JP2003292807A - Fluoran compound, its manufacturing method, and recording material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel fluoran compound, a manufacturing method thereof, and a recording material using such a compound. <P>SOLUTION: The fluoran compound represented by formula (1), such as 3-di(n-amyl)amino-6-methyl-7-(N-p-tolylsulfonylaminocarbonyl)anilinofluoran, is obtained by the reaction of a fluoran compound, e.g. 3-di(n-amyl)amino-6- methyl-7-anilinofluoran, with an isocyanate compound such as p-tolylisocyanate and p-tolylsulfonyl isocyanate. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluoran compound, a method for producing the same, and a recording material using the compound.

[0002]

2. Description of the Related Art Conventionally, as a recording material utilizing a coloring reaction between a leuco dye composed of a fluoran compound and a color developing agent,
The heat-sensitive recording material, the pressure-sensitive recording material, or the thermal transfer recording material is widely used. Especially, the heat-sensitive recording material is relatively inexpensive, the recording equipment is compact, and the maintenance thereof is easy. It is used in a wide range of fields as a recording medium for various computers and other applications.

Various heat-sensitive recording materials capable of multicolor recording containing at least two kinds of leuco dyes composed of fluoran compounds having different color tones depending on the difference in applied heat energy are commercially available. Such heat-sensitive recording materials are color-separable. I have a problem.

[0004]

An object of the present invention is to provide a novel fluorane compound, a method for producing the same, and a recording material using such a compound.

[0005]

The fluoran compound represented by the general formula (1) or (2) is, for example, the fluoran compound represented by the general formula (4) or (5) and the general formula (6). It is obtained by a reaction with an isocyanate compound represented by

[0006]

[Chemical 7]

[0007]

[Chemical 8]

In the general formulas (1) and (2), R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkoxy group having 2 to 12 carbon atoms. It represents an alkyl group or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.
R ₁ and R ₂ may form a pyrrolidino group or a piperidino group together with the adjacent nitrogen atom. R ₃ is a hydrogen atom,
Represents a halogen atom or a methyl group. R ₄ is a phenyl group which may be substituted with at least one group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a trichloromethyl group and a trifluoromethyl group, and a carbon number 1
To 12 alkyl groups or benzyl groups. R ₅
Is a phenyl group, a phenylsulfonyl group, a naphthyl group or a naphthylsulfonyl group which may be substituted with at least one group selected from an alkyl group having 1 to 20 carbon atoms, a halogen atom and an alkyl group having 1 to 4 carbon atoms. Represents

[0009]

[Chemical 9]

[0010]

[Chemical 10]

In the general formulas (4) and (5), R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkoxy group having 2 to 12 carbon atoms. It represents an alkyl group or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.
R ₁ and R ₂ may form a pyrrolidino group or a piperidino group together with the adjacent nitrogen atom. R ₃ is a hydrogen atom,
Represents a halogen atom or a methyl group. R ₄ is a phenyl group which may be substituted with at least one group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a trichloromethyl group and a trifluoromethyl group, and a carbon number 1
To 12 alkyl groups or benzyl groups.

[0012]

[Chemical 11]

In the general formula (6), R ₅ has 1 to 2 carbon atoms.
It represents a phenyl group, a phenylsulfonyl group, a naphthyl group or a naphthylsulfonyl group which may be substituted with at least one group selected from an alkyl group of 0, a halogen atom and an alkyl group having 1 to 4 carbon atoms.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorane compound represented by the general formula (1) or (2) is, for example, a commercially available fluorane compound represented by the general formula (4) or (5) and a general formula (6). ) Is obtained by heating and melting with an isocyanate compound represented by the formula (1). It is obtained by dissolving the fluorane compound represented by and the isocyanate compound represented by the general formula (6) and heating the solution.

In the solution, at least one selected from the following general formula (3) and hindered phenolic compounds is allowed to coexist as a catalyst to increase the reaction rate, and the general formula (1 ) Or (2), the fluoran compound is obtained and preferred.

[0016]

[Chemical 12]

In the general formula (3), R _{1 to} R ₄ each represent a hydrogen atom or an optionally branched alkyl group having 1 to 5 carbon atoms.

In particular, when the isocyanate compound represented by the general formula (6) does not have a sulfonyl group, it is preferable that at least one selected from the general formula (3) and the hindered phenol compound is allowed to coexist as a catalyst. The amount used is not particularly limited, but is about 0.1 to 30% by weight with respect to the isocyanate compound.

Specific examples of the compound represented by the general formula (3) include 2-mercaptobenzimidazole and 2
-Mercapto-5-methylbenzimidazole and the like.

Specific examples of the hindered phenolic compound include 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone and 2,2'-butylidenebis (4-methyl-). 6-te
rt-butylphenol), 4,4′-thiobis (6-
tert-butyl-m-cresol), 4,4′-thiobis (6-tert-butyl-o-cresol), 4,
4'-thiobis (2,6-di-tert-octylphenol), 2,2'-thiobis (2,6-di-tert.
-Butylphenol), 4,4'-butylidene bis (6
-Tert-butyl-m-cresol), 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -6,
6-dimethylheptane, 4-methyl-2,6-di-te
Examples include rt-butylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) butane, and the like.

The fluorane compound represented by the general formula (1) or the general formula (2) is represented by the general formula (4) or the general formula (5).
It is synthesized by reacting the hydrogen atom bonded to the nitrogen atom of the amino group of the fluorane compound represented by with the isocyanate group of the isocyanate compound represented by the general formula (6).

Specific examples of the fluorane compound represented by the general formula (4) include 3-pyrrolidino-6-methyl-7-anilinofluorane and 3- (N-ethyl-p-toluidino) -6-. Methyl-7-anilinofluorane, 3
-Diethylamino-7-benzylaminofluorane, 3
-Diethylamino-7- (o-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (2,6
-Dimethylanilino) fluorane, 3-diethylamino-6-methyl-7- (2,4-dimethylanilino) fluorane, 3-diethylamino-6-methyl-7-methylaminofluorane, 3-diethylamino-6-methyl −
7-benzylaminofluorane, 3-diethylamino-
6-methyl-7-anilinofluorane, 3-diethylamino-7-benzylaminofluorane, 3-diethylamino-7-ethylaminofluorane, 3-diethylamino-7-methylaminofluorane, 3-diethylamino-7- (M-Trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7- (m-methylanilino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-
7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, 3-di (n-
Amyl) amino-6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-7- (o-chloroanilino) fluorane, 3- (N-isoamyl-N-ethylamino) -7-ani Rinofluorane, 3- (N-isoamyl-N-ethylamino) -7- (o-chloroanilino) fluorane, 3- (N-isoamyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3-
(N-isoamyl-N-ethylamino) -6-methyl-
7-anilinofluorane, 3- (N-cyclohexyl-
N-methylamino) -6-methyl-7-anilinofluorane, 3- (Nn-hexyl-N-ethylamino)-
7-anilinofluorane, 3- [N- (3-ethoxypropyl) -N-ethylamino] -6-methyl-7-anilinofluorane, 3- [N- (3-ethoxypropyl)
-N-methylamino] -6-methyl-7-anilinofluorane and the like can be mentioned.

Specific examples of the fluorane compound represented by the general formula (5) include 3-diethylamino-7-benzylamino-benzo (a) fluorane and 3-diethylamino-7-methylamino-benzo (a) fluorane. ,
3-di (n-butyl) amino-7-benzylamino-benzo (a) fluorane, 3-di (n-butyl) amino-
7-Methylamino-benzo (a) fluorane, 3-diethylamino-9-benzylamino-benzo (a) fluorane, 3-diethylamino-9-methylamino-benzo (a) fluorane, 3-di (n-butyl) amino -9-
Benzylamino-benzo (a) fluorane, 3-di (n
-Butyl) amino-9-methylamino-benzo (a) fluorane, 3-diethylamino-7-anilino-benzo (a) fluorane, 3-di (n-butyl) amino-7-
Anilino-benzo (a) fluorane, 3- (Nn-amyl-N-ethylamino) -7-benzylamino-benzo (a) fluorane, 3- (Nn-amyl-N-ethylamino) -7 -Methylamino-benzo (a) fluorane and the like.

Specific examples of the isocyanate compound represented by the general formula (6) include phenyl isocyanate, p-tolyl isocyanate, a-naphthyl isocyanate, 2,6-diisopropylphenyl isocyanate, octadecyl isocyanate, phenylsulfonyl isocyanate, p. -Tolyl sulfonyl isocyanate, a-naphthyl sulfonyl isocyanate, octadecyl isocyanate, etc. are mentioned.

Examples of the fluorane compound represented by the general formula (1) include 3-pyrrolidino-6-methyl-7-
(Np-tolylsulfonylaminocarbonyl) anilinofluorane, 3-diethylamino-6-methyl-7-
[(Np-tolylsulfonylaminocarbonyl) anilino] fluorane, 3-diethylamino-7-[(N-
p-tolylsulfonylaminocarbonyl) -m-trifluoromethylanilino] fluorane, 3-diethylamino-6-methyl-7-[(Np-tolylsulfonylaminocarbonyl) -2,6-dimethylanilino] fluorane, 3-Diethylamino-6-methyl-7-[(N-
p-tolylsulfonylaminocarbonyl) -2,4-dimethylanilino] fluorane, 3-di (n-butyl) amino-6-methyl-7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane, 3 -Di (n-butyl) amino-7-[(Np-tolylsulfonylaminocarbonyl) -o-chloroanilino] fluorane, 3
-Di (n-butyl) amino-7-[(Np-tolylsulfonylaminocarbonyl) -o-chloroanilino] fluorane, 3-di (n-amyl) amino-6-methyl-
7- (N-phenylsulfonylaminocarbonyl) anilinofluorane, 3-di (n-amyl) amino-6-methyl-7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane, 3- (N -Isoamyl-N-
Ethylamino) -6-methyl-7- (N-phenylsulfonylaminocarbonyl) anilinofluorane, 3-
(N-isoamyl-N-ethylamino) -7- (Np
-Tolylsulfonylaminocarbonyl) anilinofluorane, 3- (N-isoamyl-N-ethylamino) -6
-Methyl-7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane, 3- (N-isoamyl-
N-ethylamino) -7- (N-1-naphthylsulfonylaminocarbonyl) anilinofluorane, 3- (N-
Ethyl-N-p-toluidino) -6-methyl-7- (N
-P-tolylsulfonylaminocarbonyl) anilinofluorane, 3- (Nn-hexyl-N-ethylamino) -7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane, 3- (N- Cyclohexyl
N-methylamino) -6-methyl-7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane,

3-pyrrolidino-6-methyl-7- (N-
Phenylaminocarbonyl) anilinofluorane, 3-
Pyrrolidino-6-methyl-7- (N-p-tolylaminocarbonyl) anilinofluorane, 3-diethylamino-6-methyl-7-[(N-phenylaminocarbonyl) -2,6-dimethylanilino] fluorane , 3-diethylamino-7-[(N-phenylaminocarbonyl) -m-trifluoromethylanilino] fluorane,
3-Diethylamino-6-methyl-7-[(Np-tolylaminocarbonyl) -2,4-dimethylanilino]
Fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7- (Np-tolylaminocarbonyl) anilinofluorane, 3-diethylamino-7
-[N- (phenylaminocarbonyl) -N-benzylamino] fluorane, 3-diethylamino-6-methyl-7- (N-phenylaminocarbonyl) anilinofluorane, 3-diethylamino-7- [N- (phenyl Aminocarbonyl) -N-methylamino] fluorane, 3
-Diethylamino-7- [N- (2,6-dimethylphenylaminocarbonyl) -N-benzylamino] fluorane, 3-diethylamino-7- [N- (2,6-diisopropylphenylaminocarbonyl) -N-benzylamino ] Fluoran, 3-diethylamino-7- [N-
(Octadecylaminocarbonyl) -N-benzylamino] fluorane, 3-diethylamino-7-[(Np
-Tolylaminocarbonyl) -m-trifluoromethylanilino] fluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7- (Np-tolylaminocarbonyl) anilinofluorane, 3- Diethylamino-6
-Methyl-7- (Np-tolylaminocarbonyl) anilinofluorane, 3-di (n-butyl) amino-6-
Methyl-7- (Np-tolylaminocarbonyl) anilinofluorane, 3-di (n-butyl) amino-7-
[(N-phenylaminocarbonyl) -o-chloroanilino] fluorane, 3-di (n-amyl) amino-6-
Methyl-7- [N- (octadecylaminocarbonyl)
Anilino] fluorane, 3-di (n-amyl) amino-
6-methyl-7- (N-phenylaminocarbonyl) anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7- (N-phenylaminocarbonyl) anilinofluorane, (N -Isoamyl-N-ethylamino) -7- [N- (phenylaminocarbonyl)
Anilino] fluorane, 3- (N-isoamyl-N-ethylamino) -6-methyl-7- (N-phenylaminocarbonyl) anilinofluorane, 3- (N-isoamyl-N-ethylamino) -6- Methyl-7- (N-p-
Trilylaminocarbonyl) anilinofluorane, 3-
(N-isoamyl-N-ethylamino) -7- (N-1
-Naphthylaminocarbonyl) anilinofluorane, 3
-(N-n-hexyl-N-ethylamino) -7- (N
-P-tolylaminocarbonyl) anilinofluorane and the like.

Specific examples of the compound represented by the general formula (2) include 3-diethylamino-7- (N-benzyl-N-phenylaminocarbonylamino) -benzo (a) fluorane and 3-diethylamino-7. -(N-benzyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane, 3-diethylamino-7- (N-methyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane , 3-di (n-butyl) amino-7- (N-benzyl-Np-
Tolylsulfonylaminocarbonylamino) -benzo (a) fluorane, 3-di (n-butyl) amino-7-
(N-methyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane, 3-diethylamino-9- (N-benzyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane, 3-diethylamino-9- (N-benzyl-N-1
-Naphthylsulfonylaminocarbonylamino) -benzo (a) fluorane, 3-diethylamino-9- (N-
Methyl-N-phenylsulfonylaminocarbonylamino) -benzo (a) fluorane, 3-di (n-butyl)
Amino-9- (N-benzyl-N-phenylsulfonylaminocarbonylamino) -benzo (a) fluorane, 3
-Di (n-butyl) amino-9- (N-methyl-N-phenylruaminocarbonylamino) -benzo (a) fluorane, 3-diethylamino-7- (N-phenylaminocarbonyl) anilino-benzo (a) Fluoran, 3
-Di (n-butyl) amino-7- (N-phenylaminocarbonyl) anilino-benzo (a) fluorane, 3-
(Nn-amyl-N-ethylamino) -7- (N-benzylaminocarbonyl) anilino-benzo (a) fluorane, 3- (Nn-amyl-N-ethylamino)-
7- (N-methylaminocarbonyl) anilino-benzo (a) fluorane and the like can be mentioned.

Recording materials using the fluoran compound represented by the general formula (1) or (2) include heat-sensitive recording materials, pressure-sensitive recording materials and heat transfer recording materials. Will be described in detail.

Generally, a leuco dye-based thermal recording material basically comprises a support and a thermosensitive coloring layer containing a leuco dye and a coloring agent thereon, and is exposed to a leuco dye by heat energy. Although the leuco dye develops color by reacting with a coloring agent, those having a sulfonyl group in the fluoran compound represented by the general formula (1) and the general formula (2) (hereinafter referred to as a specific leuco dye) are It has a property of developing color by heat energy even without a color-developing agent, but it may be used in combination with a color-developing agent.

The specific leuco dye develops a first color tone by heat energy, and changes to a second color tone different from the first color tone by heating with higher heat energy. Although the mechanism of this color development and discoloration is not clear, it is considered that the aminocarbonylamino group or the sulfonylaminocarbonylamino group is thermally decomposed to produce a coloring agent, and the electronic state of a specific leuco dye is changed.

Among the heat-sensitive recording materials using a specific leuco dye, the heat-sensitive recording material having a fluoran compound represented by the general formula (1) develops a red color due to heat energy and becomes black by heating with higher heat energy. The heat-sensitive recording material having a color tone and having the fluorane compound represented by the general formula (2) has a characteristic that the color tone develops red color due to heat energy and the color tone develops into a blue color tone when heated with higher heat energy.

The specific leuco dye is preferably used in an amount of about 3 to 40% by mass based on the total solid content of the thermosensitive coloring layer, and has excellent storage stability in the recording portion and excellent color separation. The material can be obtained.

The specific leuco dye is used in the form of solid particles formed from the specific leuco dye, in the form of composite particles of a resin and the specific leuco dye, or in the form of being encapsulated in microcapsules.

The specific leuco dye may be used alone, or may be used in combination with other leuco dyes. Specific examples of other leuco dyes include, for example, 3- (N-ethyl-p
-Toluidino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluorane, 3- (N-ethyl-N-isoamyl ) Amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane, 3
-Diethylamino-6-methyl-7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, 3-di (n-amyl) amino-6-
Methyl-7-anilinofluorane, 3-diethylamino-7- (o-chlorophenylamino) fluorane, 3-
Di (n-butyl) amino-7- (o-chlorophenylamino) fluorane, 3-diethylamino-7- (o-fluorophenylamino) fluorane, 3-di (n-butyl) amino-7- (o-fluorophenyl Amino) fluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3
-Diethylamino-6-chloro-7-anilinofluorane, 3-di (n-butyl) amino-6-methyl-7-m
-Toluidinofluorane, 3- (N-ethyl-N-isobutyl) amino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-p-ethoxyanilinofluorane, 3 -Pyrrolidino-6-methyl-
7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 2,2-bis {4- [6 '
-(N-cyclohexyl-N-methylamino) -3'-
Methylspiro [phthalide-3,9'-xanthene-2 '
-Ylamino] phenyl} propane, 3-diethylamino-7- (3'-trifluoromethylphenyl) aminofluorane and other black color-forming dyes,

3,3-Bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino2-methylphenyl) -3- (4-dimethylaminophenyl) -6-dimethylaminophthali A blue-coloring dye such as 3-diethylamino-7-dibenzylamino-benzo [a] fluorane,

3- (N-ethyl-Np-tolyl) amino-7-N-methylanilinofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7-dibenzylaminofluorane Green coloring dyes, such as

3,6-bis (diethylamino) fluorane-γ-anilinolactam, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7.
-Chlorofluorane, rhodamine (o-chloroanilino) lactam, rhodamine (p-chloroanilino) lactam, 3-diethylamino-7,8-benzofluorane, 3- (N-ethyl-p-toluidino) -7-methylfluorane , 3-diethylamino 6,8-dimethylfluorane, 3-diethylamino-7-phenoxyfluorane, 3- (N-ethyl-N-isoamylamino) -7-phenoxyfluorane, and other red-coloring dyes,

3,3-bis [1- (4-methoxyphenyl) -1- (4-dimethylaminophenyl) ethylene-
2-yl] -4,5,6,7-tetrachlorophthalide,
3- [p- (p-anilinoanilino) anilino] -6-
Methyl-7-chlorofluorane, 3- [p- (p-dimethylaminoanilino) anilino] -6-methyl-7-chlorofluorane, 3- [p- (p-dimethylaminoanilino) anilino]- 6-methylfluorane, 3-p-
(P-Chloroanilino) anilino-6-methyl-7-chlorofluorane, 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-dimethylamino)
Phthalide, 3,3'-bis (4-diethylamino2-ethoxyphenyl) -4-azaphthalide, 3- (Np-
Tolyl-N-ethylamino) -6,8,8-trimethyl-9-ethyl-8,9-dihydro- (3,2, e) pyridfluorane, 3-di (n-butyl) amino-6,8,
Near red such as 8-trimethyl-8,9-dihydro- (3,2, e) pyridfluorane and 3- [1,1-bis (p-diethylaminophenyl) ethylene-2-yl] -6-dimethylaminophthalide A dye having an absorption wavelength in the outer region can be used.

In the heat-sensitive recording material of the present invention, a color-developing agent is not always necessary, but it can be contained in order to increase the color-developing sensitivity. Examples of such colorants include 4,4'-dihydroxydiphenylmethane and 4,4'-
Isopropylidene diphenol, 4,4'-cyclohexylidene diphenol, 1,1-bis (4-hydroxyphenyl) -ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, p-tolylsulfonyl p-aminophenol, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-benzoic acid benzyl ester, N, N'-di -M-chlorophenylthiourea, N-
p-tolylsulfonyl N'-3- (p-tolylsulfonyloxy) phenylurea, 4,4'-bis (p-tolylsulfonylaminocarbonylamino) diphenylmethane, 4- [2- (p-methoxyphenoxy) ethyloxy] salicylic acid , 4- {3- (p-tolylsulfonyl)
Zinc propyloxy] salicylate, 5- [p- (2-p
-Methoxyphenoxyethoxy) cumyl] zinc salicylate and the like.

In the composite fine particles or in the thermosensitive coloring layer, a sensitizer for increasing the recording sensitivity and a preservative improving agent for further improving the preservability of the recording portion are added to the total solid content of the thermosensitive coloring layer. It may be contained in an amount of about 5 to 30% by mass.
As the sensitizer, compounds conventionally known as sensitizers for heat-sensitive recording materials can be used. Specific examples of such sensitizers include stearic acid amide, ethylenebisstearic acid amide, parabenzyl biphenyl, dibenzyl terephthalate, 2-naphthylbenzyl ether, di-o-chlorobenzyl adipate, 1,2.
-Diphenoxyethane, 1,2-bis (3-methylphenoxy) ethane, dibenzyl oxalate, di-p oxalate
-Methylbenzyl, di-p-chlorobenzyl oxalate,
1,2-bis (3,4-dimethylphenyl) ethane,
1,3-bis (2-naphthoxy) propane, m-terphenyl, diphenyl sulfone, benzophenone and the like can be mentioned.

Specific examples of the storability improver include 2,2'-bis [4- (hydroxyphenylsulfonyl) phenoxy] diethyl ether and 1,1,3-tris (2-methyl-4-hydroxy). -5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (4-tert-butyl-3-hydroxy) -2,6-dimethylbenzyl) isocyanuric acid,
4-benzyloxyphenyl-4 '-(2-methyl-
2,3-epoxypropyloxy) phenyl sulfone,
1,1-bis (2-methyl-4-hydroxy-5-tert
-Butylphenyl) butane, 2,2'-methylenebis (4,6-di-tert-butylphenyl), 4,4'-dihydroxy-3,3 ', 5,5'-tetrabromodiphenylsulfone, 4- ( 2-methyl-1,2-epoxyethyl) diphenyl sulfone, terephthalic acid diglycidyl ether, 4,4 ′

Further, the thermosensitive coloring layer has an average particle size of 5
calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcined clay, amorphous silica, diatomaceous earth, synthetic aluminum silicate, zinc oxide, titanium oxide, aluminum hydroxide, barium sulfate, urea-formalin resin filler, etc. Pigments, dimethylol urea, glyoxal, polyamide epichlorohydrin resin, boric acid, water resistant agents such as borax, paraffin wax, carnauba wax, microcrystalline wax, polyolefin wax, and lubricants such as polyethylene wax, zinc stearate and calcium stearate, Colored dyes, colored pigments, fluorescent dyes and the like can also be contained.

The heat-sensitive color forming layer contains, for example, water as a medium, and comprises a specific leuco dye, a coloring agent, an adhesive and, if necessary, other leuco dye, a sensitizer, a storability improver, a pigment, a lubricant and the like. The coating liquid for the thermosensitive coloring layer prepared by mixing and stirring the composition is applied to a support such as high-quality paper having a thickness of about 40 to 200 μm, transparent (opaque) film, and synthetic paper at a coating amount after drying of 2 to 2 15 g / ^{m 2,} more preferably formed by coating and drying so as 4~10g / ^{m 2.} The thermosensitive coloring layer may be a single layer or a multilayer.

Examples of the adhesive in the coating liquid for the thermosensitive color developing layer include polyvinyl alcohol and its derivatives, starch and its derivatives, hydroxy-methyl cellulose, hydroxy-ethyl cellulose, hydroxy-propyl cellulose, methyl cellulose, ethyl cellulose, and other cellulose derivatives, polyvinyl. Pyrrolidone, acrylamide-acrylic acid ester copolymer, acrylamide-acrylic acid ester-methacrylic acid ester copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, casein, water-soluble gelatin etc. Examples thereof include adhesives, vinyl acetate latex, urethane latex, acrylic latex, styrene-butadiene latex and the like.

On the thermosensitive coloring layer, a protective layer containing an organic polymer compound as a main component, which is excellent in film-forming property, is provided in order to further improve recording runnability, storage stability against chemicals in the recording area and transparency. preferable.

The protective layer is made of, for example, partially (fully) saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, gelatin or casein as an organic polymer compound having an excellent film-forming property. A coating solution for the protective layer prepared by mixing and stirring an aqueous solution and, if necessary, an auxiliary agent that can be added to the coating solution for the thermosensitive color developing layer, has a coating amount of about 1 to 6 g / m 2 after drying on the thermosensitive color developing layer. It is formed by coating and drying so that

The method of applying the heat-sensitive color forming layer coating liquid and the protective layer coating liquid is not particularly limited, and examples thereof include methods such as air knife coating, blade coating, die coating, curtain coating, and slide bead coating.

After coating and drying the heat-sensitive color-developing layer, if necessary, smoothing treatment such as super calendering may be carried out, or a gloss layer cured by irradiation with ultraviolet rays or electron beams may be provided on the protective layer. Thermal sensitivity such as providing an undercoat layer containing pigment or organic hollow particles having an oil absorption of 70 ml / 100 g or more between the support and the thermosensitive coloring layer, or providing a magnetic recording layer on the other surface of the support. Various known techniques relating to the production of recording materials may be added.

[0049]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention.
Unless otherwise specified, "part" and "%" indicate "part by mass" and "% by mass", respectively.

Example 1 80 g of 3-di (n-amyl) amino-6-methyl-7-anilinofluorane was dissolved in 200 ml of toluene under heating, cooled to 20 ° C., and 40 g of p-tolylsulfonyl isocyanate was added dropwise. Then, the mixture was reacted at 20 ° C. for 12 hours. After the reaction, the precipitated crystals were filtered. Then, it was recrystallized from toluene to give white 3-di (n-amyl) amino-6.
70 g of -methyl-7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane was obtained. Yield 70
%Met. Melting point 149-151 [deg.] C. The infrared absorption spectrum of this compound is shown in FIG. It was red on silica gel when not heated, but when heated to 250 ° C., it developed black on silica gel.

Example 2 20 g of 3- (N-isoamyl-N-ethylamino) -7-anilinofluorane was dissolved in 50 ml of toluene under heating and cooled to 20 ° C., then 10 g of p-tolylsulfonyl isocyanate was added dropwise. The mixture was reacted at 20 ° C for 12 hours. After the reaction, the precipitated crystals were filtered. Then, it was recrystallized from toluene to obtain 20 g of white 3- (N-isoamyl-N-ethylamino) -7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane. Yield 7
It was 2%. It had a melting point of 160 to 162 ° C. and was red on silica gel when not heated, but when heated to 250 ° C., it developed green.

Example 3 20 g of 3-di (n-butyl) amino-7- (o-chloroanilino) fluorane was dissolved in 50 ml of toluene under heating and cooled to 20 ° C., then 10 g of p-tolylsulfonyl isocyanate was added dropwise. The reaction was carried out at 20 ° C for 12 hours. After the reaction, the precipitated crystals were filtered. Then, it was recrystallized with toluene to give white 3-di (n-butyl) amino-7.
-[(N-p-tolylsulfonylaminocarbonyl)-
21 g of o-chloroanilino] fluorane was obtained. The yield was 77%. The melting point was 169 to 171 ° C., which was red on silica gel when not heated, but the one heated to 250 ° C. developed a black color.

Example 4 3- (N-Ethyl-p-toluidino) -6-methyl-7
-Toluene 150m under heating 20g of anilinofluorane.
After dissolving in 1 and cooling to 20 ° C., 10 g of p-tolylsulfonyl isocyanate was added dropwise and the reaction was carried out at 20 ° C. for 12 hours. After the reaction, the precipitated crystals were filtered. Then, it was recrystallized with toluene and white 3- (N-ethyl-N-p
-Toluidino) -6-methyl-7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane 24 g
Got The yield was 89%. Melting point 163-165
℃, red color on silica gel when not heated, 250 ℃
Those that were heated to developed a black color.

Example 5 40 g of 3-di (n-amyl) amino-6-methyl-7-anilinofluorane was dissolved in 100 ml of toluene under heating, and after cooling to 20 ° C., 20 g of phenylsulfonyl isocyanate was added dropwise. The reaction was carried out at 20 ° C for 12 hours. After the reaction, the precipitated crystals were filtered. Then, it was recrystallized from toluene to give white 3-di (n-amyl) amino-6.
34 g of -methyl-7- (N-phenylsulfonylaminocarbonyl) anilinofluorane was obtained. 70% yield
Met. Melting point 146 to 150 ° C., red color on silica gel when not heated, but what was heated to 250 ° C. developed black color on silica gel.

Example 6 59 g of 3-di (n-amyl) amino-6-methyl-7-anilinofluorane and 3 g of 2-mercaptobenzimidazole were dissolved in 200 ml of toluene with heating, and 15 g of phenyl isocyanate was added dropwise. Reflux for hours. After the reaction, a 10% aqueous solution of sodium hydroxide was added, and the reaction product was extracted with toluene. After removing the toluene solvent, the obtained crystals were dissolved in cyclohexane and recrystallized to give white 3-di (n-amyl) amino-6-methyl-
59 g of 7- (N-phenylaminocarbonyl) anilinofluorane was obtained. The yield was 83%. Melting point 97-
It is red on silica gel when it is not heated at 99 ℃.
Those heated to 0 ° C developed a black color on silica gel.

Example 7 27 g of 3- (N-isoamyl-N-ethylamino) -7-anilinofluorane and 3 g of 2-mercaptobenzimidazole were dissolved in 100 ml of toluene under heating and 8 g of phenylisocyanate was added dropwise for 6 hours. Refluxed. After the reaction, the precipitated crystals were filtered. Then, the obtained crystals were dissolved in toluene and recrystallized, and white (N-isoamyl-
24 g of N-ethylamino) -7- (N-phenylaminocarbonyl) anilino) fluorane was obtained. Yield 74
%Met. The melting point was 98 to 100 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a green color on silica gel.

Example 8 3-Diethylamino-7-benzylaminofluorane 3
4 g of 2-mercaptobenzimidazole 2 g was dissolved in 150 ml of toluene under heating, and phenyl isocyanate 1 was added.
2 g was added dropwise and the mixture was refluxed for 3 hours. After the reaction, a 10% aqueous solution of sodium hydroxide was added, and the reaction product was extracted with toluene. After removing the toluene solvent, the obtained crystals were dissolved in methanol and recrystallized to give white 3-diethylamino-7.
34 g of-[N- (phenylaminocarbonyl) -N-benzylamino] fluorane was obtained. The yield was 80%. Melting point 169 to 171 ° C., red color on silica gel when not heated, but what was heated to 300 ° C. developed black color on silica gel.

Example 9 3-Diethylamino-7-methylaminofluorane 34
g, 2-mercaptobenzimidazole 2 g was dissolved in toluene 150 ml under heating, and phenyl isocyanate 12 was added.
g was added dropwise, and the mixture was refluxed for 3 hours. After the reaction, a 10% aqueous solution of sodium hydroxide was added, and the reaction product was extracted with toluene.
After removing the toluene solvent, the obtained crystals were dissolved in methanol and recrystallized to give white 3-diethylamino-7-
20 g of [N- (phenylaminocarbonyl) -N-methylamino] fluorane was obtained. The yield was 77%.
Melting point 203-205 ° C, red color on silica gel when not heated, but what was heated to 300 ° C developed black color on silica gel.

Example 10 3-Diethylamino-7-benzylaminofluorane 2
0 g and 2 g of 2-mercaptobenzimidazole were dissolved in 150 ml of toluene under heating, 15 g of 2,6-dimethylphenyl isocyanate was added dropwise, and the mixture was refluxed for 3 hours. After the reaction, the precipitated crystals were filtered. Then, the obtained crystals were dissolved in toluene and recrystallized to obtain 21 g of white 3-diethylamino-7- [N- (2,6-dimethylphenylaminocarbonyl) -N-benzylamino] fluorane. The yield was 82%. Melting point 187 to 189 ° C., red on silica gel when not heated, but what was heated to 300 ° C. developed black on silica gel.

Example 11 3-Diethylamino-7-benzylaminofluorane 2
7 g and 2 g of 2-mercaptobenzimidazole were dissolved in 150 ml of toluene under heating, 15 g of 2,6-diisopropylphenyl isocyanate was added dropwise, and the mixture was refluxed for 3 hours. After the reaction, add 10% aqueous solution of sodium hydroxide,
Extract the reaction product with toluene. After removing the toluene solvent, the obtained crystals were dissolved in cyclohexane and recrystallized to obtain 20 g of white 3-diethylamino-7- [N- (2,6-diisopropylphenylaminocarbonyl) -N-benzylamino] fluorane. Obtained. The yield was 79%.
The melting point was 118 to 120 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a black color on silica gel.

Example 12 3-Diethylamino-7-methylaminofluorane 30
g, 2 g of 2-mercaptobenzimidazole were dissolved in 150 ml of toluene under heating, 20 g of octadecylphenyl isocyanate was added dropwise, and the mixture was refluxed for 20 hours. After the reaction, a 10% aqueous solution of sodium hydroxide was added, and the reaction product was extracted with toluene. After removing the toluene solvent, the obtained crystals were dissolved in cyclohexane and recrystallized to obtain 22 g of white 3-diethylamino-7- [N- (octadecylaminocarbonyl) -N-benzylamino] fluorane. The yield was 45%. The melting point was 103 to 110 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a black color on silica gel.

Example 13 30 g of 3-di (n-amyl) amino-6-methyl-7-anilinofluorane and 2 g of 2-mercaptobenzimidazole were dissolved in 150 ml of toluene under heating, and 20 g of octadecylphenyl isocyanate was added dropwise. Refluxed for 20 hours. After the reaction, a 10% aqueous solution of sodium hydroxide was added, and the reaction product was extracted with toluene. After removing the toluene solvent, the obtained crystals were dissolved in cyclohexane and recrystallized to give white 3-di (n-amyl) amino-6-methyl-
20 g of 7- [N- (octadecylaminocarbonyl) anilino] fluorane was obtained. The yield was 44%.
Melting point 107-115 ° C., red color on silica gel when not heated, but what was heated to 300 ° C. developed black color on silica gel.

Example 14 27 g of 3-diethylamino-7-benzylamino-benzo (a) fluorane and 1.5 g of 2-mercaptobenzimidazole were dissolved in 200 ml of toluene under heating.
Cool to 0 ° C., add 8 g of phenyl isocyanate dropwise,
Refluxed for 12 hours. After the reaction, remove the toluene solvent,
The obtained crystals were recrystallized from methanol to give white 3-
Diethylamino-7- (N-benzyl-N-phenylaminocarbonylamino) -benzo (a) fluorane 25
g was obtained. The yield was 74%. Melting point 228-230
℃, red color on silica gel when not heated, 300 ℃
What was heated to the above developed a blue color on silica gel.

Example 15 27 g of 3-diethylamino-7-benzylamino-benzo (a) fluorane was dissolved in 200 ml of toluene under heating and cooled to 20 ° C., 12 g of p-tolylsulfonyl isocyanate was added dropwise, and 12 g at 20 ° C. Reacted for hours. After the reaction, the toluene solvent was removed, and the obtained crystals were recrystallized from cyclohexane to give white 3-diethylamino-7- (N-benzyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane. Thirty
g was obtained. The yield was 82%. Melting point 146-150
℃, red color on silica gel when not heated, 300 ℃
What was heated to the above developed a blue color on silica gel.

Example 16 27 g of 3-diethylamino-9-benzylamino-benzo (a) fluorane was dissolved in 200 ml of toluene under heating and cooled to 20 ° C., 12 g of p-tolylsulfonyl isocyanate was added dropwise, and 12 g at 20 ° C. Reflux for hours. After the reaction, the toluene solvent was removed, and the obtained crystals were recrystallized from cyclohexane to give white 3-diethylamino-9- (N-benzyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane. 25
g was obtained. The yield was 68%. Melting point 146-152
℃, red color on silica gel when not heated, 300 ℃
What was heated to the above developed a blue color on silica gel.

Example 17 3-Diethylamino-7-methylamino-benzo (a)
23 g of fluoran is dissolved in 200 ml of toluene under heating,
Cool to 20 ° C. and phenylsulfonyl isocyanate 1
2 g was added dropwise and reacted at 20 ° C. for 12 hours. After the reaction, the toluene solvent was removed, and the obtained crystals were recrystallized from cyclohexane to give white 3-diethylamino-9-
20 g of (N-methyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane was obtained.
The yield was 70%. The melting point was 140 to 150 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a blue color on silica gel.

Example 18 In the same manner as in Example 6 except that 3 g of 2,5-di-tert-amylhydroquinone was used instead of 3 g of 2-mercaptobenzimidazole, white 3-di ( n-amyl) amino-6-methyl-7- (N-
Phenylaminocarbonyl) anilinofluorane 61g
Got The yield was 86%. The melting point was 97 to 99 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a black color on silica gel.

Example 19 Example 6 was repeated except that 3 g of 4,4′-thiobis (6-tert-butyl-o-cresol) was used instead of 3 g of 2-mercaptobenzimidazole in Example 6.
And white 3-di (n-amyl) amino-6-
57 g of methyl-7- (N-phenylaminocarbonyl) anilinofluorane was obtained. The yield was 80%. The melting point was 97 to 99 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a black color on silica gel.

Example 20 In Example 6, instead of 3 g of 2-mercaptobenzimidazole, 4,4'-butylidenebis (6-te) was used.
(rt-butyl-m-cresol) except that 3 g was used.
In the same manner as in Example 6, 55 g of white 3-di (n-amyl) amino-6-methyl-7- (N-phenylaminocarbonyl) anilinofluorane was obtained. The yield was 77%. The melting point was 97 to 99 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a black color on silica gel.

Example 21 Same as Example 6 except that 3 g of 2,2′-butylidenebis (4-methyl-6-tert-butylphenol) was used in place of 3 g of 2-mercaptobenzimidazole in Example 6. Thus, 56 g of white 3-di (n-amyl) amino-6-methyl-7- (N-phenylaminocarbonyl) anilinofluorane was obtained. Yield 7
It was 9%. The melting point was 97 to 99 ° C., which was red on silica gel when not heated, but what was heated to 300 ° C. developed a black color on silica gel.

Example 22 White 3-di (n-amyl) amino-6-methyl-7- (as in Example 6 except that 3 g of 2-mercaptobenzimidazole was not used. N
-Phenylaminocarbonyl) anilinofluorane 18
g was obtained. The yield was 25%. Melting point 97-99 ° C,
It was red on silica gel when not heated, but what was heated to 300 ° C. developed black on silica gel.

Example 23 (Preparation of Leuco Dye Dispersion) Example 2 as leuco dye
3- (N-isoamyl-N-ethylamino) obtained in
-7- (N-p-tolylsulfonylaminocarbonyl)
Anilino fluoran 40 parts, polyvinyl alcohol 10
% Vertical aqueous sand mill (sand grinder, IMEX Co., Ltd.)
(Manufactured by Mitsui Chemical Co., Ltd.) to obtain a leuco dye dispersion liquid.

(Preparation of Coloring Agent Dispersion) N-as a coloring agent
A composition comprising 40 parts of p-tolylsulfonyl-N′-3- (p-tolylsulfonyloxy) phenylurea, 40 parts of a sulfone-modified polyvinyl alcohol 10% aqueous solution and 20 parts of water was used as a vertical sand mill (sand grinder, IMEX ( Manufactured by K.K.) and the average particle size is 0.
The colorant dispersion liquid was prepared by pulverizing to 8 μm.

(Preparation of Sensitizer Dispersion) A composition comprising 40 parts of a sensitizer (di-p-methylbenzyl oxalate), 40 parts of a sulfone-modified polyvinyl alcohol 10% aqueous solution and 20 parts of water was used in a vertical sand mill. (Sand grinder,
The average particle size is 0.8μ using IMEX Co., Ltd.
The sensitizer dispersion liquid was prepared by pulverizing so as to obtain m.

(Preparation of storage stability improving agent dispersion) As a storage stability improving agent, 25 parts of 2,2'-bis [4- (hydroxyphenylsulfonyl) phenoxy] diethyl ether and 1,2'-bis [4- (hydroxyphenylsulfonyl) phenoxy] diethyl ether were added.
3,5-tris (4-tert-butyl-3-hydroxy-
Average composition of a composition comprising 15 parts of 2,6-dimethylbenzyl) isocyanuric acid, 40 parts of a 10% aqueous solution of sulfone-modified polyvinyl alcohol, and 20 parts of water using a vertical sand mill (sand grinder, manufactured by AIMEX Co., Ltd.) It was pulverized to have a diameter of 1.0 μm to prepare a storage stability improving agent dispersion.

(Preparation of Coating Liquid for Protective Layer) Aluminum hydroxide (Hijilite H-42, Showa Light Metal Industry Co., Ltd.)
50 parts, 5 parts of 10% aqueous solution of sodium polyacrylate (dispersant), 21% aqueous dispersion of zinc stearate (Z-
7, Chukyo Yushi Co., Ltd. 50 parts, carboxy-modified polyvinyl alcohol 10% aqueous solution 400 parts, and water 10
A composition consisting of 0 parts was mixed and stirred to prepare a coating liquid for protective layer.

(Preparation of coating liquid for thermosensitive coloring layer) 20 parts of leuco dye dispersion liquid, 80 parts of coloring agent dispersion liquid, 30 parts of sensitizer dispersion liquid
Parts, preservative improver dispersion 40 parts, light calcium carbonate 50% dispersion 10 parts, zinc stearate 21% aqueous dispersion (Z-7, Chukyo Yushi Co., Ltd.) 20 parts, polyvinyl alcohol 10 % 120% aqueous solution was mixed and stirred to prepare a coating liquid for the thermosensitive color developing layer.

(Preparation of Coating Liquid for Undercoat Layer) 40 parts of calcined kaolin (Ansilex, manufactured by Engelhard), organic hollow particle dispersion liquid having a solid content concentration of 40% (wall film material: styrene resin, outer diameter: 1 μm) , Inner diameter: 0.6 μm, shape: sphere) 100 parts, light calcium carbonate 6 parts, sodium polyacrylate (dispersant) 10% aqueous solution 5 parts, polyvinyl alcohol (NM11Q, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) A composition comprising 50 parts of a 10% aqueous solution, 14 parts of a styrene-butadiene latex (solid content concentration 50%) and 100 parts of water was mixed and stirred to prepare a coating liquid for undercoat layer.

(Preparation of Thermosensitive Recording Material) Basis Weight 60 g / m^Two
Coating solution for undercoat layer and thermosensitive coloring layer on high quality paper (neutral paper)
The coating amount after drying the coating liquid for the protective layer and the coating liquid for the protective layer is
10g / m each^Two, 7 g / m ^Two3 g / m^TwoSo that
Sequential coating and drying to undercoat layer, thermosensitive coloring layer and protective layer
To prepare a heat-sensitive recording material. In addition, each layer was provided.
After that, super calendering is applied, and the beck on the protective layer side
The smoothness (JIS P 8119) is 1.2 × 10 3 seconds.
It was.

Example 24 In the preparation of the coating solution for the thermosensitive color developing layer of Example 23, 80 parts of the following leuco dye-containing composite fine particle dispersion liquid and 100 parts of the color former dispersion liquid were used instead of 20 parts of the leuco dye dispersion liquid. 30 parts sensitizer dispersion, 40 parts storability improver dispersion, 10 parts 50% light calcium carbonate dispersion, 2 parts zinc stearate
20% of 1% aqueous dispersion (Z-7, manufactured by Chukyo Yushi Co., Ltd.),
A thermosensitive recording material capable of forming multicolor was prepared in the same manner as in Example 23, except that a composition comprising 40 parts of a 10% aqueous solution of polyvinyl alcohol was mixed and stirred to prepare a coating solution for the thermosensitive color developing layer.

(Preparation of Leuco Dye Containing Composite Fine Particle Dispersion) 3- (N-isoamyl-N-ethylamino) -7- (Np-tolylsulfonylaminocarbonyl) ani obtained in Example 2 as a leuco dye Dicyclohexylmethane-4 obtained by heating 8 parts of Rinofluorane to 100 ° C,
Dissolve 4'-diisocyanate in 24 parts and add 2 parts of this solution.
After cooling to 5 ° C, gradually added to 100 parts of an 8% aqueous solution of polyvinyl alcohol (Gosenol GM-14L, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) at the same temperature, TK homomixer (model HV-M, special machine). Using Industrial Co., Ltd., the mixture was emulsified and dispersed by stirring at a rotation speed of 5000 rpm, and 28 parts of water was added to this emulsion dispersion for homogenization. This emulsified dispersion is heated to 80 ° C. and cured for 10 hours to give a leuco dye-containing composite fine particle dispersion having an average particle diameter of 1.1 μm (so that the solid content concentration becomes 25% after the reaction. Water was added).

Example 25 The procedure of Example 23 was repeated except that 80 parts of the following leuco dye-containing microcapsule dispersion was used instead of 80 parts of the leuco dye-containing composite fine particle dispersion. A thermal recording material was prepared in the same manner as in Example 23.

(Preparation of Leuco Dye-Encapsulating Microcapsules) 3- (N-isoamyl-N-ethylamino) -7- (Np-tolylsulfonylaminocarbonyl) anilinoflu obtained as a leuco dye in Example 2 After dissolving 8 parts of orane in 18 parts of mono (di) isopropylnaphthalene heated to 100 ° C., dicyclohexylmethane-4,
6 parts of 4'-diisocyanate was added, and this solution was gradually added to 100 parts of an 8% aqueous solution of polyvinyl alcohol (trade name: Gohsenol GM-14L manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and a TK homomixer (model HV-M, special Using Kika Kogyo Co., Ltd., the mixture was emulsified and dispersed by stirring at a rotation speed of 5000 rpm, and then 20 parts of water was added to this emulsion for homogenization. This emulsified dispersion is heated to 80 ° C. and allowed to undergo a curing reaction for 10 hours to obtain a dispersion of leuco dye-encapsulated microcapsules having an average particle size of 1.2 μm (so that the solid content concentration becomes 25% after the reaction. To which water was added).

Example 26 In the preparation of the leuco dye dispersion of Example 23, 3-
(N-isoamyl-N-ethylamino) -7- (Np
-Tolylsulfonylaminocarbonyl) anilinofluorane 3-di (n-amyl) amino-6-methyl-7- (Np-tolylsulfonylaminocarbonyl) anilinofluorane obtained in Example 1 A thermal recording material was prepared in the same manner as in Example 23 except that was used.

Example 27 In the preparation of the leuco dye dispersion of Example 23, 3-
(N-isoamyl-N-ethylamino) -7- (Np
The 3-di (n-amyl) amino-6-methyl-7- [N- (phenylaminocarbonyl) anilino] fluorane obtained in Example 6 was used instead of -tolylsulfonylaminocarbonyl) anilinofluorane. A thermal recording material was produced in the same manner as in Example 23 except for the above.

Example 28 In the preparation of the leuco dye dispersion of Example 23, 3-
(N-isoamyl-N-ethylamino) -7- (Np
-(N-isoamyl-N-ethylamino) -7- [N- (phenylaminocarbonyl) anilino] fluorane obtained in Example 7 was used in place of -tolylsulfonylaminocarbonyl) anilinofluorane. A thermal recording material was prepared in the same manner as in Example 23.

Example 29 A thermosensitive recording material was prepared in the same manner as in Example 23 except that the coloring agent dispersion liquid was not used in the preparation of the coating liquid for the thermosensitive coloring layer of Example 23.

Example 30 In the preparation of the leuco dye dispersion of Example 23, 3-
(N-isoamyl-N-ethylamino) -7- (Np
-Tolylsulfonylaminocarbonyl) anilinofluorane was replaced by 3-diethylamino-7- (N-benzyl-N-phenylaminocarbonylamino) -benzo (a) fluorane obtained in Example 14.
A thermal recording material was prepared in the same manner as in Example 23.

Example 31 In the preparation of the leuco dye dispersion of Example 23, 3-
(N-isoamyl-N-ethylamino) -7- (Np
-Toluylsulfonylaminocarbonyl) anilinofluorane was replaced by 3-diethylamino-7- (N-benzyl-N-p-tolylsulfonylaminocarbonylamino) -benzo (a) fluorane obtained in Example 15. A thermal recording material was produced in the same manner as in Example 23 except for the above.

Reference Example 1 In the preparation of the leuco dye dispersion of Example 23, 3-
(N-isoamyl-N-ethylamino) -7- (Np
-Tolylsulfonylaminocarbonyl) anilinofluorane was replaced with 3- (N-isoamyl-N-ethylamino) -6-methyl-7-anilinofluorane in the same manner as in Example 23. A recording material was prepared.

With respect to the obtained thermal recording material, a thermal facsimile machine (model: HIFAX-) modified for testing was used.
45, manufactured by Hitachi Ltd.), 1 line recording time 5 m
128 line solid recording (low temperature recording part) under the conditions of sec, scanning line density 8 lines / mm, applied energy per dot 0.8 mJ, and 1 line recording time 5 mse
Solid recording (high temperature recording portion) of 128 lines under the conditions of c, scanning line density of 8 lines / mm and applied energy per dot of 2.4 mJ is shown in Table 1.

Further, in order to evaluate the chemical resistance, a vinyl chloride film was overlaid on the heat-sensitive recording paper after recording and left in an atmosphere of 40 ° C. for 100 hours (plasticizer resistance). The state and the fading condition of the recorded image were visually evaluated, and the results are shown in Table 1.

[Evaluation Criteria] A: Excellent. ◯: Excellent.

[0094]

[Table 1]

[0095]

INDUSTRIAL APPLICABILITY The fluoran compound of the present invention is industrially useful as a leuco dye for recording materials because it is easy to produce and has excellent color developability and storability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B41M 5/30 C07D 493/10 E C07D 493/10 B41M 5/18 105 F term (reference) 2H026 AA07 BB14 4C071 AA04 AA07 BB01 CC12 DD19 EE05 FF17 HH09 JJ01 KK11 LL05 4G069 AA06 BA21A BA21B BE13A BE13B BE21A BE21B BE36A BE36B BE37B CB25 DA02 FA01 4H056 BA02 BB05 BB14 BD03 BF02F BF26E BF26E BF26E BF26E BF26E BF26E

Claims (5)

[Claims] 1. A fluoran compound represented by the general formula (1) or the general formula (2). [Chemical 1] [Chemical 2] [In the general formulas (1) and (2), R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms. Represents a group or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. R ₁ and R
₂ may form a pyrrolidino group or a piperidino group together with the adjacent nitrogen atom. R ₃ represents a hydrogen atom, a halogen atom or a methyl group. R ₄ is a phenyl group which may be substituted with at least one group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a trichloromethyl group and a trifluoromethyl group, and 1 to 12 carbon atoms.
Represents an alkyl group or a benzyl group. R ₅ is an alkyl group having 1 to 20 carbon atoms, or a phenyl group which may be substituted with at least one group selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms, a phenylsulfonyl group, a naphthyl group or a naphthyl group. Represents a sulfonyl group. ] 2. A recording material comprising the fluoran compound according to claim 1. 3. A thermosensitive recording material comprising a thermosensitive coloring layer containing the fluorane compound according to claim 1 on a support. 4. The thermosensitive recording material according to claim 3, wherein the thermosensitive coloring layer contains a color former. 5. When the fluoran compound according to claim 1 is produced, the compound represented by the general formula (3) is used in the presence of the compound represented by the general formula (3) and a hindered phenolic compound as a catalyst. The method for producing a fluorane compound according to claim 1, wherein the fluorane compound represented by 4) or (5) is reacted with the organic compound having an isocyanate group represented by the general formula (6). [Chemical 3] [In the general formula (3), R _{1 to} R ₄ each represent a hydrogen atom or an optionally branched alkyl group having 1 to 5 carbon atoms. ] [Chemical 4] [Chemical 5] [In the general formulas (4) and (5), R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms. Represents a group or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms. R ₁ and R
₂ may form a pyrrolidino group or a piperidino group together with the adjacent nitrogen atom. R ₃ represents a hydrogen atom, a halogen atom or a methyl group. R ₄ is a phenyl group which may be substituted with at least one group selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a trichloromethyl group and a trifluoromethyl group, and 1 to 12 carbon atoms.
Represents an alkyl group or a benzyl group. ] [Chemical 6] [In the general formula (6), R ₅ is an alkyl group having 1 to 20 carbon atoms, or a phenyl group which may be substituted with at least one group selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms, It represents a phenylsulfonyl group, a naphthyl group or a naphthylsulfonyl group. ]