JP3349763B2 - Reversible thermosensitive recording material - Google Patents

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 images by controlling thermal energy.

[0002]

2. Description of the Related Art In general, a heat-sensitive recording material comprises a support having thereon a heat-sensitive recording layer mainly composed of an electron-donating usually colorless or pale-color 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 Nos. 43-4160 and 45-160
It is disclosed in, for example, Japanese Patent Publication No. 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 capable of repeatedly forming and erasing images have been devised to address such problems. For example, JP-A-54-119377 and JP-A-63-119377 disclose a reversible thermosensitive recording material. 39377, JP-A-63-4
Japanese Patent No. 1186 describes a heat-sensitive recording material composed of a resin base material and an organic low-molecular compound dispersed in the resin base material. However, this method reversibly changes the transparency of the heat-sensitive recording material by heat energy,
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.

As described above, in the prior art, there is a reversible thermosensitive recording material which has a good image contrast, can form and erase an image, and can maintain a stable image with time in an environment of daily life. Although it did not do, Japanese Patent Application No. 4-34703
In No. 2, the present applicants have disclosed that an electron-accepting compound (reversible developer) that causes a colorless or pale-colored electron-donating dye precursor to undergo a reversible color change upon heating, that is, a color development and a decoloration, is obtained. I found it to exist.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording material capable of forming and erasing an image with good contrast and capable of maintaining a stable image over time in an environment of daily life. That is.

[0010]

Means for Solving the Problems The present inventors have generally proposed a colorless or pale-colored dye precursor and a reversible color developer which causes a reversible color change in the dye precursor due to a difference in cooling rate after heating. Reversible thermosensitive recording material containing
As a result of intensive studies to further improve the image stability, one or more of the compounds represented by Chemical Formula 1 were used ,
By using the compound represented by the formula 2 as a reversible color developer, it was found that a reversible thermosensitive recording material having more excellent image stability was obtained, and the present invention was completed. Was.

In the compounds represented by Chemical Formula 1, A represents an alkyl group, an alkenyl group, an allyl group, an alkoxy group, a formyl group, an alkylcarbonyl group, an allylcarbonyl group, an alkylcarbonyloxy group, an allylcarbonyloxy group, Alkyloxycarbonyl group, allyloxycarbonyl group, alkylmercapto group, allylmercapto group, carbamoyl group, alkylcarbonylamino group, alkylaminocarbonyl group, ureido group, allylcarbonylamino group, allylaminocarbonyl group, alkylureylene group, allylureylene Group, alkylsulfonyl group, allylsulfonyl group, alkylsulfinyl group, allylsulfinyl group, alkylsulfonamide group, allylsulfonamide group, sulfamoyl group, alkylaminosulfone group, Aminosulfonic group, a nitro group, an amino group, an alkylamino group, an arylamino group, amidino group, guanidino group, a cyano group, an aromatic ring or heterocyclic ring is substituted with a halogen atom or the like, or unsubstituted aromatic ring or heterocyclic ring However, Chemical formula 1 has the chemical structure of Chemical formula 2
Never .

Further, R represents an aliphatic hydrocarbon group, and it is preferable that the number of carbon atoms is large. If the number of carbon atoms is 5 or less, the effect of improving storage stability is not sufficient. Further, since R having 23 or more carbon atoms has a high production cost, R is particularly preferably an aliphatic hydrocarbon group having 6 to 22 carbon atoms.

Specific examples of the compound of the formula 1 include the following compounds, but the present invention is not limited thereto.

N-phenyl-N'-n-octylurea,
N-phenyl-N'-n-dodecyl urea, N-phenyl-N'-n-tetradecyl urea, N-phenyl-N'-
n-octadecyl urea, N- (p-methylphenyl)-
N'-n-tetradecyl urea, N- (p-methylphenyl) -N'-n-octadecyl urea, N- (m-methylphenyl) -N'-n-octadecyl urea, N- (p-
Methoxyphenyl) -N′-n-tetradecylurea, N
-(P-methoxyphenyl) -N'-n-octadecyl urea, N- (m-methoxyphenyl) -N'-n-octadecyl urea, N- (p-ethoxyphenyl) -N'-
n-octadecyl urea, N- (p-benzyloxyphenyl) -N'-n-tetradecyl urea, N- (p-biphenylyl) -N'-n-tetradecyl urea, N- (p-
Phenoxyphenyl) -N′-n-tetradecylurea,
N- (p-tolyloxyphenyl) -N'-n-octadecyl urea, N- (p-acetylphenyl) -N'-n
-Tetradecyl urea, N- (p-acetylphenyl)-
N'-n-octadecyl urea, N- (p-benzoylphenyl) -N'-n-tetradecyl urea, N- (p-benzoyl phenyl) -N'-n-octadecyl urea, N
-(P-chlorophenyl) -N'-n-tetradecyl urea, N- (p-chlorophenyl) -N'-n-octadecyl urea, N- (m-chlorophenyl) -N'-n-octadecyl urea, N- ( p-nitrophenyl) -N'-
n-tetradecyl urea, N- (p-nitrophenyl)-
N'-n-octadecyl urea, N- (p-cyanophenyl) -N'-n-tetradecyl urea, N- (p-cyanophenyl) -N'-n-octadecyl urea, N- (p-
Trifluoromethylphenyl) -N'-n-octadecyl urea, N- (p-methylthiophenyl) -N'-n-
Tetradecyl urea, N- (p-methylthiophenyl)-
N'-n-octadecyl urea, N- (p-phenylthiophenyl) -N'-n-octadecyl urea, N- (p-
Toluenesulfonylphenyl) -N'-n-octadecyl urea, N- (p-toluenesulfonylaminophenyl) -N'-n-octadecyl urea, N- (3-pyridyl) -N'-n-tetradecyl urea, N- (3-pyridyl) -N'-n-octadecyl urea, N- (4-pyridyl) -N'-n-tetradecyl urea, N- (4-pyridyl) -N'-n-octadecyl urea, N- ｛3 − (6-
Methylpyridyl) {-N'-n-tetradecyl urea, N
-(2-pyrimidyl) -N'-n-octadecyl urea,
N- (2-thiazoyl) -N'-n-octadecyl urea, N- {3- (5-methylisoxazoyl)}-N
'-N-tetradecyl urea, N- {3- (5,6-dimethyl-1,2,4-triazinyl)}-N'-n-octadecyl urea, N- (2-benzimidazoyl) -N'
-N-octadecyl urea, N- (2-benzoxazoyl) -N'-n-octadecyl urea, N- (2-benzothiazoyl) -N'-n-octadecyl urea, N- ｛2
-(6-methoxybenzothiazoyl)}-N'-n-octadecylurea, 1,4-bis (n-tetradecylureyl) benzene, 1,4-bis (n-octadecylureyl) benzene and the like.

The preferred amount of the compound of the formula (1) is from 0.05% by weight to 100% by weight based on the dye precursor. If it is less than this, the effect is not sufficient, and if it exceeds this, there is a possibility that either of the heat-resistant storage stability or the decoloring property of the image is adversely affected.

The usually colorless or light-colored electron-donating dye precursor used in the present invention is typified by those generally used for pressure-sensitive recording paper and heat-sensitive recording paper, but is not particularly limited. Specific examples include, for example, the following, but the present invention is not limited thereto.

(1) Triarylmethane compounds 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) benzhydrylbenzyl ether, N-chlorophenylleucouramine, N-2,4,5-trichlorophenylleucouramine, 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-N-tolyl) amino-6-methyl-7-anilinofluoran, 3-piperidino-6-methyl- 7-anilinofluoran, 3-
(N-ethyl-N-tolyl) amino-6-methyl-7-
Phenethylfluoran, 3-diethylamino-7- (4
-Nitroanilino) fluoran, 3-dibutylamino-
6-methyl-7-anilinofluoran, 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6 Methyl-7-anilinofluoran, 3- (N-
Methyl-N-cyclohexyl) amino-6-methyl-7
-Anilinofluoran, 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran and the like,

(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 colorless or pale color dye precursors may be used alone or in combination of two or more.

The reversible developer used in the present invention is preferably an electron-accepting compound, which is capable of maintaining a reversible color tone change due to a difference in cooling rate after heating in the presence of the above dye precursor. It is not particularly limited. Particularly preferred compounds in terms of color density and color erasing properties, include those represented by the following general formalized 3. Departure
In the light, the compound represented by the above formula 1
Is used. The method of synthesizing the compound of Chemical Formula 3 is described in Japanese Patent Application No. 4-34732 by the present applicant.
No.

[0025]

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In Formula 3, n represents an integer of 1 to 3 , and l1 and l2 each represent an integer of 0 or 1. R ₁ ,
R ₂ represents a substituent or a hydrogen atom selected from an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom, and may be the same or different. X ₁ and X ₂ are each at least 1
Represents a divalent group having two heteroatoms,
May also be different. Ar is a group which may have a substituent
Represents an aromatic group. As Ar, an aromatic group represented by the following formula 4 is particularly preferable. Also, it is preferable that R ₃ has a large number of carbon atoms.
When the carbon number of R ₃ is 5 or less, the decolorizing effect is not sufficient.
Not a minute. On the other hand, R ₃ having 23 or more carbon atoms
Has a high production cost, so R ₃ has 6 to 22 carbon atoms.
Is an aliphatic hydrocarbon group.

[0027]

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In Formula 4, k1 and k2 each represent an integer of 0 or 1, and X ₃ and X ₄ each represent a divalent group having at least one hetero atom, and may be the same or different from each other. . When k1 is 0, R ₄ is an aliphatic hydrocarbon group,
Represents a substituent selected from an alkoxy group, a halogen atom or a hydrogen atom, and when k1 is 1, R ₄ represents an aliphatic hydrocarbon group. When k2 is 0, R ₅ represents a substituent or a hydrogen atom selected from an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom. When k2 is 1, R ₅ represents an aliphatic hydrocarbon group.

In Formula 4, when R ₄ and R ₅ are an aliphatic hydrocarbon group, it is particularly preferable that each of R ₄ and R ₅ is an aliphatic hydrocarbon group having 6 to 22 carbon atoms.

In Formulas 3 and 4, when R _{1 to} R ₅ are an aliphatic hydrocarbon group, R _{1 to} R ₅ are particularly preferably an alkyl group, a cycloalkyl group or an alkenyl group. .

In Formulas 3 to 4, the divalent group having at least one hetero atom represented by X _{1 to} X ₄ includes, for example, an amide bond, a sulfonamide bond, an ester bond, a carbonate bond, and an ether bond. , Sulfide bond, thioester bond, carbonyl group, amino bond, urea bond,
Examples include a thiourea bond, a urethane bond, and an azomethine bond. Particularly, a divalent group selected from an amide bond, a sulfonamide bond, a sulfide bond, a urea bond, and an azomethine bond is particularly preferable, but the present invention is not limited thereto. Not something.

[0032] Among the electron-accepting compound represented by the general formalized 3, the compound represented by the general formalized 5 is particularly preferred.

[0033]

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In Formula 5, n, l1, l2, R _{1 to} R ₃ , A
r and X ₂ are the same as above. X ₅ represents an amide bond, a sulfonamide bond, a sulfide bond, a urea bond, a bond selected from the azomethine bond.

In Formula 5, for example, amide compounds represented by Chemical Formulas 6 and 7, sulfonamide compounds represented by Chemical Formula 8, sulfide compounds represented by Chemical Formula 9, and urea compounds represented by Chemical Formula 10 The azomethine compounds represented by the following formulas, 11 and 12, are particularly preferred. In the formulas 6 to 12, n,
11, 12, R _{1 to} R ₃ , Ar and X ₂ are the same as described above.

[0036]

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In Formula 6, R ₆ represents an aliphatic hydrocarbon group or a hydrogen atom.

[0038]

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In Formula 7, R ₇ represents an aliphatic hydrocarbon group or a hydrogen atom.

[0040]

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In Formula 8, R ₈ represents an aliphatic hydrocarbon group or a hydrogen atom.

[0042]

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[0043]

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[0044]

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In Formula 11, R ₉ represents an aliphatic hydrocarbon group or a hydrogen atom.

[0046]

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In Formula 12, R ₁₀ represents an aliphatic hydrocarbon group or a hydrogen atom.

The compound represented by the general formula 3 is an electron-accepting compound and has a specific decoloring effect, that is, a reversible effect, despite having the ability to form a leuco dye. The electron-accepting compounds used in ordinary thermosensitive recording materials, that is, 2,2-bis (4-hydroxyphenyl) propane and bis (4-hydroxyphenyl)
Such reversible effects are not seen at all with sulfone, benzyl 4-hydroxybenzoate and the like. Next, specific examples of preferable electron-accepting compounds as the reversible color developer according to the present invention will be described, but the present invention is not limited thereto.

[0049] For example, such an amide compound represented by formalized 6, 4'-hydroxy-heptane anilide, 4 '
-Hydroxy-3-methyloctaneanilide, 4'-hydroxytridecaneanilide, 4'-hydroxyheptadecaneanilide, 4'-hydroxynonadecananilide, 3'-hydroxynonadecananilide, 4'-hydroxy-10-octadecene Anilide, 4'-hydroxy-docasananilide, 15-cyclohexyl-4'-
Hydroxypentadecaneanilide, 4'-hydroxy-
5-tetradeceneanilide, 4'-hydroxy-3'-
Methylnonaneanilide, 3'-cyclohexyl-4'-
Hydroxyheptadecaneanilide, 3'-allyl-4 '
-Hydroxypentadecaneanilide, 4'-hydroxy-3'-methoxyoctadecaneanilide, 3'-chloro-4'-hydroxyoctadecaneanilide, 3'-hydroxydodecaneanilide, 2 ', 4'-dihydroxyheptadecaneanilide,

[0050] 4'-hydroxy-4-hexyl-benzanilide, 4'-hydroxy-4-dodecyl-benzanilide, 4'-hydroxy-4-tetradecyl-benzanilide, 4'-hydroxy-4-octadecyl-benzanilide, 4 ' -Hydroxy-4-pentadecylaminocarbonylbenzanilide, 4'-hydroxy-4-hexylcarbonylaminobenzanilide, 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- Pentadecylideneamino) benzanilide, 4'-hydroxy-4- (N-heptadecylideneamino) benzanilide,

[0051] 4'-hydroxy-3,4-di-octyloxy-benzanilide, 4'-hydroxy-3,4,5
Trioctadecyloxybenzanilide, 4'-hydroxy-3-octyl-4- (octylthio) benzanilide, 4'-hydroxy-3- (heptadecylthio)-
5-pentadecyloxybenzanilide, 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-docosyl Denamino) benzanilide,

[0052] 4'-hydroxy-4-octadecyl carbonylamino benzanilide, 4'-hydroxy-3-
Octadecylcarbonylamino-5-octadecyloxybenzanilide, 4'-hydroxy-3'-methyl-
4-nonylbenzanilide, 3'-allyl-4'-hydroxy-4-pentadecylbenzanilide, 4'-hydroxy-3'-methoxy-4-octadecylbenzanilide, 4'-hydroxy-3'-methyl-4 -Nonyloxybenzanilide, 4'-hydroxy-3'-propyl-4-nonadecylcarbonyloxybenzanilide,
3'-butyl-4'-hydroxy-4-octadecyloxycarbonylbenzanilide, 3'-hydroxy-4
-Pentadecylcarbonyloxybenzanilide, 3 '
-Hydroxy-4-nonadecylsulfonylbenzanilide, 3 ', 4'-dihydroxy-4-heptadecylsulfonyloxybenzanilide, 3', 4 ', 5'-trihydroxy-4-tetracosylaminosulfonylbenzanilide, 3 ', 5'-dihydroxy-4-pentacosylaminocarbonylbenzanilide, 3'-hydroxy-4- (N-dodecylideneamino) benzanilide, N
-[4- (3-hydroxyphenylaminocarbonyl)
Benzylidene] pentadecylamine and the like.

[0053] Further, as the such amide compound represented by formalized 7, N- cyclohexyl-4-hydroxybenzamide, N- cyclohexylmethyl-4-hydroxybenzamide, N- octyl-4-hydroxybenzamide, N- dodecyl - 4-hydroxybenzamide, N-
Octadecyl-4-hydroxybenzamide, N-methyl-N-octadecyl-4-hydroxybenzamide,
N-octacosyl-4-hydroxybenzamide, N-
(3-methylhexyl) -4-hydroxybenzamide, N- (8-octadecenyl) -4-hydroxybenzamide,

[0054] 4-hydroxy-4'-dodecyl-benzanilide, 4-hydroxy-4'-tetradecyl-benzanilide, N- methyl-4-hydroxy-4'-octadecyl benzanilide, 4-hydroxy-4'-octyloxy Benzanilide, 4-hydroxy-4'-octadecyloxybenzanilide, 4-hydroxy-4'-
(Octadecylthio) benzanilide, 4-hydroxy-4'-pentylcarbonylbenzanilide, 4-hydroxy-4'-hexadecylcarbonylbenzanilide, 4-hydroxy-4'-heptadecyloxycarbonyloxybenzanilide, 4-hydroxy- 4'-dodecyloxycarbonyl benzanilide, 4-hydroxy-4'-docosyloxycarbonyl benzanilide,
4-hydroxy-4'-heptadecylcarbonyloxybenzanilide, 4-hydroxy-4'-cyclohexylaminobenzanilide, 4-hydroxy-4'-octylaminobenzanilide, 4-hydroxy-4'-octadecylaminobenzanilide,

[0055] 4-hydroxy-4'-heptyl carbonylamino benzanilide, 4-hydroxy-4'-heptadecyl carbonylamino benzanilide, 4-hydroxy-4'-octadecyl amino carbonyl benzanilide, 4-hydroxy-4'- (8-octadecenyl)
Aminocarbonyl benzanilide, 4-hydroxy-
4'-dodecylsulfonylbenzanilide, 4-hydroxy-4'-octyloxysulfonylbenzanilide, 4-hydroxy-4'-octadecyloxysulfonylbenzanilide, 4-hydroxy-4'-dodecylsulfonyloxybenzanilide, N-4 -Hydroxybenzoyl-N'-octadecylidene-1,4-
Phenylenediamine, N-4- (4-hydroxyphenylcarbonylamino) benzylidenedecylamine, 4
-Hydroxy-4'-octyloxycarbonylaminobenzanilide, 4-hydroxy-4'-tetradecyloxycarbonylaminobenzanilide, 4-hydroxy-4'-octadecylureylenebenzanilide,

[0056] N- dodecyl-3-hydroxybenzamide, N- octadecyl-3,4-dihydroxy-benzamide, N- octadecyl-2,3,4-tri-hydroxybenzamide, 3-hydroxy-4'-dodecyloxy-benzanilide, N -Methyl-4-hydroxy-3'-
Octadecyloxybenzanilide, 3-hydroxy-
4'-octylbenzanilide, 3-hydroxy-4 '
-Tetradecylbenzanilide, N-methyl-3-hydroxy-4'-octadecylbenzanilide, N-dodecyl-4-hydroxy-3-methylbenzamide, 3-
Methoxy-4-hydroxy-4'-octadecyloxybenzanilide, 3-allyl-4-hydroxy-4'-
Octadecyloxybenzanilide, 3-chloro-4-
Hydroxy-4'-octadecylbenzanilide, N-
Octadecyl-4-hydroxy-2,5-dimethylbenzamide, N-octadecyl-4-hydroxy-3-ethylbenzamide, 4-hydroxy-4'-octyloxy-3'-methylbenzanilide, 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 and the like.

[0057] As such sulfonamide compound represented by formalized 8, 4-(N-octyl-sulfonylamino) phenol, 4-(N-dodecyl-sulfonylamino) phenol, 4-(N-octadecylsulfonylamino) phenol, 4- (N-methyl-N-octadecylsulfonylamino) phenol, 4- (N-3-methylhexylsulfonylamino) phenol,

[0058] 4'-hydroxy-4-cyclohexylbenzene sulfonanilide, 4'-hydroxy-4-octylbenzenesulfonic anilide, 4'-hydroxy-4
-Dodecylbenzenesulfonanilide, 4'-hydroxy-4-dodecyloxybenzenesulfonanilide,
4'-hydroxy-4-octadecyloxybenzenesulfonanilide, 4'-hydroxy-4- (dodecylthio) benzenesulfonanilide, 4'-hydroxy-4
-Hexylcarbonylbenzenesulfonanilide, 4 '
-Hydroxy-4-hexadecylcarbonylbenzenesulfonanilide, 4'-hydroxy-4- (8-heptadecenyl) carbonylbenzenesulfonanilide, 4 '
-Hydroxy-4-octyloxycarbonyloxybenzenesulfonanilide, 4'-hydroxy-4-dodecyloxycarbonylbenzenesulfonanilide, 4 '
-Hydroxy-4-octacosyloxycarbonylbenzenesulfonanilide, 4'-hydroxy-4-dodecylcarbonyloxybenzenesulfonanilide, 4'-
Hydroxy-4-hexylaminobenzenesulfonanilide, 4'-hydroxy-4-octadecylaminobenzenesulfonanilide

[0059] 4'-hydroxy-4-heptadecyl-carbonyl aminobenzenesulfonic anilide, 4'-hydroxy-4-dodecyl-aminocarbonyl benzene sulfonanilide, 4'-hydroxy-4-dodecyl-sulfonyl benzene sulfonanilide, 4'-hydroxy - 4-octyloxysulfonylbenzenesulfonanilide,
4'-hydroxy-4-octadecyloxysulfonylbenzenesulfonanilide, 4'-hydroxy-4-dodecylsulfonyloxybenzenesulfonanilide, N
-Octylidene-4- (4-hydroxyphenyl) aminosulfonylaniline, N-dodecylidene-4- (4-
(Hydroxyphenyl) aminosulfonylaniline, N-
4- (4-hydroxyphenylaminosulfonyl) benzylideneoctadecylamine, 4'-hydroxy-4-
Octyloxycarbonylaminobenzenesulfonanilide, 4'-hydroxy-4-octadecyloxycarbonylaminobenzenesulfonanilide, 4'-hydroxy-4-octadecylureylenebenzenesulfonanilide,

[0060] 3- (N- dodecyl sulfonylamino) phenol, 4-(N-octadecyl sulfonate amino) catechol, 4-(N-octadecyl sulfonamino) resorcinol, 4-(N-octadecylsulfonylamino) pyrogallol, 4' Hydroxy-3-octyloxybenzenesulfonanilide, 3'-hydroxy-4
-Dodecyloxybenzenesulfonanilide, N-methyl-4'-hydroxy-3-octadecyloxybenzenesulfonanilide, 3'-hydroxy-4-dodecylbenzenesulfonanilide, 3-methyl-4- (N-dodecylsulfonamino) phenol , 4-methyl-3-
(N-tetradecylsulfonamino) phenol, 3 '
-Methoxy-4'-hydroxy-4-octadecyloxybenzenesulfonanilide, 3'-chloro-4'-hydroxy-4-octadecylbenzenesulfonanilide, 4'-hydroxy-2,5-dimethyl-4-octadecylbenzenesulfonanilide , 3-methyl-4-
(N-octadecylsulfonamino) phenol, 4 '
-Hydroxy-3,4-dioctadecyloxybenzenesulfonanilide and the like.

[0061] As such sulfide compound represented by formalized 9, 1- (4-hydroxyphenyl thio) hexane, 1- (4-hydroxyphenyl thio) dodecane, 1
-(4-hydroxyphenylthio) octadecane, 1-
(3-hydroxyphenylthio) octadecane, 1-
(4-hydroxyphenylthio) docosan, 1- (4-
(Hydroxyphenylthio) tetracosane, 2-heptyl-1- (4-hydroxyphenylthio) octane, 1-
(4-hydroxyphenylthio) -9-octadecene,
1- (4-hydroxy-3-methylphenylthio) octadecane, 1- (3-allyl-4-hydroxyphenylthio) hexadecane, 1- [4-hydroxy-3-
(1,1-dimethylethyl) phenylthio] tetracosane, 1- (4-hydroxy-3-methoxyphenylthio) octadecane, 1- (2-ethoxy-4-hydroxyphenylthio) octadecane, 1- (3-chloro-4
-Hydroxyphenylthio) octadecane, 1- (2-
Fluoro-4-hydroxyphenylthio) octadecane, 1- (2-hydroxyphenylthio) octane, 1
-(3-hydroxyphenylthio) octadecane, 1-
(3,4-dihydroxyphenylthio) octadecane,
1- (3,4-dihydroxyphenylthio) icosane,

[0062] 4'-hydroxy-4-hexyl diphenyl sulfide, 4'-hydroxy-4-dodecyl sulfide, 4'-hydroxy-4-tetradecyl diphenyl sulfide, 4'-hydroxy-4-octadecyl sulfide, 4 ' -Hydroxy-4-
Octadecylcarbonylaminodiphenyl sulfide,
4'-hydroxy-4-dodecyloxydiphenyl sulfide, 4'-hydroxy-4-octadecyloxydiphenyl sulfide, 4'-hydroxy-4-dodecylsulfonyl diphenyl sulfide, 4'-hydroxy-
4-octadecyloxysulfonyldiphenyl sulfide, 4'-hydroxy-4-octadecylsulfonylaminodiphenyl sulfide, 4'-hydroxy-4-tridecylcarbonyldiphenyl sulfide, 4'-hydroxy-4- (N-heptadecylideneamino) diphenyl Sulfide,

[0063] 4'-hydroxy-3,4-di-decyl oxy diphenyl sulfide, 4'-hydroxy-3,4
Dioctadecyloxydiphenyl sulfide, 4'-hydroxy-3-octyl-4- (octylthio) diphenyl sulfide, 4'-hydroxy-3-octadecyl-5-tridecylsulfonyl diphenyl sulfide,
4'-hydroxy-3- (heptadecylthio) -5-pentadecyloxydiphenyl sulfide, 4'-hydroxy-3-heptadecylcarbonylamino-5-dodecyldiphenyl sulfide, 4'-hydroxy-3-octadecylcarbonylamino-5 Octadecyloxydiphenyl sulfide, 4'-hydroxy-3-heptadecyloxysulfonyl-5-tetradecyloxysulfonyldiphenyl sulfide, 4'-hydroxy-3,5
-Bis (N-docosylideneamino) diphenyl sulfide, 4- (15-cyclohexylpentadecyl) -4 '
-Hydroxydiphenyl sulfide, 4'-hydroxy-4- (5-tetradecenyl) diphenyl sulfide,
4'-hydroxy-4- (10-octadecenyloxycarbonyl) diphenyl sulfide, 4'-hydroxy-3'-methyl-4-nonyl diphenyl sulfide,

[0064] 3'-allyl-4'-hydroxy-4-pentadecyl diphenyl sulfide, 3'-chloro-4 '
-Hydroxy-4-octadecyldiphenyl sulfide, 3'-chloro-4'-hydroxy-4-octadecyl-5-pentadecyloxydiphenyl sulfide,
4'-hydroxy-3'-methyl-4-nonyloxydiphenyl sulfide, 4'-hydroxy-3 '-(1-
Methylethyl) -4-pentacosylsulfonylaminodiphenyl sulfide, 4'-hydroxy-3 '-(2-
Methylpropyl) -4-nonadecyloxysulfonyldiphenyl sulfide, 3'-hydroxy-4-dodecyldiphenyl sulfide, 3'-hydroxy-4-octadecyldiphenyl sulfide, 2 ', 4'-dihydroxy-4-heptadecyl diphenyl sulfide, 3 ',
4'-dihydroxy-4-heptadecyldiphenyl sulfide, 3'-hydroxy-4-dodecyloxycarbonyldiphenyl sulfide, and the like.

The urea compounds represented by Formula 10 include N- (4-hydroxyphenyl) -N'-hexylurea, N- (4-hydroxyphenyl) -N'-octylurea, and N- (4 -Hydroxyphenyl) -N'-dodecyl urea, N- (4-hydroxyphenyl) -N'-octadecyl urea, N- (4-hydroxyphenyl)-
N'-docosylurea, N- (4-hydroxyphenyl)
-N '-(2-heptyloctyl) urea, N- (4-hydroxyphenyl) -N'-(14-cyclohexyltetradecyl) urea, N- (3-methyl-4-hydroxyphenyl) -N'-octadecyl Urea, N- (4-hydroxyphenyl) -N '-(9-octadecenyl) urea, N- (3-allyl-4-hydroxyphenyl)-
N'-octadecyl urea, N- [3- (1,1-dimethylethyl) -4-hydroxyphenyl] -N'-octadecyl urea, N- (3,5-dimethyl-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'-tricosylurea

[0066] N-(4-hydroxyphenyl)-N'-
(4-tetradecylphenyl) urea, N- (4-hydroxyphenyl) -N '-(4-hexylphenyl) urea, N- (4-hydroxyphenyl) -N'-(3,4
-Dioctadecylphenyl) urea and the like.

As the azomethine compound represented by the formula (11), N- (4-hydroxybenzylidene) dodecylamine, N- (4-hydroxybenzylidene) octadecylamine,

[0068] N-(4-hydroxy-benzylidene) -
4'-hexylaniline, N- (4-hydroxybenzylidene) -4'-octylaniline, N- (4-hydroxybenzylidene) -4'-tetradecylaniline, N
-(4-hydroxybenzylidene) -4'-dodecyloxyaniline, N- (4-hydroxybenzylidene)-
4'-octadecyloxyaniline, N- (4-hydroxybenzylidene) -4 '-(octylthio) aniline, N- (4-hydroxybenzylidene) -4'-hexadecylcarbonylaniline, N- (4-hydroxybenzylidene)- 4'-octyloxycarbonylaniline, N- (4-hydroxybenzylidene) -4'-octadecyloxycarbonylaniline, N- (4-hydroxybenzylidene) -4'-dodecylcarbonyloxyaniline, N- (4-hydroxybenzylidene) -4 '
-Tetradecylcarbonyloxyaniline, N- (4-
(Hydroxybenzylidene) -4'-octadecyloxycarbonyloxyaniline, N- (4-hydroxybenzylidene) -4'-cyclohexylaminoaniline, N
-(4-hydroxybenzylidene) -4'-dodecylaminoaniline,

[0069] N-(4-hydroxy-benzylidene) -
4'-heptadecylcarbonylaminoaniline, N-
(4-hydroxybenzylidene) -4'-dodecylaminocarbonylaniline, N- (4-hydroxybenzylidene) -4'-octadecylaminocarbonylaniline, N- (4-hydroxybenzylidene) -4'-dodecylsulfinylaniline, N- (4-hydroxybenzylidene) -4'-dodecylsulfonylaniline, N
-(4-hydroxybenzylidene) -4'-octadecylsulfonylaniline, N- (4-hydroxybenzylidene) -4'-octyloxysulfonylaniline, N- (4-hydroxybenzylidene) -4'-octacosyloxysulfonylaniline , N- (4-hydroxybenzylidene) -4 '-(3-methylhexyl)
Oxysulfonylaniline, N- (4-hydroxybenzylidene) -4'-dodecylsulfonyloxyaniline, N- (4-hydroxybenzylidene) -4'-
(Octylthiocarbonyl) aniline, N- (4-hydroxybenzylidene) -4'-octyloxycarbonylaminoaniline, N- (4-hydroxybenzylidene) -4'-octadecyloxycarbonylaminoaniline, N- (4-hydroxybenzylidene) ) -4'-octadecylureyleneaniline,

[0070] N- (3- hydroxy benzylidene) dodecylamine, N-(3,4-dihydroxy-benzylidene) octadecylamine, N-(2,4-dihydroxy-benzylidene) octadecylamine, N-(3, 4, 5
-Trihydroxybenzylidene) octadecylamine,
N- (4-hydroxy-3-methylbenzylidene) dodecylamine, N- (3-hydroxy-4-methylbenzylidene) dodecylamine, N- (4-hydroxy-α-
Methylbenzylidene) -4'-dodecylaniline, N-
(4-hydroxy-α-methylbenzylidene) -4′-
Octadecylaniline, N- (4-hydroxy-3-methoxybenzylidene) dodecylamine, and the like.

The azomethine compound represented by the formula (12 ) includes N-octylidene-4-hydroxyaniline, N-tetradecylidene-4-hydroxyaniline,
N-octadecylidene-4-hydroxyaniline,

[0072] N-(4-dodecyl) benzylidene-4 '
-Hydroxyaniline, N- (4-octyloxy) benzylidene-4'-hydroxyaniline, N- (4-octadecyloxy) benzylidene-4'-hydroxyaniline, N- (4-octadecylthio) benzylidene-
4'-hydroxyaniline, N- (4-undecylcarbonyl) benzylidene-4'-hydroxyaniline, N
-(4-tridecylcarbonyl) benzylidene-4'-
Hydroxyaniline, N- (4-heptadecylcarbonyl) benzylidene-4'-hydroxyaniline, N-
{4- (8-heptadecenylylcarbonyl) benzylidene} -4'-hydroxyaniline, N- (4-dodecyloxycarbonyl) benzylidene-4'-hydroxyaniline, N- (4-octadecyloxycarbonyl) benzylidene-4 '-Hydroxyaniline, N- (4-octylcarbonyloxy) benzylidene-4'-hydroxyaniline, N- (4-octadecylcarbonyloxy) benzylidene-4'-hydroxyaniline, N-
(4-hexylamino) benzylidene-4'-hydroxyaniline, N- (4-octadecylamino) benzylidene-4'-hydroxyaniline,

[0073] N-(4-octadecyl carbonylamino) benzylidene-4'-hydroxyaniline, N-
(4-dodecylaminocarbonyl) benzylidene-4 '
-Hydroxyaniline, N- (4-octadecylaminocarbonyl) benzylidene-4'-hydroxyaniline, N- (4-dodecylsulfinyl) benzylidene-
4'-hydroxyaniline, N- (4-octylsulfonyl) benzylidene-4'-hydroxyaniline, N
-(4-dodecylsulfonyl) benzylidene-4'-
Hydroxyaniline, N- (4-octylsulfonyloxy) benzylidene-4'-hydroxyaniline, N
-(4-dodecylsulfonyloxy) benzylidene-
4'-hydroxyaniline, N- (4-dodecyloxysulfonyl) benzylidene-4'-hydroxyaniline, N- (4-octadecyloxysulfonyl) benzylidene-4'-hydroxyaniline, N- (4-octylthiocarbonyl) benzylidene -4'-hydroxyaniline, N- (4-dodecyloxycarbonylamino) benzylidene-4'-hydroxyaniline, N-
(4-octadecyloxycarbonylamino) benzylidene-4'-hydroxyaniline, N- (4-octadecylureylene) benzylidene-4'-hydroxyaniline,

[0074] N- dodecylidene-3-hydroxyaniline, N- Okutadeshiriden -3,4-dihydroxy aniline, N- Okutadeshiriden-3,4,5-tri-hydroxyaniline, N- (4-octadecyl) benzylidene -3 ', 4 '-Dihydroxyaniline, N- (4-tetradecyl) benzylidene-3'-methyl-4'-hydroxyaniline, N- (4-tetradecyl-3,5-dimethyl) benzylidene-4'-hydroxyaniline, N-
(4-tetradecyl) benzylidene-2'-chloro-
4'-hydroxyaniline, N- (4-octadecyl-
3-methyl) benzylidene-3 ', 4'-dihydroxyaniline and the like.

[0075] The amount of the reversible color developer may be used by mixing one or two or more, respectively, reversible color agent for a dye precursor, 5 to 5000 wt%, preferably 10 to 3000% by weight.

[0076] Next, described specific method for producing a reversible thermosensitive recording material of the present invention, the present invention is not limited thereto. As a specific example of the method for producing a reversible thermosensitive recording material of the present invention, a dye precursor and a reversible developer are used as main components, and further, the compound according to the present invention is applied as an additive component onto a support. To form a reversible thermosensitive recording layer.

A method for preparing a coating liquid for incorporating the dye precursor, the reversible developer and the compound of the present invention in the reversible thermosensitive recording layer is as follows. Each compound is dissolved alone in a solvent or dispersed in a dispersion medium. Mixing each compound, dissolving in a solvent or dispersing in a dispersion medium, mixing each compound by heating and dissolving and homogenizing, cooling, dissolving in a solvent or dispersing in a dispersion medium, etc. Is not specified. At the time of dispersion, a dispersant may be used if necessary. When water is the dispersion medium, examples of the dispersant include water-soluble polymers such as polyvinyl alcohol and various surfactants. In the case of aqueous dispersion, a water-soluble organic solvent such as ethanol may be mixed. In addition, when an organic solvent typified by hydrocarbons is a dispersion medium, lecithin, phosphates, and the like may be used as a dispersant.

Further , a binder can be added to the reversible thermosensitive recording layer for the purpose of improving the strength of the reversible thermosensitive recording layer. Specific examples of the binder include starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylate copolymer, acrylamide / acryl. Water-soluble polymers such as acid ester / methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, alkali salt of ethylene / maleic anhydride copolymer, polyvinyl acetate, polyurethane, polyacrylic acid Ester, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene / vinyl acetate copolymer, ethylene / vinyl chloride copolymer, polyvinyl chloride, ethylene Vinylidene chloride copolymers, such as latex of polyvinylidene chloride and the like but not limited thereto.

Further , a heat-fusible substance can be contained in the reversible thermosensitive recording layer as an additive for adjusting the color development sensitivity and the color erasing 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. These compounds include waxes such as N-hydroxymethyl stearamide, stearamide, palmitamide, naphthol derivatives such as 2-benzyloxynaphthalene, p-benzylbiphenyl,
Biphenyl derivatives such as allyloxybiphenyl, 1,
2-bis (3-methylphenoxy) ethane, 2,2'-
Polyether compounds such as bis (4-methoxyphenoxy) diethyl ether and bis (4-methoxyphenyl) ether; carbonic acid or oxalic acid diester derivatives such as diphenyl carbonate, dibenzyl oxalate, bis (p-methylbenzyl) oxalate And two or more kinds can be added in combination.

[0080] As the support used in the reversible thermosensitive recording material of the present invention include paper, various nonwoven fabrics, woven fabrics, polyethylene terephthalate or a synthetic resin film such as polypropylene, polyethylene, paper laminated with a synthetic resin such as polypropylene, synthetic Paper, metal foil, glass or the like, or a composite sheet combining these can be used arbitrarily according to the purpose, but is not limited thereto, and they are either opaque, translucent or transparent. Is also good. In order to make the background appear white or another specific color, a white pigment, a colored dye or a bubble may be contained in or on the support. In particular, in the case of aqueous coating of films, etc., when the hydrophilicity of the support is small and it is difficult to apply the reversible thermosensitive recording layer, the same water-soluble polymer as used for the hydrophilic treatment of the surface by corona discharge etc. or the binder May be subjected to an easy adhesion treatment such as coating on the surface of a support.

[0081] layer structure of a reversible thermosensitive recording material of the present invention,
Only the reversible thermosensitive recording layer may be used. If necessary,
Providing a protective layer on the reversible thermosensitive recording layer may also include an intermediate layer containing at least one of a water-soluble polymer, a white or colored dye or hollow particles between the reversible thermosensitive recording layer and the support. It can also be provided. In this case, the protective layer and / or the intermediate layer may be composed of two or three or more layers. The reversible thermosensitive recording layer may also be formed as a multilayer of two or more layers by containing each component in one layer or changing the mixing ratio for each layer. Further, a material capable of recording information electrically, optically, and magnetically in the reversible thermosensitive recording layer and / or on the surface opposite to the surface on which the reversible thermosensitive recording layer is provided. May be included. Further, a back coat layer can be provided on the surface opposite to the surface on which the reversible thermosensitive recording layer is provided for the purpose of preventing blocking, curling, and charging.

The method for forming the reversible thermosensitive recording material of the present invention by laminating each layer in the present invention on a support is not particularly limited, and it can be formed by a conventional method. For example, a smearing apparatus such as an air knife coater, a blade coater, a bar coater, and a curtain coater, and various printing machines using a method such as lithographic, letterpress, intaglio, flexo, gravure, screen, and hot melt can be used. In addition to the usual drying process, UV irradiation and
Each layer can be held by EB irradiation.

The reversible thermosensitive recording layer is prepared by mixing each dispersion obtained by pulverizing each component, coating the mixture on a support and drying the mixture, and dissolving each solution obtained by dissolving each component in a solvent. It can be obtained by, for example, a method of mixing and coating and drying on a support. Drying conditions vary depending on a dispersion medium or solvent such as water. In addition, there is a method in which the components are mixed and heated to melt a fusible component, and the mixture is heated and applied.

The reversible thermosensitive recording layer and / or the protective layer and / or the intermediate layer include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, and hydroxide. Aluminum, pigments such as urea-formalin resin, etc., in addition to head abrasion prevention, anti-sticking, zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearamide, Waxes such as caster wax, and a dispersant such as dioctyl sodium sulfosuccinate, a surfactant, a fluorescent dye, and the like can also be contained.

[0085] Next, described coloring and decoloring process of the reversible thermosensitive recording material of the present invention. In order to perform color development, rapid cooling may be performed following heating, and for example, heating by a thermal head, laser light, or the like is possible. or,
The color can be erased by slow cooling after heating, for example, by using radiant heat from a light source such as a thermal head, a hot roll, a hot stamp, high-frequency heating, hot air, an electric heater, a tungsten lamp, a halogen lamp, or the like.

[0086]

The present invention will be described in more detail with reference to the following examples. Parts and percentages in the examples are on a weight basis.

[0087] Example 1 (A) Preparation of reversible heat-sensitive coating solution 3-diethylamino-6-methyl-7-Ani Reno fluoran 40 parts of 2.5% aqueous solution of polyvinyl alcohol 90
The resulting mixture was pulverized with a paint conditioner to obtain a dye precursor dispersion. Then , 100 parts of N- (4-hydroxyphenyl) -N'-n-octadecyl urea was added to 2.5%
Pulverized by a paint conditioner together with 400 parts of polyvinyl alcohol aqueous solution to obtain a reversible color developer dispersion.
Further, N-(p-methoxyphenyl)-N'-n-octadecyl urea 5 parts with a 2.5% aqueous polyvinyl alcohol solution 20 was ground by a paint conditioner to give an additive dispersion. After mixing these three dispersions, 1
200 parts of a 0% aqueous polyvinyl alcohol solution and 400 parts of water were added and mixed well to prepare a reversible thermosensitive coating liquid.

[0088] (B) The prepared reversible thermosensitive coating solution on a polyethylene terephthalate (PET) sheet made action of a reversible thermosensitive recording material (A), solid coating amount 2.6 g /
After smear drying as a m ^2, thereon 5% aqueous solution of polyvinyl alcohol was spread and dried so as the solid coating amount 2 g / m ^2, to obtain a reversible heat-sensitive recording material was treated with a super calender.

[0089] used in Example 2 Example 1 N-(p-methoxyphenyl) -N '
A reversible thermosensitive recording material was obtained in the same manner as in Example 1, except that N- (p-acetylphenyl) -N'-n-octadecylurea was used instead of -n-octadecylurea.

[0090] N- used in Example 3 Example 1 (p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that N- (p-benzoylphenyl) -N'-n-octadecylurea was used instead of -n-octadecylurea.

[0091] N- used in Example 4 Example 1 (p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1, except that N- (4-pyridyl) -N'-n-octadecyl urea was used instead of -n-octadecyl urea.

[0092] N- used in Example 5 Example 1 (p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that N- (3-pyridyl) -N'-n-octadecyl urea was used instead of -n-octadecyl urea.

[0093] N- used in Example 6 Example 1 (p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that N- (2-pyrimidyl) -N'-n-octadecyl urea was used instead of -n-octadecyl urea.

[0094] N- used in Example 7 Example 1 (p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1, except that N- (2-benzothiazoyl) -N'-n-octadecyl urea was used instead of -n-octadecyl urea.

[0095] N- used in Example 8 Example 1 (p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that 5 parts of -n-octadecyl urea was changed to 2.5 parts.

[0096] used in Comparative Example 1 Example 1 N-(p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that -n-octadecyl urea was omitted.

[0097] used in Comparative Example 2 Example 1 N-(p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that 2-benzyloxynaphthalene was used instead of -n-octadecyl urea.

[0098] N- used in Comparative Example 3 Example 1 (p-methoxyphenyl)-N'
A reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that stearamide was used instead of -n-octadecyl urea.

[0099] Test 1 (color density = thermoresponsive) Examples 1 to 8 and a heat-sensitive recording material obtained in Comparative Example 1-3, Kyocera print head KJT-256-8MGF1 with Ohkura Electric Ltd. thermosensitive facsimile printing tester TH-PMD
Were printed under the conditions of an applied pulse of 1.0 millisecond and an applied voltage of 26 volts, and the density of the obtained color image was measured using a densitometer Macbeth RD918. The results are shown in Table 1.

[0100] Test 2 (deletion of the image) Examples 1 to 8 and a heat-sensitive recording material obtained in Comparative Example 1-3, Kyocera with the print head KJT-256-8MGF1 Ohkura Electric Ltd. thermosensitive facsimile printing tester TH- PMD
Was applied under the conditions of an applied pulse of 1.0 millisecond and an applied voltage of 26 volts, and was heated at 120 ° C. for 1 second using a heat stamp, and the concentration was measured in the same manner as in Test 1. The results are shown in Table 1.

[0102] Test 3 A heat sensitive recording material was obtained in Examples 1 to 8 and Comparative Examples 1 to 3 (change over time = image stability of developed color density), Kyocera print head KJT-256-8MGF1 with Ohkura Electric Ltd. thermosensitive facsimile Printing tester TH-PMD
After printing under the conditions of an applied pulse of 1.0 millisecond and an applied voltage of 26 volts, and stored in an atmosphere of a temperature of 40 ° C. and a relative humidity of 10% for 24 hours, the color developing portion The density was measured, and the image residual ratio was calculated by the following equation (1). The results are shown in Table 1.

[0102]

A = (C / B) × 100 A: Image residual ratio (%) B: Image density before test C: Image density after test

[0103] The heat-sensitive recording material was obtained in Test 4 Examples 1 to 8 and Comparative Examples 1 to 3 were printed under the same conditions as in Test 3, the temperature 40 ° C., and stored 24 hours in an atmosphere of 90% relative humidity Thereafter, the density of the color-developed portion was measured in the same manner as in Test 1, and the image remaining ratio was calculated in the same manner as in Test 3. The results are shown in Table 1.

[0104] The heat-sensitive recording material was obtained in Test 5 Examples 1 to 8 and Comparative Examples 1 to 3 were printed under the same conditions as in Test 3, the temperature 50 ° C., and stored 24 hours in an atmosphere of 10% relative humidity Thereafter, the density of the color-developed portion was measured in the same manner as in Test 1, and the image remaining ratio was calculated in the same manner as in Test 3. The results are shown in Table 1.

[0105]

[Table 1]

[0106]

As shown in Table 1, a reversible thermosensitive dye containing a colorless or pale color dye precursor and a reversible color developer which causes the dye precursor to reversibly change color tone upon heating. By including a compound represented by the general formula (1) in a recording material, an image can be formed and erased with good contrast, and a more stable image can be retained over time in an environment of daily life. A reversible thermosensitive recording material was obtained.

Claims (1)

(57) [Claims] 1. A reversible thermosensitive recording material containing a colorless or pale-colored dye precursor and a reversible color developer which causes a reversible color change in the dye precursor due to a difference in cooling rate after heating. Wherein 1 of the compound represented by the following formula 1
Use of one or more species and the following as a reversible developer
Reversible thermosensitive recording material characterized in that Ru using the compound represented by 2. Embedded image In (Formula 1, A represents a substituted or unsubstituted aromatic ring or heterocyclic ring, R represents an aliphatic hydrocarbon group. However,
Chemical formula 1 excludes chemical formula 2 below. ) ## STR2 ## (In the chemical formula 2, n represents an integer of 1 or more and 3 or less;
1 and 12 each represent an integer of 0 or 1. R ₁ and R ₂ are
Select from aliphatic hydrocarbon groups, alkoxy groups, and halogen atoms
Represents a substituent or a hydrogen atom.
It may be. X ₁ and X ₂ each have at least one
Represents a divalent group having a terrorist atom,
May be. Ar is an aromatic group which may have a substituent
Represents R ₃ is an aliphatic hydrocarbon having 6 to 22 carbon atoms
Represents a group. )