JPH10193792A - Reversible heat-sensitive recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To minimize the deterioration of color forming and extinguishing properties and improve repeatability thereof even in the case of repeated used of color development and erasure by allowing a chlorinated polypropylene resin to be contained in a reversible heat-sensitive recording layer. SOLUTION: A chlorinated polypropylene resin is contained in a reversible heat-sensitive recording layer together with an electron-donating dyestuff precursor and a reversible developer. A principal role of a binder resin which is a resin component in the recording layer is to prevent a reversible thermo-color forming composition from being aggregated by repeated color development and erasure. By using a highly heat-resistant chlorinated polypropylene for a binder resin, durability in repeat of image formation and erasure due to a heating means such as a thermal head is improved, and not only the service life of a recording medium is prolonged to a great extent, but also color development erasure characteristics are improved. It is estimated that a reason for improvement in durability is due to the fact that the chlorinated polypropylene resin holds a high softening point without deteriorating a binder effect.

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 high durability. It provides a recording material.

[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, it is impossible for such a heat-sensitive recording material to form an image once and erase that portion and return to the state before image formation. There was no choice but to add to the formation. 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, reversible thermosensitive recording materials which can be used repeatedly for image formation and image erasure have been devised in order to cope with such a problem.
7, JP-A-63-39377, JP-A-63-39377
JP-A-41186 describes a heat-sensitive recording material composed of a resin base material and low-molecular organic molecules dispersed in the resin base material. However, in this method, the transparency of the heat-sensitive recording material is reversibly changed by heat energy, so that the contrast between the image forming portion and the non-image forming portion is insufficient.

In the methods described in Japanese Patent Application Laid-Open Nos. 50-81157 and 50-105555, since the image to be formed changes according to the environmental temperature, the image forming state and the erasing state are changed. Are different from each other, and these two states cannot be maintained for an arbitrary period at room temperature.

Further, Japanese Patent Application Laid-Open No. Sho 59-120492 discloses that an image forming state is controlled by keeping a recording material in a hysteresis temperature range by utilizing a hysteresis characteristic of a coloring component.
Although a method for 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 range. 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.
No. 11898 describes a reversible thermosensitive recording medium comprising a leuco dye and a color-reducing agent which causes the leuco dye to develop and decolor the color 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 between the coloring reaction and the decoloring reaction only by controlling the heat energy, and since both reactions occur at a certain ratio at the same time, a sufficient coloring density cannot be obtained. Can't do it perfectly. Therefore, sufficient image contrast cannot be obtained. Also,
Since the decolorizing action of the basic group also acts on the colored portion at room temperature,
The phenomenon that the density of the color-developed portion decreases over time is inevitable.

Further, Japanese Patent Application Laid-Open No. 5-124360 describes a reversible thermosensitive recording medium for coloring and decoloring a leuco dye by heating. Specific phenol compounds such as carboxylic acids, fatty acid dicarboxylic acids, and alkylthiophenols having alkyl groups having 12 or more carbon atoms, alkyloxyphenols, alkylcarbamoylphenols, and alkyl gallates are exemplified. However, even with this recording medium, the two problems of low color density and incomplete erasing cannot be solved at the same time, and there is no practically satisfactory image stability over time.

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 JP-A-6-210954. However, in such a reversible thermosensitive recording material having a recording layer that develops color by heat, its properties such as color developability, decolorability, and repeatability of color development and decoloration are necessary for forming the recording layer. It was also found that the resin composition was affected by various types of resin components, and that some types of resin caused practical problems. That is, the resin component of the reversible thermosensitive recording layer in the reversible thermosensitive recording material includes polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, gelatin, casein, starch, sodium polyacrylate, polyvinylpyrrolidone, polyacrylamide, and various maleic acid copolymers. Coalescing, various acrylic acid copolymers, polystyrene,
Polyvinyl chloride, polyvinyl acetate, polyacrylates, polymethacrylates, vinyl chloride / vinyl acetate copolymers, various styrene copolymers, polyesters, polyurethanes and the like are used. When a resin is used, the developer particles tend to aggregate due to heat and pressure at the time of applying heat, and therefore, there is a problem that the coloring property of the thermosensitive recording layer is reduced when the resin is used repeatedly many times.

[0011]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the reversible thermosensitive recording material, and improves the reproducibility of the reversible thermosensitive recording material even when the color reproducibility and the decolorability are reduced even by repeated use of the color reproducibility. It is an issue to provide such products.

[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,
In the reversible thermosensitive recording material provided with a reversible thermosensitive recording layer containing a reversible color developer containing a reversible color developer that causes the dye precursor to develop a color by heating and decoloring by reheating, by using a chlorinated polypropylene resin, This problem has been solved.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION A reversible thermosensitive recording material utilizing a reaction between a dye precursor such as a leuco compound and a reversible color developer has a reversible color developer having a relatively long chain aliphatic hydrocarbon group. Because of this, there is a problem that the durability of the recording layer is low. For example, if color development and decoloration are repeated at the same location, the reversible coloring matter aggregates or the reversible thermosensitive recording layer leaks out because the thermal head is repeatedly exposed to the pressure and the heat source. Tends to occur.

In order to solve these problems, in the present invention, a chlorinated polypropylene resin is contained in the reversible thermosensitive recording layer together with an electron-donating dye precursor and a reversible developer. The resin component in the recording layer is also called a binder resin, and its main role is to prevent the reversible thermochromic composition from aggregating due to repetition of color development and decoloration. Is used as a binder resin, the durability of repeated image formation and erasing by a heating means such as a thermal head is improved, the life of the recording material is greatly increased, and the color development and decoloration characteristics are also improved. The commercial value of the material also increases.

Although the reason for improving the durability of the recording layer according to the present invention is not sufficiently clear, the chlorinated polypropylene resin does not impair the binder effect as compared with vinyl chloride or polypropylene resin widely used as a binder resin. It is estimated that it has a high softening point. Chlorinated polypropylene has a high softening point temperature of 80 to 100 ° C., while a normal unchlorinated resin has a softening point of 50 to 60 ° C. That is, when the chlorinated polypropylene resin is used as the binder resin, compared to the case of the polypropylene resin or the like, the same reversible developer and dispersibility of the dye precursor, such as the initial color development and decoloring properties, It is presumed that the quality is improved because it inherits the same properties as when a polypropylene resin is used and also prevents the difficulty that the reversible developer particles aggregate to improve the softening temperature. The reversible developer particles are likely to aggregate in the low softening point resin due to the effect of the surrounding binder resin being deformed by the temperature and pressure at the time of heat application when heat is applied, which affects the color developability. In the case of the functionalized polypropylene resin, since the softening point is high, the reversible developer particles are not affected by the binder resin, and the reversible developer particles maintain the initial state even after long-term use.

In the present invention, a chlorinated propylene resin can be appropriately mixed with a conventional binder resin as a binder resin for the recording layer. The purpose of mixed use is
It is an improvement in the adhesiveness between the base and the protective layer, and an improvement in the solvent resistance typified by the prevention of erosion of the recording layer by a solvent during the application of the protective layer. Taking into account the type of the protective layer and the solvent at the time of lamination, single use or mixed use is considered.

The resin suitable for use in combination with the chlorinated polypropylene resin has good compatibility with the chlorinated polypropylene,
It is a conventional binder resin that maintains transparency when mixed and used, and specific examples are as follows. That is,
Polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinyl acetate / vinyl alcohol copolymer, vinyl chloride / vinyl acetate / maleic acid copolymer, vinyl chloride / acryl Acid ester copolymer, polyvinylidene chloride, vinylidene chloride
Vinyl chloride copolymer, vinylidene chloride / acrylonitrile copolymer, various polyesters, various polyamides, various polyacrylates, various polymethacrylates, acrylate / methacrylate copolymers, silicone resins, etc. Alternatively, two or more kinds may be mixed and used with the chlorinated polypropylene resin.

The electron-donating dye precursor used in the present invention is typified by those generally used for pressure-sensitive recording paper and thermosensitive 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 compounds 4,4'-bis (dimethylaminophenyl) benzhydryl benzyl ether, N-chlorophenylleuco auramine, N-2,4,5-trichlorophenyl leuco auramine, etc.

(3) Xanthene compounds rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3- Diethylamino-7-phenylfluoran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3 -Diethylamino-7
-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 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-anilinofluoran, 3- (N-ethyl) isoamylamino-6-methyl-7-anilinofluoran, 3- (N-methyl) cyclohexylamino- 6-methyl-7-anilinofluoran, 3- (N-ethyl) tetrahydrofurylamino-6-methyl-7-anilinofluoran, etc.

(4) Thiazine compounds Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc.

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

As the colorless or light-colored electron-donating dye precursor, one kind or a mixture of two or more kinds may be used.

Examples of the reversible color developer used in the present invention include, but are not limited to, those represented by the following general formula 1, and the reversible color change of the dye precursor upon heating is not limited thereto. There is no particular limitation as long as it is a compound that causes the following, but from the viewpoint of image contrast, repetition durability and the like, the present applicant has included a reversible color developer composed of a phenolic compound proposed in JP-A-6-210954.
An electron-accepting compound represented by the following general formula 1 is preferably used.

[0025]

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 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- and -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 is a group containing 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.

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 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 hydrogen atom and the atoms constituting the aromatic ring among the atoms contained in X and R is 8 or more, especially 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 '
-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- 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 '-( 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] -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) undecanamido] -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.

Each of these can be used alone or in combination of two or more. The ratio of the electron-donating dye precursor to the reversible developer in the reversible thermosensitive recording layer constituting the reversible thermosensitive recording material of the present invention needs to be appropriately selected depending on the physical properties of the compound used. The range is roughly
The molar ratio of the reversible developer to the dye precursor 1 is in the range of 1 to 20, preferably 2 to 10. At least, and even if the amount of reversible developer is larger than this range, the density of the color-developed state becomes low, which is a practical problem.

As the ratio of the binder resin, it is necessary to select an appropriate ratio depending on the physical properties of the compound used. Generally, the range is from 10 to 3 parts by weight of the binder resin to 100 parts in total of the dye precursor and the reversible developer used.
00, preferably 20 to 100. If the amount of the binder resin is less than this range, sufficient adhesive strength cannot be obtained, and the durability of the resin composition will be reduced. Conversely, if the amount of the binder resin is large, the color density is reduced, and the image contrast cannot be obtained.

Further, a heat-fusible substance can be contained in the reversible thermosensitive recording layer as an additive for adjusting the coloring sensitivity and the decoloring temperature of the reversible thermosensitive recording layer. 60 ° C
Those having a melting point of 200 ° C to 200 ° 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, palmitic acid amide, naphthol derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as p-benzylbiphenyl and 4-allyloxybiphenyl, 1,2 -Screw (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 deterioration of the reversible thermosensitive recording layer, it is possible to provide a known protective layer, or to provide a protective layer provided on the reversible thermosensitive recording layer as an intermediate layer and further provide a known protective layer. 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, 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. In addition, in advance in the state of a transparent film such as polyethylene, polyethylene terephthalate, etc.,
A protective layer can also be formed on the reversible thermosensitive recording material by means such as bonding. In this case, if necessary, the protective layer or the intermediate layer may be composed of two or three or more layers.

In 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 nonwoven fabrics, woven fabric, synthetic resin film, synthetic resin laminated paper, synthetic paper, metal foil, glass, etc. A composite sheet combining these can be used arbitrarily according to the purpose, and may be transparent, translucent, or opaque, but is not limited thereto. The thickness of the support is
There is no particular limitation as long as it can withstand repeated use, but 20 to 1300 μm, preferably 40 to 1000 μm
m.

The constitution 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 further subjected to an adhesive process or the like.

The method for 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, smearing devices such as air knife coaters, blade coaters, bar coaters, curtain coaters, etc., lithographic, letterpress,
Various printing machines and the like using intaglio, flexo, gravure, screen, hot melt, and the like can be used. Further, each layer can be held by UV irradiation or EB irradiation in addition to the usual drying step. By these methods, smearing and printing can be performed one layer at a time or simultaneously at multiple layers.

In the reversible heat-sensitive recording material of the present invention, rapid cooling may be performed following heating to form a color-recorded image, and the cooling rate after heating may be reduced in order to erase the recorded image. Good if it is 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 heating is performed for a very short time using a thermal head, a laser beam, or the like, cooling is performed immediately after the heating is completed, so that a color-developed state can be maintained.

On the other hand, heating by a suitable heat source (thermal head, laser light, heat roll, heat stamp, high frequency heating, electric heater, radiant heat from a light source such as a tungsten lamp or a halogen lamp, hot air, etc.) for a relatively long time Then, since not only the recording layer but also the support and the like are heated, even if the heat source is removed, the cooling speed is low and the color is erased. Thus, using the same heating temperature and / or the same heat source,
By controlling the cooling rate, a colored state and a decolored state can be arbitrarily developed.

[0068]

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

Example 1 (A) Preparation of reversible thermosensitive coating solution 13 parts of 3-di-n-butylamino-6-methyl-7-anilinofluorane as a dye precursor and N- as a reversible developer [3- (p-hydroxyphenyl) propiono]
65 parts of -N'-n-octadecanohydrazide, 125 parts of chlorinated polypropylene 803 MW (manufactured by Nippon Paper Industries Co., Ltd., trade name: Supercron) as a binder resin,
A reversible thermosensitive coating liquid was prepared by pulverizing toluene as a diluting solvent together with 450 parts by a ball mill for 24 hours.

(B) Coating of reversible thermosensitive recording material The reversible thermosensitive coating solution prepared in (A) was coated on a polyethylene terephthalate (PET) sheet at a solid coating amount of 4 g / m 2.
It was applied in ² to become like, after drying, to obtain a coated sheet B.

(C) Coating of protective layer On the coating layer of the coated sheet B obtained in the above (B), 90 parts of Aronix M8030 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), 5 parts of N-vinyl-2-pyrrolidone, 1 part 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 was sufficiently stirred.
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 a protective layer was obtained.

Example 2 Except for changing the binder resin to 125 parts of chlorinated polypropylene 822 (manufactured by Nippon Paper Industries Co., Ltd.) in the preparation of (A) the reversible thermosensitive coating solution of Example 1. Was the same as in Example 1.

Example 3 In the preparation of the reversible thermosensitive coating solution (A) of Example 1, the binder resin was changed from chlorinated polypropylene S-309 (manufactured by Nippon Paper Industries Co., Ltd., trade name: Supercron) to 125 parts. Except having performed, it carried out similarly to Example 1.

Example 4 In the preparation of (A) the reversible heat-sensitive coating liquid of Example 1, the binder resin was 125 parts of modified chlorinated polypropylene 214 (manufactured by Nippon Paper Co., Ltd., trade name: Supercron) and 15 parts of Coronate L The procedure was the same as that of Example 1 except for changing to.

Example 5 In the preparation of the reversible thermosensitive coating solution (A) of Example 1, the binder resin was modified with 125 parts of modified chlorinated polypropylene 224H (manufactured by Nippon Paper Co., Ltd., trade name: Supercron) and 15 parts of Coronate L. The procedure was the same as that of Example 1 except for changing to.

Comparative Example 1 In the preparation of the reversible thermosensitive coating solution (A) of Example 1, the binder resin was a vinyl chloride / vinyl acetate copolymer VYHH.
(Union Carbide) The procedure was the same as in Example 1 except that the quantity was changed to 45 parts.

Comparative Example 2 The procedure of Example 1 was repeated except that the binder resin was changed to 125 parts of a polypropylene resin (trade name: Viscol, manufactured by Sanyo Chemical Industry Co., Ltd.) in the preparation of the reversible thermosensitive coating solution (A).
It was the same as in Example 1.

The following evaluation test was performed on the reversible thermosensitive recording material produced as described above. <Printing test method> Using the reversible thermosensitive recording materials obtained in the examples and comparative examples, an applied pulse width of 2.0 milliseconds and an applied voltage of 2 were applied by a Kyocera 8-dot / mm thermal head.
Printing was performed under the condition of 1 volt, and the resulting color image was measured as a color density using a densitometer Macbeth RD918. Further, a heat stamp is applied to the obtained color image portion,
After heating at 1 ° C. for 1 second to erase the color, the density was measured in the same manner, and the measurement results shown in Table 1 were obtained as the erase color density. After repeating the coloring and decoloring 20 times, the coloring density and the decoloring density were measured. In addition, the places where printing was repeated 20 times were observed with an optical microscope, and the degree of damage on the printing recording surface was evaluated.
The evaluation criteria are as follows. ：: No damage on the recording surface was observed and good. ○: Slight print scratches were observed on the recording surface, but no problem in practical use. ×: Many destructions and scratches were observed on the recording print surface.

[0079]

[Table 1]

As is clear from Table 1, in the examples in which chlorinated polypropylene was used as the binder resin in the reversible thermosensitive layer, there was almost no change in the reflection density of the colored portion and the decolored portion from the first time to the twentieth time. There was almost no damage on the recording surface. In the comparative example, it was observed that the color developability deteriorated from around the third time, the erasing density also increased, and the contrast of the image tended to decrease. On the recording surface, many cracks in the protective layer were observed, and there were some places where the reversible thermosensitive recording layer was confirmed to be broken. 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.

[0081]

The reversible thermosensitive recording material of the present invention can be colored by the thermal energy of a thermal head or the like, and can be changed to the decolored state by heating the composition in the colored state again. Such coloring and erasing can be performed repeatedly, 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 chlorinated polypropylene resin in the reversible thermosensitive recording layer, the reversible thermosensitive recording material is used as a reversible thermosensitive recording material with little damage even by repeated use of color development and decoloration. I can do it.

Claims (1)

[Claims] At least one surface of a support contains a generally colorless or light-colored electron-donating dye precursor, and a reversible developer that causes the dye precursor to develop color by heating and to be decolorized by reheating. A reversible thermosensitive recording material provided with a reversible thermosensitive recording layer comprising a chlorinated polypropylene resin in the reversible thermosensitive recording layer.