JPH10203016A - Reversible thermal recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reversible thermal recording material wherein good image contrast is held and forming and erasing of the image is possible and damage is hardly caused by repeated use of color developing and erasing and strong water resistance is provided in a reversible thermal recording material where in on at least one face of a substrate, a reversible thermal recording layer contg. an ordinarily colorless or light-colored leuco dye and a reversible color developer which develops the color of the leuco dye by heating and erases this by reheating is provided. SOLUTION: A zirconium compd. is incorporated in a reversible thermal recording layer in a reversible thermal recording material. It can be incorporated in a protective layer which is provided on the top face of this thermal recording layer or in an anchor layer provided between a substrate and the reversible thermal recording layer, and also incorporated in each layer in parallel. In addition, it is pref. that both the zirconium compd. and a binder with carboxyl group, hydroxyl group, amino group, amide group and imino group are used in parallel.

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 heat-sensitive recording material generally comprises a support provided with a heat-sensitive recording layer mainly comprising an electron-donating, usually colorless or pale-colored leuco dye and an electron-accepting developer. By heating with a thermal head, a hot pen, a laser beam, or the like, the leuco dye and the developer react instantaneously to obtain a recorded image. JP-B-43-4160, JP-B-43
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 the reversible thermosensitive recording material obtained by this method, if the coloring and decoloring are repeated at the same location, the recording layer is deteriorated and the coloring density is lowered, or the water resistance of the recording layer is insufficient. Therefore, there has been a problem that the recording layer swells or peels off when immersed in water for a long time. In contrast,
JP-A-6-8626 proposes a cured product of polyvinyl butyral and an isocyanate compound for the protective layer. However, when the number of repetitions is increased, the coloring density is reduced, and water resistance is insufficient. 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 made of a colorless or pale-colored leuco dye, and the leuco dye is colored by heating. This problem has been solved by using a zirconium compound in a reversible thermosensitive recording material provided with a reversible thermosensitive recording layer containing a reversible color developer that reheats and decolors the material.

[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.

In order to solve these problems, the present inventor has studied leuco dyes, reversible developers and adhesives thereof. As a result, by using a zirconium compound in the reversible thermosensitive recording material, the coloring and decoloring properties were improved. It has succeeded in obtaining a reversible thermosensitive recording material having good repetition durability without impairment and having sufficient water resistance. The zirconium compound is a cross-linking agent that forms a strong surface bond with polymers such as polyvinyl alcohol, starch, and latex, and as a result, exhibits strong water repellency. In particular, zirconium compounds
Compared to other cross-linking agents, there are no drawbacks such as inhibition of color development and coloring of the background, and no coloration occurs even when repeatedly exposed to a heat source due to reheating at the time of decoloring, impairing coloring and decoloring at all The feature is that it can be crosslinked without any problems. These zirconium compounds are very effective to be added not only to the reversible thermosensitive layer but also to the anchor layer between the reversible thermosensitive layer and the support, and to the protective layer, and the zirconium compounds added to the anchor layer and the protective layer are very effective. Crosslinks between the layers to improve the adhesion of the reversible thermosensitive recording layer without impairing the color development and decoloration,
It is possible to obtain a reversible thermosensitive recording material having good durability which is not easily destroyed by heat due to repeated coloring and decoloring.

As such a zirconium compound, various known compounds can be used, but particularly important ones are zirconium hydroxide, zirconium sulfate, zirconium carbonate, zirconium oxychloride, zirconium nitrate, zirconium stearate, and zirconium stearate. Examples include zirconium ammonium, zirconium acetate, zirconium propionate, zirconium methacrylate, zirconium acrylate, and zirconium hydroxychloride.

These zirconium compounds can be used in a reversible thermosensitive recording layer, or an anchor layer is provided in a protective layer provided with a protective layer on the upper surface, or between a support and a reversible thermosensitive recording layer. It can be used in the anchor layer, and if used in each layer, the adhesion between the layers is improved. Therefore, it is also preferable to use it in combination with each layer.

When using the above zirconium compound,
It is preferable that a binder having a functional group that undergoes a cross-linking reaction is present in the layer, and examples thereof include a binder having a hydroxyl group, an amino group, an amide group, an imino group, an imide group, and the like. Specific examples include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol,
Modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylate copolymer, acrylamide / acrylate / 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, polyacrylate, styrene / butadiene copolymer,
Latexes such as acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene / vinyl acetate copolymer, and the like are included, but are not limited thereto.

The weight ratio of the zirconium compound to the binder used is arbitrarily determined depending on the selected components, but is preferably in the range of 2 to 0.05: 1. In the present invention, the crosslinking reaction is carried out in the recording layer. The reaction may be carried out at a reaction temperature of 80 ° C. or higher, preferably 100 ° C. or higher and a color development temperature or lower, and a reaction time of 0.1 to 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.

The leuco dye used in the present invention includes:
Generally, it is represented by those used for pressure-sensitive recording paper, heat-sensitive recording paper, and the like, but is not particularly limited. Specific examples include the following, but the present invention is not limited thereto. (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.

The above usually colorless or pale leuco dyes 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 following general formula 1, but is not limited thereto, and causes a reversible color change in the leuco dye upon heating. The compound is not particularly limited as long as it is a compound to be used, but includes the following general formulas including a reversible developer composed of a phenolic compound proposed by the present applicant in Japanese Patent Application Laid-Open No. 6-210954 in consideration of image contrast, repetition durability and the like. The electron accepting compound represented by 1 is preferably used.

[0026]

Embedded image

In the formula, n represents 1, 2 or 3. m is 0,
Represents 1 or 2. Q represents an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. The ring represented by A is an aromatic ring. X is a divalent group bonded to the aromatic ring represented by A via a nitrogen atom, a divalent group containing two or more 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.

X is a divalent group containing two or more heteroatoms
Examples of -SO_TwoNH-, -SS-, -CON
HNH-, -CONHNHCO-, -CONHCH_TwoC
O-, -CONHNHCOO-, -CONHCH_TwoCO
O-, -CONHNHCONH-, -CONHCH_TwoC
ONH-, -CONHNHCONHNH-, -CONH
CH_TwoCONHNH-, -CH_TwoNHCONH-, -CH
_TwoCH_TwoNHCONH-, -CH_TwoCH_TwoCH_TwoNHCON
H-, -CH_TwoCH_TwoCH_TwoNHCONH-, -SCH_TwoC
ONH-, -SCH_TwoCH_TwoCONH-, -S (CH_Two)_Five
CONH-, -S (CH_Two)_TenCONH-, -S (p-
C₆H_Four) CONH-, -SCH_TwoNHCO-, -SCH_Two
CH_TwoNHCO-, -S (CH_Two)₆NHCO-, -S
(P-C₆H_Four) NHCO-, -SCH_TwoNHCONH
-, -SCH_TwoCH_TwoNHCONH-, -S (CH_Two)₆N
HCONH-, -S (p-C₆H_Four) NHCONH-,-
S (CH _Two)_{1 0}NHCONH-, -SCH_TwoCH_TwoNHC
OO-, -S (CH_Two)₆NHCOO-, -S (p-C₆
H_Four) NHCOO-, -S (CH_Two)₆OCONH-,-
S (p-C₆H_Four) OCONH-, -S (CH_Two)₁₁OC
ONH-, -SCH_TwoCH_TwoCONH-, -S (CH_Two)_Five
CONH-, -SCH_TwoCH_TwoNHCO (p-C₆H_Four)
-, -SCH_TwoCONHNHCO-, -SCH_TwoCH_TwoC
ONHNHCO-, -S (CH_Two)₆CONHNHCO
-, -S (CH_Two)₆CONNHNHCO (p-C₆H_Four)
-, -S (CH_Two)_TenCONHNHCO-, -S (p-
C₆H_Four) CONHNHCO-, -SCH_Two(P-C
₆H_Four) CONHNHCO-, -SCH_TwoCH_TwoNHCOC
ONH-, -SCH_TwoCH_TwoCH_TwoNHCOCONH-,
-S (CH_Two)₁₁NHCOCONH-, -S (p-C₆H
_Four) NHCOCONH-, -SCH_TwoCONHCONH
-, -SCH_TwoCH_TwoCONHCONH-, -S (p-C
₆H_Four) CONHCONH-, -SCH_TwoCH_TwoNHCON
HCO-, -S (p-C₆H_Four) NHCONHCO-,-
SCH_TwoCH_TwoCONHNHCONH-, -S (CH_Two)
_TenCONHNHCONH-, -SCH_TwoCH_TwoNHNHC
ONH-, -S (p-C₆H_Four) NHNHCONH-,-
SCH_TwoCH_TwoNHCONHNH-, -S (p-C₆H_Four)
NHCONHNH-, -SCH_TwoCONHCONHNH
-, -SCH_TwoCH_TwoCONHCONHNH-, -S (C
H_Two)_TenCONHCONHNH-, -S (p-C₆H_Four)
CONHNHCONH-, -S (p-C₆H_Four) CONH
CONHNH-, -SCH_TwoCONHCONHNHCO
-, -SCH_TwoCH_TwoCONHCONHNHCO-, -S
(CH_Two)_TenCONHCONHNHCO-, -S (p-
C₆H_Four) CONHNHCONHCO-, -S (p-C₆
H_Four) CONHCONHNHCO-, -SCH_TwoCONH
(CH_Two) NHCO-, -SCH_TwoCH_TwoCONH (C
H_Two) NHCO-, -S (p-C₆H_Four) CONH (C
H_Two) NHCO-, -S (CH_Two)_TenCONH (CH_Two)
NHCO-, -SCH_TwoCON (CH_Two) NHCONH
-, -SCH_TwoCH_TwoCON (CH_Two) NHCONH-,
-S (CH_Two)_TenCONHCONH (CH_Two) NHCO
-, -S (p-C₆H_Four) CONH (CH_Two) NHCO
-, -SCH_TwoCH_TwoNHCONH (CH_Two) NHCO
-, -SCH_TwoCH_TwoNHCOCH_TwoCONH-, -S
(P-C₆H_Four) NHCONH (CH_Two) NHCO-,-
S (p-C₆H_Four) NHCOCH_TwoCONH- and the like
It is. Specific examples of the hetero atom include an oxygen atom and a nitrogen atom.
Atom, sulfur atom, phosphorus atom, boron atom, silicon atom, selenium
Atom, fluorine atom, chlorine atom, bromine atom, iodine atom, tin
Atoms.

X is an unsaturated bond or an aromatic ring containing 2
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'-octadecyl urea, N- (2-hydroxyphenyl) -N'-octyl urea, 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.

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

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 the deterioration of the reversible thermosensitive recording layer, a known protective layer may be provided, or the protective layer containing a zirconium compound provided on the reversible thermosensitive recording layer may be used as an intermediate layer, and the known protective layer may be further provided. It is also possible to provide layers. Examples of a material for forming such a protective layer include a water-soluble polymer, latex, and a polymerizable compound. For example, zirconium compound, polyester resin, epoxy resin, melamine resin, polyvinyl alcohol, nitrocellulose, methacrylate, acrylic acid oligomer,
Acrylic ester oligomers 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.

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, when heated by an appropriate 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, recording is performed. 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 low and the color is erased. Therefore, even if the same heating temperature and / or the same heat source is used, the color development state and the decoloration state can be arbitrarily developed by controlling the cooling rate.

[0067]

The present invention will be described in more detail with reference to the following examples. Example 1 (A) Preparation of Reversible Thermal Sensitive Coating Solution A 40-part leuco dye, 3-di-n-butylamino-6-methyl-7-anilinofluoran, was ball-milled together with 90 parts of a 2.5% aqueous solution of polyvinyl alcohol. For 24 hours to obtain a leuco dye dispersion. Next, 100 parts of N- [3- (p-hydroxyphenyl) propiono] -N'-n-octadecanohydrazide as a reversible developer was ground and dispersed in a ball mill for 24 hours together with 400 parts of a 2.5% aqueous solution of polyvinyl alcohol. 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, 120 parts of a 20% aqueous solution of zirconium ammonium carbonate as a zirconium compound and 30 parts of water
0 parts were added and mixed well to prepare a reversible thermosensitive coating solution.

(B) Coating of the 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 calender to obtain a coated sheet B.

(C) Coating of protective layer Aronix M was applied on the coating layer of the coated sheet B obtained in (B).
8030 (manufactured by Toa Gosei Chemical Industry) 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 then cured with an ultraviolet irradiation device (Rapid Cure, manufactured by Ushio Inc.). Next, heat treatment was performed at 120 ° C. for 1 hour to obtain a reversible thermosensitive recording material having a protective layer.

Example 2 The procedure of Example 1 was repeated except that the zirconium compound was changed to a 20% aqueous solution of zirconium oxychloride in the preparation of the reversible thermosensitive coating solution (A) of Example 1.

Example 3 The procedure of Example 1 was repeated, except that the zirconium compound was changed to a 20% aqueous solution of zirconium acetate in the preparation of the reversible thermosensitive coating solution (A) of Example 1.

Example 4 The procedure of Example 1 was repeated except that the binder was changed to 600 parts of a 10% aqueous solution of carboxy-modified polyvinyl alcohol in the preparation of the reversible thermosensitive coating solution (A) of Example 1.

Example 5 Example 1 was repeated except that the binder was changed to 200 parts of a 30% aqueous solution of maleic anhydride / isobutylene / acrylic copolymer in the preparation of the reversible thermosensitive coating solution (A) of Example 1.
Same as.

Example 6 The procedure of Example 1 was repeated except that the coating of the reversible thermosensitive recording material (B) 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, 40% solids), 25 parts of a 20% aqueous solution of zirconium ammonium carbonate as a zirconium compound, 5 parts of Mizukasil P-527 (manufactured by Mizusawa Chemical), and 10 parts of water, and a solid coating amount of 1 g / m ^2. Was applied to a PET sheet so as to obtain an anchor layer. Next, the reversible heat-sensitive coating solution prepared in (A) of Example 1 was coated on the anchor layer so as to have a solid coating amount of 4 g / m ² , dried, and then treated with a super calender. Work sheet B was obtained.

Example 7 The procedure of Example 1 was repeated except that the coating of the protective layer (C) was changed as follows. (C) Coating of protective layer On the coating layer of the coated sheet B obtained in (B), 25 parts of an acrylic emulsion (manufactured by Siden Chemical Co., Sibinol EK-55, solid content 40%), and zirconium carbonate 20 as a zirconium compound. A 20% aqueous solution and 35 parts of water were mixed and applied so as to have a solid coating amount of 1 g / m ² to obtain an intermediate layer. Next, 90 parts of Aronix M8030 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), 5 parts of N-vinyl-2-pyrrolidone, 5 parts of Irgacure 500 (manufactured by Nippon Ciba Geigy), and 5 parts of Mizukasil P-527 (manufactured by Mizusawa Chemical) are added and sufficiently stirred. UV curable resin was applied so as to be 1.0 g / m ^2, and then an ultraviolet irradiation device (Rapid Cure, manufactured by Ushio Inc.)
To obtain a reversible thermosensitive recording material having an intermediate layer and a protective layer. Further, the obtained reversible thermosensitive recording material was heated at 120 ° C. for 1 hour.

Comparative Example 1 The procedure of Example 1 was repeated except that the zirconium compound was not used in the preparation of (A) the reversible thermosensitive coating liquid.

Comparative Example 2 The procedure of Example 6 was repeated except that the zirconium compound was not used in (A) preparation of the reversible thermosensitive coating solution and (B) coating of the reversible thermosensitive recording material. I did the same.

Comparative Example 3 The procedure of Example 7 was repeated except that the zirconium compound was not used in (A) the preparation of the reversible thermosensitive coating solution and (C) the coating of the protective layer. .

The following evaluation test was performed on the reversible thermosensitive recording material produced as described above. Test Method The reversible thermosensitive recording materials obtained in Examples and Comparative Examples were applied for 2.0 milliseconds with an applied pulse of 2.0 msec using a thermal facsimile printing tester TH-PMD manufactured by Okura Electric with Kyocera print head KJT-256-8MGF1. Printing was performed under the condition of a voltage of 25 volts, and the obtained color image was printed by 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 coloring and erasing were repeated 50 times, and the 50th coloring and erasing densities 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.

After immersing the obtained reversible thermosensitive recording material in water for 100 hours, the recording surface was immediately rubbed with a finger, and the surface was observed. 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.

[0082]

[Table 1]

From Table 1, it can be seen that Examples 1 to 3 in which the zirconium compound contained in the reversible thermosensitive recording layer was changed had excellent color development and decoloration even after repetition, had good image contrast, and had sufficient durability. It has water resistance. Examples 6 and 7, in which the zirconium compound was also used for the anchor layer or the intermediate layer, were particularly excellent in repetitive use, and did not show any reduction in color density. Similarly, Examples 4 and 5 in which the binder was changed exhibited good color development and decoloration, and it was possible to repeatedly perform color development and decoloration, and the water resistance was sufficient. On the other hand, Comparative Examples 1, 2, and 3 have sufficient color development density and color erasure density. However, when color development and color erasure are repeatedly performed, a decrease in the color development density and an increase in the erasure density are observed. The contrast of the image was significantly reduced. In particular, in Comparative Example 3, remarkable destruction of the recording layer presumably due to the thermal head was observed. Regarding the water resistance, peeling of the printing surface recording layer was observed after immersion in water. 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.

[0084]

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 zirconium compound in the reversible thermosensitive recording layer, or in a protective layer thereon or an anchor layer between the support, color development and decoloration are repeated. It can be used as a reversible thermosensitive recording material which is less damaged by use and has high water resistance and is practically satisfactory.

Claims (4)

[Claims] 1. A reversible thermosensitive recording comprising, on at least one surface of a support, a colorless or pale-colored leuco dye, and a reversible color developer which causes the leuco dye to develop color by heating and to be decolorized by reheating. A reversible thermosensitive recording material provided with a layer, wherein the reversible thermosensitive recording layer contains a zirconium compound. 2. A reversible thermosensitive recording comprising, on at least one surface of a support, a colorless or pale-colored leuco dye, and a reversible developer which causes the leuco dye to develop color by heating and to be decolorized by reheating. A reversible thermosensitive recording material comprising a layer, wherein a protective layer is provided on the upper surface of the reversible thermosensitive recording layer, and a zirconium compound is contained in the protective layer. 3. A reversible thermosensitive recording comprising, on at least one surface of a support, a colorless or pale-colored leuco dye, and a reversible color developer which causes the leuco dye to develop color by heating and to be decolorized by reheating. A reversible thermosensitive recording material having a layer, wherein an anchor layer is provided between the reversible thermosensitive recording layer and a support, and a zirconium compound is contained in the anchor layer. 4. In a layer containing a zirconium compound,
4. The method according to claim 1, further comprising a binder resin containing at least one kind of functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an amide group, an imino group and an imide group. 4. The reversible thermosensitive recording material according to claim 1.