased density.

Further, the above-mentioned color development and decolorization were repeated 100 times, the color development density and the decolorization density at the 100th time were measured, and the recording surface was observed and evaluated according to the following criteria. ：: good, no damage on the recording surface. ：: Slight print flaws are observed on the recording surface, but there is no practical problem. ×: Destruction of the recording surface print layer is observed.

The reversible thermosensitive recording material thus obtained was immersed in water for 100 hours, the recording surface was immediately rubbed with a finger, the surface was observed, and the water resistance was evaluated according to the following criteria. ：: No damage on the recording surface was observed, and it was good. ×: Destruction of the recording surface print layer is observed.

[0088]

[Table 1]

From Table 1, Examples 1 to 3 in which the heat-reactive water-based polyurethane resin was changed to the reversible thermosensitive recording layer were excellent in coloring and decoloring even after repeating, had good image contrast, and had high durability. Also, it is understood that it also has sufficient water resistance. Further, it can be understood that Examples 7 and 8 in which the heat-reactive water-based polyurethane was also used in the anchor layer or the intermediate layer are particularly resistant to repeated use and no reduction in print density is observed, and thus are very excellent. . Examples 4-6
Similarly, good color development and color erasure were exhibited, and it was possible to repeatedly perform color development and color erasure, and the water resistance was also sufficient. In Comparative Examples 1, 2 and 3, sufficient coloring and decoloring densities were obtained, but when the coloring and decoloring were repeated, a decrease in the coloring density and an increase in the erasing density were observed, and the image contrast Was significantly reduced. Particularly in Comparative Example 3, remarkable destruction of the recording layer, which is considered to be caused by the thermal head, was recognized.
Regarding the water resistance, peeling of the printing surface recording layer was observed after immersion in water. Further, Comparative Example 4 in which the heat treatment temperature was 40 ° C.
In comparison with the heat treatment temperature of 50 ° C. of Example 9, the erasing concentration was slightly higher and the water resistance was particularly insufficient. From this, a clear difference is observed between the example and the comparative example, and it is confirmed that the present invention has a great effect.

[0090]

INDUSTRIAL APPLICABILITY The reversible thermosensitive recording material of the present invention can be colored by heat energy of a thermal head or the like, and can be changed to a decolored state by heating the composition in the colored state again. Further, such coloring and erasing can be repeated, and the coloring and erasing states can be maintained at room temperature. Further, in the reversible thermosensitive recording material of the present invention, by containing a heat-reactive water-based polyurethane resin in the reversible thermosensitive recording layer, or a protective layer as an upper layer thereof, or an anchor layer between the support, color development It can be used as a reversible heat-sensitive recording material which has little damage even after repeated use of decoloring and is highly water resistant and which is satisfactory in practice.

Claims (5)

[Claims] 1. A support comprising, on at least one surface of a support, an usually colorless to light-colored electron-donating dye precursor and a reversible developer that develops the dye precursor by heating and reheats it to decolorize it. A reversible heat-sensitive recording material having a reversible heat-sensitive recording layer, wherein the reversible heat-sensitive recording layer contains a heat-reactive water-based urethane resin. 2. At least one surface of a support contains a usually colorless to light-colored electron-donating dye precursor and a reversible developer that causes the dye precursor to develop a color upon heating and reheats the color to decolorize it. In the reversible thermosensitive recording material provided with the reversible thermosensitive recording layer, a protective layer is provided on the upper surface of the reversible thermosensitive recording layer, and a heat-reactive water-based urethane resin is contained in the protective layer. Reversible thermosensitive recording material. 3. A support containing, on at least one side of a support, an usually colorless or pale color electron-donating dye precursor and a reversible developer that causes the dye precursor to develop color by heating and then reheats to erase the color. In the reversible heat-sensitive recording material provided with the reversible heat-sensitive recording layer, an anchor layer is provided between the reversible heat-sensitive recording layer and the support, and the heat-reactive water-based urethane resin is contained in the anchor layer. Characteristic reversible heat-sensitive recording material. 4. The reversible thermosensitive recording material according to claim 1, wherein the layer containing the heat-reactive water-based urethane resin further contains polyamines or polyols. 5. The reversible thermosensitive recording material according to claim 1, wherein after forming a layer containing a heat-reactive water-based urethane resin, heat treatment is performed at a temperature of 50 ° C. or higher and a temperature lower than the color development temperature. The reversible thermosensitive recording material according to items 3 and 4.