JP2000159769A - Pyrrolo[1,2-a]pyrimidine and thermosensitive recording material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject pyrrolo[1,2-a]pyrimidine that is useful as a coupler giving good cyanic hue with sufficient color density, particularly useful as a cyan chromogenic diazo thermosensitive recording material. SOLUTION: This compound is represented by formula I (R1 and R2 are each H, a halogen, an aryl, an alkyl, cyano, acyl, carbamoyl or the like; R3 is an electron-attractive group having a Hammett's substituent constant σp of >=0.20), typically 2-(4-chlorophenyl)-3-(2,6-di-t-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6-acetyl-pyrrolo[1,2-a]pyrimidine. The compound of formula I is prepared by reaction of an amino group-bearing pyrrolo[1,2- a]pyrimidine of formula II with a compound of the formula: R3-X (X is a halogen).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to pyrrolo [1,2-a] pyrimidine compounds useful as couplers in photographic materials and heat-sensitive recording materials. Further, the present invention relates to a heat-sensitive recording material using a diazonium salt compound and the above-mentioned coupler as color-forming components.

[0002]

2. Description of the Related Art Along with the high performance of a heat-sensitive recording material, it has a cyan coloring property, gives a good hue and a sufficient coloring density, and has a long shelf life of a recording material, preservability of an image,
There is a strong demand for a thermosensitive recording material having improved image fixing properties. A diazonium salt compound is a compound having a very high chemical activity, easily reacts with a compound called a coupler such as a phenol derivative or a compound having an active methylene group to form an azo dye, and also has photosensitivity. Decomposes by light irradiation and loses its activity. For this reason, diazonium salt compounds have long been used as optical recording materials typified by diazocopy ("Photographic Engineering Fundamentals-Non-Silver Salt Photographs", edited by The Photographic Society of Japan, Corona Co., Ltd. (1982)).
89-117, 182-201).

Further, by utilizing the property of decomposing by light and losing activity, it has recently been applied to recording materials requiring fixing of an image. As a typical example, a diazonium salt compound and a coupler are used in accordance with an image signal. A photo-fixing type thermosensitive recording material has been proposed in which an image is formed by heating and reacting to form an image, and then irradiating with light to fix the image (Koji Sato, et al., Journal of the Institute of Image Electronics Engineers of Japan, Vol. 11, No. 4, (1982)). 290-2
96 pages).

However, in these recording materials using a diazonium salt compound as a color-forming element, the activity of the diazonium salt compound is extremely high, and even in a dark place, the diazonium salt compound gradually decomposes and loses reactivity. Therefore, there is a disadvantage that the shelf life as a recording material is short. As a means for improving this disadvantage, there is a method of encapsulating a diazonium salt compound in microcapsules. According to this method, the diazonium salt compound is
It can be isolated from substances that promote decomposition such as water and bases, and the shelf life as a recording material can be dramatically improved (Masamasa Usami et al. Journal of the Institute of Electrophotographic Photography Vol. 26, No. 2) No. (1987) 115-1
25).

[0005] When the microcapsules have a glass transition temperature like a urea resin or a urethane resin and have walls whose glass transition temperature is slightly higher than room temperature, the capsule walls at room temperature have a material impermeability. On the other hand, it shows substance permeability above the glass transition temperature, so that it is called a thermoresponsive microcapsule and is useful for a thermosensitive recording material. That is, by preparing a recording material on which a thermoresponsive microcapsule containing a diazonium salt compound and a thermosensitive recording layer containing a coupler and a base are coated on a support, the diazonium salt compound is stably held for a long period of time. In addition to being able to form a color image easily by heating, it has become possible to fix the image by light irradiation. As described above, the stability of a diazonium salt compound can be significantly improved by microencapsulation.

When 2-hydroxy-3-naphthoic acid anilides are used as couplers, they exhibit particularly excellent performance as color-forming materials for thermal recording, and are subjected to a coupling reaction with a 4-substituted amino-2-alkoxybenzenediazonium salt compound. In this case, it is known that a blue dye is produced (Japanese Patent Application Laid-Open No. H2-225082).

However, when a diazonium salt compound having λ _max on the longer wavelength side is used as the diazonium salt compound, there is a disadvantage that the raw preservability of the recording material (the background coloring during pre-copy preservation) is reduced. . Further, for a diazonium salt compound having λ _max on the shorter wavelength side, the use of the aforementioned 2-hydroxy-3-naphthoic anilides impairs the fixability of an image upon light irradiation, and In terms of hue, there is a drawback that the wave length is increased to a cyan color, and further, the preservability (light fastness) of a color image is not sufficient.

Thus, it has cyan coloring property and
Gives good hue and sufficient color density, shelf life,
At present, a heat-sensitive recording material satisfying image storability and image fixability has not yet been obtained.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and is a pyrrolo [1,2-a] pyrimidine useful as a coupler which gives a good cyan hue and a sufficient color density. It is intended to provide a compound. Further, the present invention provides a novel cyan coloring type diazo thermosensitive recording material containing the above-mentioned coupler and a diazonium salt compound and having excellent shelf life, image light fastness and image fixability in addition to the above-mentioned properties. The purpose is to do.

[0010]

Means for Solving the Problems As a result of intensive studies on couplers, the present inventors have found that novel pyrrolo [1,2-a] pyrimidine compounds represented by the following general formulas (1) and (2). Has been found to be useful as a coupler that provides good cyan hue and sufficient color density. Furthermore, a heat-sensitive recording material using the above pyrrolo [1,2-a] pyrimidine compound and the following diazonium salt compound has improved shelf life, image light fastness, image fixability, and excellent cyan coloring. And completed the present invention.

That is, the present invention provides <1> a pyrrolo [1,2-a] pyrimidine compound represented by the following general formula (1).

[0012]

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(In the general formula (1), R ¹ and R ² are each a hydrogen atom, a halogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, R ³ represents an alkylsulfonyl group or an arylsulfonyl group.
Represents an electron-withdrawing group having a Hammett's substituent constant σ _P value of 0.20 or more. <2> A pyrrolo [1,2-a] pyrimidine compound represented by the following general formula (2).

[0014]

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(In the general formula (2), R ¹ and R ² are each a hydrogen atom, a halogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, X represents an alkylsulfonyl group or an arylsulfonyl group.
Represents CO or SO ₂ . <3> In a heat-sensitive recording material provided on a support with a heat-sensitive recording layer containing a diazonium salt compound and a coupler that reacts with the diazonium salt compound when heated, the above-mentioned <1> is used as the coupler. And a pyrrolo [1,2-a] pyrimidine compound represented by the general formula (2) described in the above <2>.
2-a] at least one selected from pyrimidine compounds
A heat-sensitive recording material comprising a seed. <4> Maximum absorption wavelength λ of the diazonium salt compound
The thermosensitive recording material according to <3>, wherein _max is 450 nm or less. <5> The thermosensitive recording material according to <3> or <4>, wherein the diazonium salt compound is at least one of the following general formulas (3) to (5).

[0016]

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(In the general formula (3), Ar represents a substituted or unsubstituted aryl group, and R ¹¹ and R ¹² represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, respectively. R ¹¹ and R ¹² may be the same or different, and X ⁻ represents an acid anion.)

[0018]

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(In the general formula (4), R ¹⁴ , R ¹⁵ and R
¹⁶ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, respectively. R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different. Y
Represents a hydrogen atom or an —OR ¹³ group. R ¹³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ^- represents an acid anion. )

[0020]

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(In the general formula (5), R ¹⁷ and R ¹⁸ each represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ⁻ represents an acid anion.) > The thermosensitive recording material according to any one of <3> to <5>, wherein the diazonium salt compound is encapsulated in microcapsules. <7> The thermosensitive recording material according to <6>, wherein the capsule wall of the microcapsule is a capsule wall containing polyurethane and / or polyurea as a constituent.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the pyrrolo [1,2-) of the present invention will be described.
a] The pyrimidine compound will be described in detail. When the pyrrolo [1,2-a] pyrimidine compound of the present invention is coupled with a diazonium salt compound as a coupler, it gives a cyan-based good hue with little yellow absorption and a sufficient color-forming density and improves light resistance. In particular, light resistance is excellent even under severe conditions, and the coloring of the background portion is significantly reduced. Specifically, it is a novel compound represented by the general formulas (1) and (2). In the general formulas (1) and (2), R ¹ and R ² are each a hydrogen atom, a halogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl Group, an alkylsulfonyl group, or an arylsulfonyl group. R ³ represents an electron-withdrawing group having a Hammett's substituent constant σ _P value of 0.20 or more. X
Represents CO or SO ₂ .

[0023] Among them, as the substituent represented by R ¹ and R ^2, at least one of Hammett substituent values of group constant sigma _P of 0.20 or more electron-withdrawing group of R ¹ and R ² It is more preferable that at least one of R ¹ and R ² is an electron-withdrawing group having a value of σ _P of 0.35 or more. Among the electron-withdrawing groups having a value of σ _P of 0.20 or more, a cyano group (σ _P value of 0.66), a perfluoroalkyl group (for example, a trifluoromethyl group σ _P value of 0.54), an acyl group ( For example, the acetyl group σ _P
Value 0.50, benzoyl group σ _P value 0.43), carbamoyl group (σ _P value 0.36), alkoxycarbonyl group (eg, ethoxycarbonyl group σ _P value 0.45) and the like. However, the present invention is not limited to these. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom and a chlorine atom are more preferable.

Hammett's substituent constant σ _P represented by R ³
Is 0.20 or more as an electron-withdrawing group, an aryl group,
Preferred are, but not limited to, cyano, acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, alkylphosphoryl, arylphosphoryl, perfluoroalkyl, and the like. Not something.

Among the substituents of R ^{1 to} R ³ , the aryl group further includes an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amino group, Substituted oxycarbamoyl, substituted oxysulfonyl, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, aryl, hydroxy, acyl, acyloxy, substituted sulfonyloxy, substituted aminocarbonyloxy, substituted phosphoryloxy It may be substituted with a group or the like.

When R ¹ and R ² represent an aryl group,
The aryl group is preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a 2-methylphenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group,
2-ethoxyphenyl group, 2-propoxyphenyl group,
2-isopropoxyphenyl group, 2-butoxyphenyl group, 2- (2-ethylhexyloxy) phenyl group, 2
-Octyloxyphenyl group, 2-undecyloxyphenyl group, 2-trifluoromethylphenyl group, 2-
(2-ethylhexyloxy) -5-chlorophenyl group, 2- (2-ethylhexyloxy) -3,5-dichlorophenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 2- (dibutyl (Aminocarbonylethoxy) phenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-nitrophenyl group, 3-cyanophenyl group, 3- Trifluoromethylphenyl group, 3-methoxyphenyl group, 3-ethoxyphenyl group, 3-butoxyphenyl group, 3- (2
-Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3,4-
Dimethoxyphenyl group, 3,5-dibutoxyphenyl group, 3-octyloxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 3- (di-2-
Ethylhexylaminocarbonylmethoxy) phenyl group, 3-dodecyloxyphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group,
4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4-isopentyloxyphenyl Group, 4- (octadecyloxy) phenyl group, 4-benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2
-Ethylhexyloxycarbonyl) phenyl group, 4-
t-octylphenyl group, 4-fluorophenyl group, 3
-Acetylphenyl group, 2-acetylaminophenyl group, 2,4-di-t-pentylphenyl group, 4- (2-
Ethylhexyloxy) carbonylphenyl group, 4-methylthiophenyl group, 4- (4-chlorophenylthio)
In addition to a phenyl group, a hydroxyphenyl group, a phenylsulfonylphenyl group, a phenylsulfonyloxyphenyl group, a phenylcarbonyloxyphenyl group, a dimethylaminocarbonyloxyphenyl group, a butylcarbonyloxyphenyl group, and the like can be mentioned.

When R ³ represents an aryl group, the aryl group is preferably an aryl group having 6 to 30 carbon atoms, such as 3-nitrophenyl group, 4-nitrophenyl group, 4-cyanophenyl group, -Trifluoromethylphenyl group, 4-methylsulfonylphenyl group, 4-ethylsulfonylphenyl group, 4-octylsulfonylphenyl group, 4-phenylsulfonylphenyl group, pentafluorophenyl group, pentachlorophenyl group, and the like.

Among the substituents of R ¹ and R ² , the alkyl group may be linear or branched, and may have an unsaturated bond. Further, these alkyl groups may be substituted with an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, a halogen atom, or the like. The aryl group may be further substituted with an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxy group, or a halogen atom. When R ¹ and R ² represent an alkyl group, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, a trifluoromethyl group, an ethyl group, a butyl group, a hexyl group, and octyl. Group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, propyl group, isopropyl group, isobutyl group, se
c-butyl group, t-butyl group, pentyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, isopentyl group, heptyl group, nonyl group, undecyl group,
Propenyl group, heptadecenyl group, t-octyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, 1
-(Ethoxycarbonyl) ethyl group, 2 ', 4'-diisopentylphenyloxymethyl group, 2', 4'-di-
t-butylphenyloxymethyl group, ethoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, butyldecyloxycarbonylethyl group, dibutylaminocarbonylmethyl group, dibenzylaminocarbonylethyl group, ethyloxycarbonylpropyl group, 2
-Ethylhexyloxycarbonylpropyl group, 2,4
-Di-t-amylphenyloxypropyl group, 1-
(2 ′, 4′-di-t-amylphenyloxy) propyl group, 2,4-di-t-butylphenyloxypropyl group, acetylaminoethyl group, N, N-dihexylaminocarbonylethyl group, 2,4 -Di-t-amyloxyethyloxycarbonylpropyl group, isostearyloxycarbonylpropyl group, 1- (2,4-di-t-pentylphenyloxy) propyl group, 2,4-di-t-
Examples include a pentylphenyloxyethyloxycarbonylpropyl group, a naphthyloxyethyloxycarbonylethyl group, an N-methyl-N-phenylethyloxycarbonylethyl group, a methanesulfonylaminopropyl group, and the like.

Among the substituents of R ^{1 to} R ³ , the acyl group is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl, propanoyl, butanoyl, hexanoyl, octanoyl, octanoyl, 2-amino. Ethylhexanoyl, decanoyl, dodecanoyl, octadecanoyl, 2-cyanopropanoyl, 1,1-dimethylpropanoyl, benzoyl, 2- (2,4-di-t-pentylphenyloxy) Butanoyl group, phenoxyacetyl group and the like.

Among the substituents of R ^{1 to} R ³ , the carbamoyl group means a substituted or unsubstituted carbamoyl group, for example, a carbamoyl group, an N-alkylcarbamoyl group,
-Arylcarbamoyl group, N-acylcarbamoyl group, N-alkoxycarbonylcarbamoyl group, N-aryloxycarbonylcarbamoyl group, N-alkylsulfonylcarbamoyl group, N-arylsulfonylcarbamoyl group, N, N-dialkylcarbamoyl group,
N, N-diarylcarbamoyl group, N-alkyl-N
-Arylcarbamoyl groups and the like. As the substituted carbamoyl group, a substituted carbamoyl group having 1 to 30 carbon atoms is preferable, for example, an N-methylcarbamoyl group,
N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-2-ethylhexylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2
-Methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N-2-methoxyphenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyloxy) phenylcarbamoyl group, N-3 -Chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-
Cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4- (2-ethylhexyloxy) phenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-acetylcarbamoyl group, N-
Benzoylcarbamoyl, N-methoxycarbonylcarbamoyl, N-ethoxycarbonylcarbamoyl, N-butoxycarbonylcarbamoyl, N-phenoxycarbonylcarbamoyl, N-methylsulfonylcarbamoyl, N-ethylsulfonylcarbamoyl, N-isopropylsulfonyl Carbamoyl group, N-
Butylsulfonylcarbamoyl, N-octylsulfonylcarbamoyl, N-phenylsulfonylcarbamoyl, N- (4-methylphenyl) sulfonylcarbamoyl, N- (4-chlorophenyl) sulfonylcarbamoyl, N- (4-methoxyphenyl) Sulfonylcarbamoyl group, N- [4- (2-ethylhexyloxy) phenyl] sulfonylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, N-methyl-
And N-phenylcarbamoyl group.

Among the substituents of R ^{1 to} R ³ , the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group,
Butoxycarbonyl group, hexyloxycarbonyl group,
2-ethylhexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenyloxyethyloxycarbonyl group, phenyloxypropyloxycarbonyl group, 2,4-di-t-amylphenyloxyethylcarbonyl group , 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl group, isostearyloxycarbonyl group and the like.

Among the substituents of R ^{1 to} R ^3, the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 30 carbon atoms, for example, 2-methylphenyloxycarbonyl group, 2-chlorophenyloxycarbonyl Group, 2,6-dimethylphenyloxycarbonyl group, 2,4,6-trimethylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group,
2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 2,2-ethylhexylphenyloxycarbonyl group, 3- (2-ethylhexyloxy) phenyloxycarbonyl group, 4-fluoro Examples thereof include a phenyloxycarbonyl group, a 4-chlorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a 4-butoxyphenyloxycarbonyl group.

Among the substituents of R ^{1 to} R ³ , the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, Butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, decanoylsulfonyl, dodecanoylsulfonyl, octadecanoylsulfonyl, cyanomethylsulfonyl and the like.

Among the substituents of R ^{1 to} R ³ , the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 30 carbon atoms, for example, a phenylsulfonyl group,
1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethyl Phenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-
A (2-ethylhexyloxy) phenylsulfonyl group,
3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-chlorophenylsulfonyl group, 4
-Methylphenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-butoxyphenylsulfonyl group, 4-
A (2-ethylhexyloxy) phenylsulfonyl group,
4-octadecylphenylsulfonyl group and the like.

Among the substituents for R ³ , the alkyl phosphoryl group is preferably an alkyl phosphoryl group having 2 to 40 carbon atoms, for example, a methyl phosphoryl group, an ethyl phosphoryl group, a propyl phosphoryl group, an isopropyl phosphoryl group, a butyl phosphoryl group. Group, isobutyl phosphoryl group, sec-butyl phosphoryl group, t-butyl phosphoryl group, pentyl phosphoryl group, isopentyl phosphoryl group, hexyl phosphoryl group, heptyl phosphoryl group, octyl phosphoryl group, 2-ethylhexyl phosphoryl group, decyl phosphoryl group, dodecyl Phosphoryl group, octadecylphosphoryl group, ethoxycarbonylmethylphosphoryl group, 2-ethylhexyloxycarbonylmethylphosphoryl group, aminocarbonylmethylphosphoryl group,
N, N-dibutylaminocarbonylmethylphosphoryl group, N-methylaminocarbonylmethylphosphoryl group,
N-ethylaminocarbonylmethylphosphoryl group, N-
Examples include an octylaminocarbonylmethylphosphoryl group and a benzylphosphoryl group.

Among the substituents for R ³ , the arylphosphoryl group is preferably an arylphosphoryl group having 12 to 50 carbon atoms.
Naphthyl phosphoryl group, 2-naphthyl phosphoryl group, 2
-Chlorophenylphosphoryl group, 2-methylphenylphosphoryl group, 2-methoxyphenylphosphoryl group, 2-
Butoxyphenyl phosphoryl group, 3-chlorophenyl phosphoryl group, 3-trifluoromethylphenyl phosphoryl group, 3-cyanophenyl phosphoryl group, 3- (2-ethylhexyloxy) phenyl phosphoryl group, 3-nitrophenyl phosphoryl group, 4-fluorophenyl Examples thereof include a phosphoryl group, a 4-cyanophenylphosphoryl group, a 4-butoxyphenylphosphoryl group, a 4- (2-ethylhexyloxy) phenylphosphoryl group, and a 4-octadecylphenylphosphoryl group.

Among the substituents for R ³ , the perfluoroalkyl group is preferably a perfluoroalkyl group having 1 to 20 carbon atoms, for example, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluoro Butyl group and the like.

Among these substituents, the substituent for R ¹ is preferably an alkyl group or an aryl group, and more preferably an aryl group. As the substituent for R ² , a cyano group or an alkoxycarbonyl group is preferable, and an alkoxycarbonyl group is more preferable. As the substituent for R ³ , a carbamoyl group is preferable, and an N-arylsulfonylcarbamoyl group is more preferable.

Hereinafter, typical specific examples of the pyrrolo [1,2-a] pyrimidine compound represented by the general formula (1) or (2) of the present invention will be described. It is not limited. In the table, R ^{1 to} R ³ and X
Represents a symbol in the general formula (1) or the general formula (2).

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

Next, a method for producing the pyrrolo [1,2-a] pyrimidine compound represented by the general formulas (1) and (2) will be described. The compound of the present invention represented by the general formula (1) includes a pyrrolo [1,2-a] pyrimidine compound having an amino group (hereinafter, referred to as “amino form A”) and R ³
It can be obtained by reacting -X (X: halogen) (the following reaction formula (1)).

[0048]

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When R ³ is a carbamoyl group, an isocyanate can be used instead of a halide as a reaction reagent (reaction formula (2) below).

[0050]

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The compound of the present invention represented by the general formula (2) can be obtained by reacting the amino compound A with chlorosulfonyl isocyanate or chlorocarbonyl isocyanate, followed by adding a base and reacting (reaction described below). Equation (3)).

[0052]

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The amount of the halide (R ³ -X) and isocyanate used in the reaction represented by the above reaction formulas (1) and (2) is 1 to 1 equivalent of the amino compound A as a raw material. It is 10 equivalents, preferably 1 to 5 equivalents. Examples of the solvent for dissolving the amino compound A include aromatic hydrocarbons such as benzene, toluene, and xylene; linear or cyclic aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane; diethyl ether; and diisopropyl ether. Ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; nitriles such as acetonitrile; acetates such as methyl acetate and ethyl acetate; Various solvents such as -dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide, or a mixture thereof can be used. The amount of these solvents used is not particularly limited.

As a reaction method, for example, a method in which a halide or isocyanate is added dropwise or dividedly to a solution of the amino compound A can be mentioned. The reaction temperature is usually selected from the range of room temperature to the boiling point of the solvent, but is preferably 2
0-70 ° C. The reaction time depends on the reaction temperature, but is usually about 0.5 to 24 hours.

In this reaction, a catalyst can be added, if necessary, for shortening the reaction time and improving the yield. Examples of the catalyst include a boron catalyst trifluoride diethyl ether complex, a tin catalyst such as dibutyltin diacetate, and aluminum chloride. The amount of the catalyst used is up to about 0.5 equivalents, preferably up to about 0.05 equivalents, per equivalent of the amino compound A. After completion of the reaction, the target substance can be taken out by a normal post-processing operation such as extraction,
Further, if necessary, it can be purified by purification means such as silica gel column chromatography and recrystallization.
When the boiling point of the reaction solvent is low, the extraction can be omitted, and the reaction solution can be concentrated and then purified.

In the first step of the reaction represented by the reaction formula (3), that is, the isocyanate addition reaction, the reaction can be carried out under the same conditions as those shown in the reaction formulas (1) and (2). . The resulting intermediate can be treated with a base without isolation to obtain the desired product (second step). Examples of the base include organic bases such as triethylamine, pyridine and DBU; alkali metal hydrides such as sodium hydride and potassium hydride; metal alcoholates such as sodium methylate, sodium ethylate and potassium butyrate; sodium hydroxide; Alkali metal hydroxides such as potassium, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkali metal carbonates such as sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, sodium formate and sodium acetate Examples thereof include an alkali metal salt of a lower carboxylic acid. Among these, organic bases such as triethylamine and pyridine,
Alkali metal hydrides such as sodium hydride are preferred. The amount of the base used is 1 to 1 equivalent of the amino compound A.
Two equivalents are preferred.

After completion of the reaction, the target substance can be taken out by a usual post-treatment operation such as extraction, and if necessary,
Purification can also be performed by purification means such as silica gel column chromatography and recrystallization. The amino compound A as a raw material can be synthesized by the following method described in Japanese Patent Application No. 10-210029. The aminopyrrole derivative can be synthesized by a method described in Japanese Patent Application No. 9-63619.

[0058]

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Next, the heat-sensitive recording material of the present invention will be described in detail. The heat-sensitive recording material of the present invention has a heat-sensitive recording layer on a support, and further has other layers as necessary. [Thermal Recording Layer] The thermosensitive recording layer contains a coupler and a diazonium salt compound, and further contains other components as necessary.

(Coupler) The coupler contained in the heat-sensitive recording layer is a pyrrolo [1,2-) represented by the above general formula (1).
a] pyrimidine compound, and at least one selected from pyrrolo [1,2-a] pyrimidine compounds represented by the general formula (2), and may be used alone.
Two or more kinds may be used in combination.

The coupler according to the present invention forms a dye by coupling with a diazo compound in a basic atmosphere and / or a neutral atmosphere. The coupler according to the present invention can be used in combination with a known coupler according to various purposes such as hue adjustment. As a coupler to be used in combination,
There are a so-called active methylene compound having a methylene group next to the carbonyl group, a phenol derivative, a naphthol derivative, and the like.

Particularly preferred couplers that can be used in the present invention include resorcin, phloroglucin, 2,3-dihydroxynaphthalene, sodium 2,3-dihydroxynaphthalene-6-sulfonate, and morpholinopropyl 1-hydroxy-2-naphthoate. Amide,
Sodium 2-hydroxy-3-naphthalenesulfonate, 2-hydroxy-3-naphthalenesulfonic acid anilide, 2-hydroxy-3-naphthalenesulfonic acid morpholinopropylamide, 2-hydroxy-3-naphthalenesulfonic acid-2-ethylhexyloxypropyl Amide, 2-hydroxy-3-naphthalenesulfonic acid-2-
Ethylhexylamide, 5-acetamido-1-naphthol, 1-hydroxy-8-acetamidonaphthalene-
Sodium 3,6-disulfonate, 1-hydroxy-8
-Acetamidonaphthalene-3,6-disulfonic acid dianilide, 1,5-dihydroxynaphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-
Hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid anilide, 5,5-dimethyl-
1,3-cyclohexanedione, 1,3-cyclopentanedione, 5- (2-n-tetradecyloxyphenyl) -1,3-cyclohexanedione, 5-phenyl-
4-methoxycarbonyl-1,3-cyclohexanedione, 5- (2,5-di-n-octyloxyphenyl)
-1,3-cyclohexanedione, N, N'-dicyclohexylbarbituric acid, N, N'-di-n-dodecylbarbituric acid, Nn-octyl-N'-n-octadecyl barbituric acid, N- Phenyl-N '-(2,5
-Di-n-octyloxyphenyl) barbituric acid,
N, N'-bis (octadecyloxycarbonylmethyl) barbituric acid, 1-phenyl-3-methyl-5
Pyrazolone, 1- (2,4,6-trichlorophenyl)
-3-anilino-5-pyrazolone, 1- (2,4,6-
Trichlorophenyl) -3-benzamido-5-pyrazolone, 6-hydroxy-4-methyl-3-cyano-1-
(2-ethylhexyl) -2-pyridone, 2,4-bis- (benzoylacetamide) toluene, 1,3-bis- (pivaloylacetoamidomethyl) benzene, benzoylacetonitrile, thenoylacetonitrile, acetoacetanilide, benzoylacetanilide, Pivaloylacetanilide, 2-chloro-5- (Nn-butylsulfamoyl) -1-pivaloylacetamide benzene, 1- (2-ethylhexyloxypropyl) -3-
Cyano-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (dodecyloxypropyl) -3-acetyl-4-methyl-6-hydroxy-
1,2-dihydropyridin-2-one, 1- (4-n-
Octyloxyphenyl) -3-tert-butyl-5
-Aminopyrazole and the like.

For details of the coupler, see JP-A-4-4-2.
01483, JP-A-7-223267, JP-A-7-223
223368, JP-A-7-323660, Japanese Patent Application No. 5
-278608, Japanese Patent Application No. 5-297024, Japanese Patent Application No. 6-18669, Japanese Patent Application No. 6-18670, Japanese Patent Application No. 7
-316280, Japanese Patent Application No.8-027095, Japanese Patent Application No.8-027096, Japanese Patent Application No.8-030799, Japanese Patent Application No.8-12610, Japanese Patent Application No.8-132394, Japanese Patent Application No.8-358755. And Japanese Patent Application Nos. 8-358756 and 9-069990.

The amount of the coupler to be added is 0.1 to 0.1 in the heat-sensitive recording layer.
It is used in the range of 02 to 5 g / m ² , and preferably 0.1 to 4 g / m ² from the viewpoint of the effect. When the addition amount is less than 0.02 g / m ² , the color developing property is 5 g / m ^2.
If it exceeds, both are not preferred from the viewpoint of applicability.

The coupler used in the present invention can be used by adding a water-soluble polymer together with other components and solid-dispersing it by a sand mill or the like, but can also be used as an emulsified product together with a suitable emulsifying aid. . The solid dispersion method and the emulsification method are not particularly limited, and conventionally known methods can be used. Details of these methods are described in JP-A-59-190886, JP-A-2-141279, and JP-A-7-171.
No. 45, it is described.

(Diazonium Salt Compound) The diazonium salt compound used in the present invention has the following general formula: Ar—N ₂ ⁺ X ⁻ (wherein, Ar represents an aromatic moiety and X ⁻ represents an acid anion). The compound is a compound represented by the following formula, which undergoes a coupling reaction with a coupler upon heating to form a color and is decomposed by light. These can control the maximum absorption wavelength depending on the position and type of the substituent in the Ar portion.

Specific examples of the salt-forming diazonium include 4- (p-tolylthio) -2,5-dibutoxybenzenediazonium and 4- (4-chlorophenylthio)-
2,5-dibutoxybenzenediazonium, 4- (N,
N-dimethylamino) benzenediazonium, 4-
(N, N-diethylamino) benzenediazonium, 4
-(N, N-dipropylamino) benzenediazonium, 4- (N-methyl-N-benzylamino) benzenediazonium, 4- (N, N-dibenzylamino) benzenediazonium, 4- (N-ethyl-N -Hydroxyethylamino) benzenediazonium, 4- (N, N-
Diethylamino) -3-methoxybenzenediazonium, 4- (N, N-dimethylamino) -2-methoxybenzenediazonium, 4- (N-benzoylamino)-
2,5-diethoxybenzenediazonium, 4-morpholino-2,5-dibutoxybenzenediazonium, 4-
Anilinobenzenediazonium, 4- [N- (4-methoxybenzoyl) amino] -2.5-diethoxybenzenediazonium, 4-pyrrolidino-3-ethylbenzenediazonium, 4- [N- (1-methyl-2- ( 4-methoxyphenoxy) ethyl) -N-hexylamino]-
2-hexyloxybenzenediazonium, 4- [N-
(2- (4-methoxyphenoxy) ethyl) -N-hexylamino] -2-hexyloxybenzenediazonium, 2- (1-ethylpropyloxy) -4- [di-
(Di-n-butylaminocarbonylmethyl) amino] benzenediazonium, 2-benzylsulfonyl-4-
[N-methyl-N- (2-octanoyloxyethyl)] aminobenzenediazonium and the like.

The maximum absorption wavelength λ _max of the diazonium salt compound used in the present invention is preferably 450 nm or less from the viewpoint of the effect, and more preferably 290 to 440 nm. Diazonium salt compound is in terms of storability and having a lambda _max to the longer wavelength side than the wavelength range, the image fixing property in combination with the coupler to have a lambda _max in the short wavelength side, image storability, cyan forming Neither is preferred in terms of hue. The diazonium salt compound used in the present invention has 12 or more carbon atoms,
It is desirable that the solubility in water is 1% or less and the solubility in ethyl acetate is 5% or more.

Among these diazonium salt compounds,
It is more preferable to use the diazonium salt compounds represented by the general formulas (3) to (5) in terms of the hue of the dye, image storability, and image fixability.

In the general formula (3), Ar represents a substituted or unsubstituted aryl group. As the substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxamide group, a sulfonyl group, a sulfamoyl group, a sulfonamide group, a ureido group, Examples thereof include a halogen group, an amino group, and a heterocyclic group, and these substituents may be further substituted.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, for example, phenyl, 2-methylphenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-butoxy. Phenyl group, 2- (2-ethylhexyloxy) phenyl group, 2
-Octyloxyphenyl group, 3- (2,4-di-t-
Pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 2,4,6
-Trimethylphenyl group, 3-chlorophenyl group, 3-
Methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2-ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3,4 -Dimethoxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group , 4-benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4-
(2-ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-
2,5-butoxyphenyl group, 4- (N-benzyl-N
-Methylamino) -2-dodecyloxycarbonylphenyl group and the like, but are not particularly limited thereto. Further, these groups may be further substituted by an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group and the like.

R ¹¹ and R ¹² each represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ¹¹ and R ¹² may be the same or different. Examples of the substituent include, but are not limited to, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonyl group, a substituted amino group, a substituted amide group, an aryl group, and an aryloxy group.

When R ¹¹ and R ¹² each represent an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, for example, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group,
Cyclohexyl group, octyl group, t-octyl group, 2-
Ethylhexyl group, nonyl group, octadecyl group, benzyl group, 4-methoxybenzyl group, triphenylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, 2 ′, 4′-diisopentyl Phenyloxymethyl group, 2 ′, 4′-di-t-butylphenyloxymethyl group, dibenzylaminocarbonylmethyl group, 2,4-di-t-amylphenyloxypropyl group, ethoxycarbonylpropyl group, 1- ( 2 ', 4'-di-t-amylphenyloxy) propyl group, acetylaminoethyl group, 2- (N, N-dimethylamino) ethyl group, 2-
(N, N-diethylamino) propyl group, methanesulfonylaminopropyl group, acetylaminoethyl group, 2-
(N, N-dimethylamino) ethyl group, 2- (N, N-
And a diethylamino) propyl group.

When R ¹¹ and R ¹² each represent an aryl group, the aryl group has 6 to 3 carbon atoms.
An aryl group of 0 is preferable, for example, a phenyl group, 2-
Methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t- Pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group, 2,
5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2-ethylhexyl) An oxy) phenyl group, a 3,4-dichlorophenyl group,
3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4
-Benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3- Acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5-butoxyphenyl group, 4- (N-benzyl-N-methyl Amino) -2-dodecyloxycarbonylphenyl group, and the like, but are not particularly limited thereto. Further, these groups may be further substituted by an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group and the like.

In the general formula (4), R¹⁴, R¹⁵And R
¹⁶Is a substituted or unsubstituted alkyl group, or
Represents a substituted or unsubstituted aryl group. R¹⁴, R¹⁵Passing
And R ¹⁶May be the same or different. Place
Examples of the substituent include an alkyl group, an alkoxy group and an alkyl group.
O group, aryl group, aryloxy group, arylthio
Group, acyl group, alkoxycarbonyl group, carbamoyl
Group, carboamide group, sulfonyl group, sulfamoyl
Group, sulfonamide group, ureido group, halogen atom,
Examples include a mino group and a heterocyclic group.

When R ¹⁴ , R ¹⁵ and R ¹⁶ each represent an alkyl group, the alkyl group has 1 to 1 carbon atoms.
And an alkyl group of 8 is preferable, for example, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a t-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, and a hexyl group A cyclohexyl group, an octyl group, a t-octyl group,
2-ethylhexyl, nonyl, octadecyl, benzyl, 4-methoxybenzyl, triphenylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl, 2 ', 4'-di Isopentylphenyloxymethyl group, 2 ′, 4′-di-t-butylphenyloxymethyl group, dibenzylaminocarbonylmethyl group, 2,4-
Di-t-amylphenyloxypropyl group, ethoxycarbonylpropyl group, 1- (2 ′, 4′-di-t-amylphenyloxy) propyl group, acetylaminoethyl group, 2- (N, N-dimethylamino) Ethyl group, 2-
(N, N-diethylamino) propyl group, methanesulfonylaminopropyl group, acetylaminoethyl group, 2-
(N, N-dimethylamino) ethyl group, 2- (N, N-
Diethylamino) propyl group, 1-methyl-2- (4-
(Methoxyphenoxy) ethyl group, di-n-butylaminocarbonylmethyl group, di-n-octylaminocarbonylmethyl group and the like.

When R ¹⁴ , R ¹⁵ and R ¹⁶ each represent an aryl group, the aryl group is preferably an aryl group having 6 to 30 carbon atoms, for example, phenyl, 2-methylphenyl, 2-chlorophenyl group, 2
-Methoxyphenyl group, 2-butoxyphenyl group, 2-
(2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group, 2,5-dichlorophenyl group, 2,4,4 6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2-ethylhexyloxy) phenyl group, 3,4- Dichlorophenyl group, 3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxy Phenyl group, 4- (2-ethylhexyloxy) phenyl group, 4-benzylphenyi Group, 4-aminosulfonylphenyl group, 4-N, N-dibutyl-aminosulfonylphenyl group, 4-ethoxycarbonyl phenyl group, 4- (2
-Ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3-acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5 −
Examples thereof include a butoxyphenyl group and a 4- (N-benzyl-N-methylamino) -2-dodecyloxycarbonylphenyl group, but are not particularly limited thereto. Further, these groups may be further substituted by an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group and the like.

In the general formula (4), Y represents a hydrogen atom or —O
Represents an R ¹³ group. In the —OR ¹³ group, R ¹³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As the substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxamide group, a sulfonyl group,
Examples include a sulfamoyl group, a sulfonamide group, a ureido group, a halogen atom, an amino group, and a heterocyclic group. From the viewpoint of hue adjustment, Y is preferably a hydrogen atom or an alkyloxy group in which R ¹³ is an alkyl group.

When R ¹³ in the —OR ¹³ group represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, for example, a methyl group, a trifluoromethyl group, an ethyl group, a propyl group , Isopropyl group,
Butyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group,
Cyclohexyl group, octyl group, t-octyl group, 2-
Ethylhexyl group, nonyl group, octadecyl group, benzyl group, 4-methoxybenzyl group, triphenylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, 2 ′, 4′-diisopentyl Phenyloxymethyl group, 2 ′, 4′-di-t-butylphenyloxymethyl group, dibenzylaminocarbonylmethyl group, 2,4-di-t-amylphenyloxypropyl group, ethoxycarbonylpropyl group, 1- ( 2 ', 4'-di-t-amylphenyloxy) propyl group, acetylaminoethyl group, 2- (N, N-dimethylamino) ethyl group, 2-
(N, N-diethylamino) propyl group, methanesulfonylaminopropyl group, acetylaminoethyl group, 2-
(N, N-dimethylamino) ethyl group, 2- (N, N-
And a diethylamino) propyl group.

Further, when R ¹³ in the —OR ¹³ group represents an aryl group, the aryl group has from 6 to 7 carbon atoms.
30 aryl groups are preferred, for example a phenyl group, 2
-Methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2-
An ethylhexyloxy) phenyl group, a 2-octyloxyphenyl group, a 3- (2,4-di-t-pentylphenoxyethoxy) phenyl group, a 4-chlorophenyl group,
2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2 -Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group,
3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4
-Benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3- Acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5-butoxyphenyl group, 4- (N-benzyl-N-methyl Amino) -2-dodecyloxycarbonylphenyl group and the like, but are not particularly limited thereto. Further, these groups may be further substituted by an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group and the like.

In the general formula (5), R ¹⁷ and R ¹⁸ are
Each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ¹⁷ and R ¹⁸ may be the same or different. As the substituent, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxamide group, a sulfonyl group, a sulfamoyl group, a sulfonamide group, a ureido group, Examples include a halogen atom, an amino group, and a heterocyclic group.

When R ¹⁷ and R ¹⁸ each represent an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, for example, methyl, trifluoromethyl, ethyl, propyl, isopropyl Group, butyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, t-octyl group, 2-ethylhexyl group, nonyl group, octadecyl group, benzyl Group,
4-methoxybenzyl group, triphenylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group,
2 ′, 4′-diisopentylphenyloxymethyl group,
2 ′, 4′-di-t-butylphenyloxymethyl group,
Dibenzylaminocarbonylmethyl group, 2,4-di-t
-Amylphenyloxypropyl group, ethoxycarbonylpropyl group, 1- (2 ', 4'-di-t-amylphenyloxy) propyl group, acetylaminoethyl group,
-(N, N-dimethylamino) ethyl group, 2- (N, N
-Diethylamino) propyl group, methanesulfonylaminopropyl group, acetylaminoethyl group, 2- (N, N
-Dimethylamino) ethyl group, 2- (N, N-diethylamino) propyl group and the like, but are not particularly limited thereto.

When R ¹⁷ and R ¹⁸ each represent an aryl group, the aryl group has 6 to 3 carbon atoms.
An aryl group of 0 is preferable, for example, a phenyl group, 2-
Methylphenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-butoxyphenyl group, 2- (2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 3- (2,4-di-t- Pentylphenoxyethoxy) phenyl group, 4-chlorophenyl group, 2,
5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-butoxyphenyl group, 3-cyanophenyl group, 3- (2- Ethylhexyloxy) phenyl group, 3,4-dichlorophenyl group,
3,5-dichlorophenyl group, 3,4-dimethoxyphenyl group, 3- (dibutylaminocarbonylmethoxy) phenyl group, 4-cyanophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4
-Benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylaminosulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexylcarbonyl) phenyl group, 4-fluorophenyl group, 3- Acetylphenyl group, 2-acetylaminophenyl group, 4- (4-chlorophenylthio) phenyl group, 4- (4-methylphenyl) thio-2,5-butoxyphenyl group, 4- (N-benzyl-N-methyl Amino) -2-dodecyloxycarbonylphenyl group and the like. Further, these groups may be further substituted by an alkyloxy group, an alkylthio group, a substituted phenyl group, a cyano group, a substituted amino group, a halogen atom, a heterocyclic group and the like.

In the general formulas (3) to (5), X ^- is
Represents an acid anion, wherein the acid anion has 1 carbon atom
To 9 polyfluoroalkylcarboxylic acids, 1 carbon atom
To 9, polyfluoroalkylsulfonic acid, boron tetrafluoride, tetraphenylboron, hexafluorophosphoric acid, aromatic carboxylic acid, aromatic sulfonic acid and the like. Hexafluorophosphoric acid is preferred in terms of crystallinity.

Hereinafter, specific examples of the diazonium salt compounds represented by the general formulas (3) to (5) are shown, but the present invention is not limited thereto.

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In the present invention, the diazonium salt compounds represented by the general formulas (3) to (5) may be used alone or in combination of two or more. Further, the diazonium salt compounds represented by the general formulas (3) to (5) may be used in combination with an existing diazonium salt compound according to various purposes such as hue adjustment.

The diazonium salt compound used in the present invention is preferably contained in the heat-sensitive recording layer in an amount of 0.02 to 3 g / m ² , more preferably 0.1 to ² g / m ² .

The diazonium salt compound used in the present invention is preferably encapsulated in microcapsules from the viewpoint of storage stability. The method of microencapsulation is not particularly limited, and microencapsulation can be performed by a conventionally known method using a wall material such as gelatin, polyurea, polyurethane, polyimide, polyester, polycarbonate, and melamine. Among these wall materials, polyurethane and polyurea are preferred from the viewpoints of color developability and storage stability. Details of the microencapsulation method are described in JP-A-2-141279 and the like. In microencapsulation, a high-boiling organic solvent may be used as a dispersion solvent for the diazonium salt compound. The organic solvent is not particularly limited, and conventionally known ones such as alkyl phthalate, phosphate, citrate, benzoate, alkylamide, aliphatic ester and trimesate can be used. . For details, see JP-A-7-
No. 17145, for example.

(Other Components) In the present invention, tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines, morpholines and the like are used for the purpose of accelerating the coupling reaction. It is preferable to use an organic base of

Specific examples of these organic bases include N,
N′-bis (3-phenoxy-2-hydroxypropyl) piperazine, N, N′-bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine,
N, N'-bis [3- (p-methoxyphenoxy) -2
-Hydroxypropyl] piperazine, N, N'-bis (3-phenylthio-2-hydroxypropyl) piperazine, N, N'-bis [3- (β-naphthoxy) -2-
Hydroxypropyl] piperazine, N-3- (β-naphthoxy) -2-hydroxypropyl-N′-methylpiperazine, 1,4-bis {[3- (N-methylpiperazino) -2-hydroxy] propyloxy} benzene and the like Piperazines, N- [3- (β-naphthoxy) -2-hydroxy] propylmorpholine, 1,4-bis [(3-
Morpholines such as morpholino-2-hydroxy) propyloxy] benzene and 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene;
(3-phenoxy-2-hydroxypropyl) piperidines such as piperidine and N-dodecylpiperidine, triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine, 2-hydroxybenzoic acid 2-N-methyl-N-benzylaminoethyl ester 4-Hydroxybenzoic acid 2-N, N-di-n-butylaminoethyl ester, 4- (3-N, N-dibutylaminopropoxy) benzenesulfonamide, 4-
(2-N, N-dibutylaminoethoxycarbonyl) phenoxyacetic acid amide and the like. These are described in detail in JP-A-57-123086 and JP-A-60-23086.
-49991, JP-A-60-94381,
Japanese Patent Application No. 7-228731, Japanese Patent Application No. 7-23515
No. 7, Japanese Patent Application No. 7-235158, and the like. These organic bases can be used alone or in combination of two or more. The amount of the organic base used in the present invention is not particularly limited, but is preferably in the range of 1 to 30 mol per 1 mol of the diazonium salt compound.

In the present invention, in addition to the pyrrolo [1,2-a] pyrimidine compounds represented by the general formulas (1) and (2), a color-forming aid is used for the purpose of accelerating the color-forming reaction. Can be added. As these color forming aids,
Examples include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic amide compounds, and sulfonamide compounds. It is thought that these compounds reduce the melting point of the coupler or the basic substance or improve the heat permeability of the microcapsule wall, and as a result, a high color density can be obtained.

(Production method of heat-sensitive recording layer) The heat-sensitive recording layer of the heat-sensitive recording material of the present invention comprises a diazonium salt compound, a pyrrolo [1,2-) represented by the general formula (1) or (2).
a] A coating solution containing a pyrimidine compound and other additives is prepared and coated on a support such as paper or a synthetic resin film by bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, The coating is dried by a coating method such as dip coating or curtain coating to provide a thermosensitive recording layer having a solid content of ^{2 to} 30 g / m ² .

The binder used in the present invention is not particularly limited, and a conventionally known binder such as polyvinyl alcohol, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, and styrene-acrylic acid copolymer may be used. Can be. For details, see JP-A-2-1412.
No. 79, and the like. In addition, various organic or inorganic pigments, various stabilizers, antioxidants, and the like can be added as necessary.

In the heat-sensitive recording material of the present invention, a diazonium salt compound, a pyrrolo [1,2-a] pyrimidine compound represented by the general formula (1) or (2) may be used as described in the above method. They may be included in the same layer, or may be of a stacked type that is included in another layer.

[Support] As the support used in the present invention, a conventionally known support can be used. Specifically, neutral paper, acidic paper, recycled paper, polyolefin resin laminated paper, synthetic paper, polyester film, cellulose derivative film such as cellulose triacetate film, polystyrene film, polyolefin film such as polypropylene film and polyethylene film, etc. These can be used alone or bonded together. The thickness of the support is 20 to 200 μm. It is also possible to provide an intermediate layer between the support and the thermosensitive recording layer. About this,
No. 54980.

[Other Layers and the Like] In the heat-sensitive recording material of the present invention, it is preferable to provide a protective layer on the heat-sensitive recording layer, and it is more preferable to provide a protective layer on the heat-sensitive recording layer. This protective layer is composed of a water-soluble polymer compound, a pigment and the like. It is preferable that a compound having an ultraviolet transmittance adjusting function is contained in the protective layer from the viewpoint of achieving both light resistance and light fixing property. The heat-sensitive recording material containing the compound having the function of adjusting the ultraviolet transmittance is disclosed in
It is described in detail in Japanese Patent No. 276808.

The heat-sensitive recording material of the present invention can be used for multicolor heat-sensitive recording materials. The multicolor heat-sensitive recording material (heat-sensitive recording material) is disclosed in Japanese Patent Application Laid-Open No. 4-135787.
JP-A-4,144,784 and JP-A-4-144478
No. 5, No. 4-194842, No. 4-2474
Nos. 47, 4-247448, 4-340
Nos. 540, 4-340541 and 5-34
No. 860, for example. Specifically, it can be obtained by laminating thermosensitive recording layers that develop colors of different hues. Although the layer configuration is not particularly limited, as an example, two kinds of diazonium salt compounds having different photosensitive wavelengths, and a coupler which reacts with each diazonium salt compound when heated and develops a different hue are combined. A multicolor heat-sensitive recording material in which two heat-sensitive recording layers (layers B and C) and a heat-sensitive recording layer (layer A) in which an electron-donating colorless dye and an electron-accepting compound are combined is used.
Specifically, a first thermosensitive recording layer (layer A) containing a colorless electron-donating dye and an electron-accepting compound on a support, a diazonium salt compound having a maximum absorption wavelength of 360 nm ± 20 nm, and a diazonium salt compound A second heat-sensitive recording layer (B layer) containing a coupler which shows a color when reacted with heat, a diazonium salt compound having a maximum absorption wavelength of 400 ± 20 nm, and a coupler which shows a color when reacted with the diazonium salt compound when heated And a third heat-sensitive recording layer (C layer). In this example, a full-color image can be recorded by selecting the coloring hues of the respective heat-sensitive recording layers so as to be three primary colors, yellow, magenta, and cyan in the subtractive color mixing.

In the recording method of the multicolor heat-sensitive recording material, first, the third heat-sensitive recording layer (C layer) is heated, and the diazonium salt and the coupler contained in the layer are colored. Next, 400
After irradiating light of ± 20 nm to decompose the unreacted diazonium salt compound contained in the C layer and fix it by light, sufficient heat is applied to the second thermosensitive recording layer (B layer) to develop color. ,
The diazonium salt compound and the coupler contained in the layer are colored. At this time, the C layer is also heated strongly, but the diazonium salt compound has already been decomposed (fixed by light) and the color forming ability has been lost, so that no color is formed. Further, the diazonium salt compound contained in the layer B is decomposed by irradiating light of 360 ± 20 nm, and finally the first
The heat-sensitive recording layer (layer A) is colored by applying sufficient heat to develop the color. At this time, the heat-sensitive recording layers C and B are also strongly heated at the same time, but the diazonium salt compound has already been decomposed and the color-forming ability has been lost, so that no color is formed.

Further, all the heat-sensitive recording layers (A layer, B layer, and C layer, in order from the upper layer) were heated and reacted with three kinds of diazonium salt compounds having different photosensitive wavelengths and different diazonium salt compounds. It can also be composed of a heat-sensitive recording layer in combination with a coupler that develops a hue. In particular, by making the yellow layer having low visibility into the lowermost layer, the influence on the image quality due to the roughness on the surface of the support can be reduced, and the image quality can be improved. All thermal recording layers (A
(Layer, B layer, and C layer) are diazo-based heat-sensitive recording layers, it is necessary to fix the layer A and the layer B after color development. For the layer C, it is not necessary to perform light fixing.

Various fluorescent lamps, xenon lamps, mercury lamps and the like are used as the fixing light source used for the above-mentioned light fixing. It is preferable that this emission spectrum substantially coincides with the absorption spectrum of the diazonium salt compound used in the heat-sensitive recording material, because the light can be efficiently fixed.

In recording on the heat-sensitive recording material of the present invention, the material is exposed through a manuscript to decompose a diazonium salt compound other than at the image forming portion to form a latent image. It can also be used as a heat-developable photosensitive material for obtaining an image.

[0106]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight". Tables 1 to 7 exemplify specific examples of couplers.
No. in Represents

[Pyrrolo [1,2-a] pyrimidine compound represented by formula (1) or (2)] (Example 1) 2- (4-chlorophenyl) -3- (2,6- Di-t-
Synthesis of (butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6-acetyl-pyrrolo [1,2-a] pyrimidine (coupler (6)). 2- (4-chlorophenyl) -3- (2,6-di-t-
Butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-pyrrolo [1,2-a] pyrimidine 10 g
(19.5 mmol) was dissolved in 60 ml of tetrahydrofuran (heated to 50 ° C.), and 7.7 g of acetyl chloride was dissolved.
(97.7 mmol) was added dropwise at 50 ° C. Thereafter, the mixture was stirred under reflux for 7 hours. After cooling, water was added to the reaction solution, extracted with ethyl acetate, washed with water and dried. After evaporating the solvent, methanol was added to the residue, and the precipitated solid was collected by filtration, and the solid was washed with methanol and then with hexane to give 2- (4-chlorophenyl) -3- (2,6-di-t-butyl- 4-
5. Methyl) cyclohexyloxycarbonyl-5-amino-6-acetyl-pyrrolo [1,2-a] pyrimidine
3 g was obtained as a white solid (yield 58%). The melting point is 1
95 ° C. ^{By 1} H-NMR (CDCl ₃ ) analysis, δ 12.6 (s, 1H), 11.20 (s, 1)
H), 9.50 (brs, 1H), 7.36 (d, 2
H), 7.27 (d, 2H), 5.80 (s, 1H),
2.73 (s, 3H), 1.10 to 1.35 (m),
0.95 to 1.05 (m), 0.77 (s, 21H),
A result of 0.42 to 0.58 (m) was obtained.

Example 2 2- (4-chlorophenyl) -3- (2,6-di-t-
Butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6-phenoxyacetyl-pyrrolo [1,
2-a] Synthesis of pyrimidine (coupler (7)). 2- (4-chlorophenyl) -3- (2,6-di-t-
Butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-pyrrolo [1,2-a] pyrimidine 10 g
(19.5 mmol) was dissolved in 60 ml of tetrahydrofuran (heated to 50 ° C.), and 16.6 g (97.7 mmol) of phenoxyacetyl chloride was added dropwise at 50 ° C. Thereafter, the mixture was stirred under reflux for 2 hours. After cooling, water was added to the reaction solution, extracted with ethyl acetate, washed with water and dried. After evaporation of the solvent, the residue was recrystallized from ethyl acetate / methanol to give 2- (4-chlorophenyl) -3- (2,6-di-
9.4 g of (t-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6-phenoxyacetyl-pyrrolo [1,2-a] pyrimidine was obtained as a white solid (yield 74%). Melting point was 192 ° C. ¹ H-N
According to the MR (CDCl ₃ ) analysis, δ 12.60 (s, 1)
H), 11.20 (s, 1H), 9.50 (brs, 1
H), 7.37 (d, 2H), 7.23-7.30
(M, 4H), 6.91 to 6.98 (m, 3H), 5.
81 (s, 1H), 5.46 (s, 2H), 1.10
1.35 (m), 0.95 to 1.05 (m), 0.76
(S, 2H), results of 0.42 to 0.58 (m) were obtained.

Example 3 2- (3,4-dichlorophenyl) -3- (2,6-di-tert-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6- (4-methylphenyl ) Synthesis of sulfonylcarbamoyl-pyrrolo [1,2-a] pyrimidine (coupler (18)). 1.09 g (2 mmol) of 2- (3,4-dichlorophenyl) -3- (2,6-di-t-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-pyrrolo [1,2-a] pyrimidine To tetrahydrofuran 10m
l, and 0.512 g (2.6 mmol) of p-toluenesulfonyl isocyanate was added dropwise.
For a minute. After adding water to the reaction solution and extracting with ethyl acetate,
Washed and dried. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane / ethyl acetate),
2- (3,4-dichlorophenyl) -3- (2,6-di-t-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6- (4-methylphenyl) sulfonylcarbamoyl-pyrrolo [1, 0.89 g of 2-a] pyrimidine was obtained as a white solid (yield 60%). The melting point was 298 ° C (dec.). ¹ H-NMR (CD
Cl ₃ ) analysis revealed that δ 12.58 (s, 1H), 1
1.20 (s, 1H), 9.47 (brs, 1H),
8.20 (brs, 1H), 7.99 (d, 2H),
7.47 (d, 1H), 7.42 (d, 1H), 7.3
0 (d, 2H), 7.16 (dd, 1H), 7.05
(S, 1H), 5.85 (s, 1H), 2.42 (s, 1H)
3H), 1.20 to 1.40 (m), 1.00 to 1.1
0 (m), 0.84 (s, 18H), 0.72 (d, 3
H), 0.40 to 0.50 (m).

Example 4 2- (3,4-Dichlorophenyl) -3- (2,6-di-tert-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6-phenylsulfonylcarbamoyl-pyrrolo [1,2-a] pyrimidine (coupler (1
Synthesis of 1)). The coupler (11) was obtained in the same manner as in Example 3 except that phenylsulfonyl isocyanate was used instead of p-toluenesulfonyl isocyanate used in Example 3 (yield: 63%). The melting point was 210 ° C. ^{According to 1} H-NMR (CDCl ₃ ) analysis, δ12.
60 (s, 1H), 11.20 (s, 1H), 9.45
(Brs, 1H), 8.30 (brs, 1H), 8.1
3 (dd, 2H), 7.50 to 7.65 (m, 3H),
7.49 (d, 1H), 7.41 (d, 1H), 7.1
7 (dd, 1H), 7.08 (s, 1H), 5.87
(S, 1H), 1.20 to 1.40 (m), 1.00
1.08 (m), 0.80 (s, 18H), 0.72
(D, 3H), results of 0.40 to 0.53 (m) were obtained.

Example 5 2- (3,4-dichlorophenyl) -3- (2,6-di-tert-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6- (4-chlorophenyl) Synthesis of sulfonylcarbamoyl-pyrrolo [1,2-a] pyrimidine (coupler (10)). The coupler (10) was obtained in the same manner as in Example 3 except that p-chlorophenylsulfonyl isocyanate was used instead of p-toluenesulfonyl isocyanate used in Example 3 (63% yield). Melting point 209
° C. ^{According to 1} H-NMR (CDCl ₃ ) analysis, δ 12.65 (s, 1H), 11.27 (s, 1
H), 9.40 (brs, 1H), 8.35 (brs,
1H), 8.05 (d, 2H), 7.49 (d, 1
H), 7.48 (d, 2H), 7.40 (d, 1H),
7.15 (dd, 1H), 7.05 (s, 1H),
86 (s, 1H), 1.20 to 1.40 (m), 1.0
0 to 1.10 (m), 0.84 (s, 18H), 0.7
1 (d, 3H), results of 0.40 to 0.53 (m) were obtained.

Example 6 2- (3,4-dichlorophenyl) -3- (2,6-di-tert-butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-6-ethoxycarbonylcarbamoyl-pyrrolo [1,2-a] pyrimidine (coupler (2
6)) Synthesis. The coupler (26) was obtained in the same manner as in Example 3 except that ethoxycarbonyl isocyanate was used instead of p-toluenesulfonyl isocyanate used in Example 3 (yield: 50%). The melting point was 300 ° C. or higher. ^{By 1} H-NMR (CDCl ₃ ) analysis, δ1
2.60 (s, 1H), 10.68 (s, 1H), 1
0.03 (brs, 1H), 9.31 (brs, 1H)
H), 7.50 (d, 1H), 7.45 (d, 1H),
7.20 (dd, 1H), 7.08 (s, 1H);
84 (s, 1H), 4.59 (q, 2H), 1.20
1.40 (m), 1.00 to 1.10 (m), 0.86
(S, 18H), 0.75 (d, 3H), 0.40
A result of 0.54 (m) was obtained.

Example 7 Synthesis of coupler (49) 2- (4-chlorophenyl) -3- (2,6-di-t-
Butyl-4-methyl) cyclohexyloxycarbonyl-5-amino-pyrrolo [1,2-a] pyrimidine 5.1
2 g (10 mmol) was dissolved in 50 ml of tetrahydrofuran, and 1.84 g of chlorosulfonyl isocyanate was dissolved.
(13 mmol) was added dropwise, followed by stirring at room temperature for 30 minutes. Thereafter, 1.01 g (10 mmol) of triethylamine was added, and the mixture was further stirred at room temperature for 2 hours. Add water to the reaction solution,
After extraction with ethyl acetate, the extract was washed with water and dried. After evaporating the solvent, silica gel chromatography (hexane / ethyl acetate)
To give 2.44 g of the above coupler (49) as a white solid (40% yield). Melting point was 202 ° C. ^{By 1} H-NMR (CDCl ₃ ) analysis, δ11.
09 (s, 1H), 10.14 (brs, 1H), 9.
35 (brs, 1H), 7.37 (d, 2H), 7.3
0 (d, 2H), 7.07 (s, 1H), 5.88
(S, 1H), 1.20 to 1.40 (m), 1.00
1.10 (m), 0.84 (s, 18H), 0.80
(D, 3H), results of 0.47 to 0.60 (m) were obtained.

[Thermal Recording Material] (Example 8) <Preparation of Microcapsule Liquid A> A diazonium salt (exemplified compound (4) -1, maximum absorption wavelength 3) was added to 19 parts of ethyl acetate.
2.8 parts, tricresyl phosphate 10
Parts were added and mixed uniformly. Next, Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) was added to this mixed solution as a wall material.
7.6 parts were added and mixed uniformly to obtain a liquid I. Next, 46 parts of an 8% by weight aqueous solution of phthalated gelatin, 17.5 parts of water, and 10 parts of sodium dodecylbenzenesulfonate were added to the solution I.
% Aqueous solution at 40 ° C and 10,000 r. p. m.
For 10 minutes. After adding 20 parts of water to the obtained emulsion and homogenizing, a microcapsulation reaction was performed at 40 ° C. for 3 hours with stirring to obtain a microcapsule liquid A. The average particle size of the microcapsules is 0.7-0.8μ
m.

<Preparation of coupler emulsion B> Ethyl acetate 1
0.5 part of coupler (6) 3.0 parts, triphenylguanidine 3.0 parts, tricresyl phosphate 0.5
Parts, 0.24 parts of maleic acid diethyl ester were dissolved
Solution II was obtained. Next, 49 parts of a 15% by weight aqueous solution of lime-processed gelatin, 9.5 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate, and 35 parts of water were uniformly mixed at 40 ° C.
Solution II was added, and the mixture was added at 40 ° C. and 1000 using a homogenizer.
0r. p. m. For 10 minutes. After stirring the obtained emulsion at 40 ° C. for 2 hours to remove ethyl acetate, the weight of the stripped ethyl acetate and water was supplemented with water to obtain a coupler emulsion B.

<Preparation of Coating Solution C for Thermosensitive Recording Layer> 3.6 parts of microcapsule solution A, 3.3 parts of water, coupler emulsion B
9.5 parts were uniformly mixed to obtain a heat-sensitive recording layer coating solution C.

<Preparation of Protective Layer Coating Solution D> 100 parts of a 6% aqueous solution of itaconic acid-modified polyvinyl alcohol (KL-318; trade name, manufactured by Kuraray Co., Ltd.) and epoxy-modified polyamide (FL-71; trade name, Toho Chemical Co., Ltd.) 30)
15 parts of a dispersion of 40% zinc stearate (Hydrin Z; trade name, manufactured by Chukyo Yushi Co., Ltd.) was uniformly mixed with a liquid obtained by mixing 10 parts of a 10% dispersion liquid to obtain a protective layer coating liquid D. .

<Coating> On a photographic paper support obtained by laminating polyethylene on a high-quality paper, a heat-sensitive recording layer coating solution C and a protective layer coating solution D were sequentially coated and dried at 50 ° C. in order with a wire bar. The desired heat-sensitive recording material was obtained. The application amounts as solids were 8.0 g / m ² and 1.2 g / m ² , respectively.

[Coloring Test] After applying a thermal head (KST type) manufactured by Kyocera Corporation and determining the applied power and pulse width to the thermal head so that the recording energy per unit area is 50 mJ / mm ^2, and performing thermal printing, The entire surface was irradiated for 15 seconds using an ultraviolet lamp having an emission center wavelength of 365 nm and an output of 40 W. The density of the image portion and the background portion of the obtained sample was measured with a Macbeth densitometer.

[Evaluation of Hue] An image portion developed using a thermal head (KST type) manufactured by Kyocera Corporation was subjected to UV irradiation.
The reflection spectrum was measured using a / VIS spectrometer, and the maximum absorbance was normalized to 1.0. Wavelength region 400-4
A lower absorbance at 75 nm means that a better cyan hue with less yellowness is given.

[Test of Image Lightfastness] The image portion, which was colored using a thermal head (KST type) manufactured by Kyocera Corporation, was examined at 32,000 lux using a fluorescent lamp lightfastness tester.
After continuous light irradiation for 2 hours, the density of the image area was measured.
The higher the density of the image area after light irradiation, the better the image light resistance.

[Test of Image Fixing Property] In the test of image fixing property, the background portion (unprinted portion) of the fixed sample was measured using a thermal head (KST type) manufactured by Kyocera Corporation, and the recording energy per unit area was reduced. Thermal printing was performed with the power applied to the thermal head and the pulse width determined so as to be 40 mJ / mm ^2, and the density change was examined. The lower the density after printing, the better the image fixability.

Example 9 A thermosensitive recording material was prepared in the same manner as in Example 8, except that an emulsion was obtained using the coupler (7) instead of the coupler (6) used in Example 8. ,evaluated.

Example 10 A thermosensitive recording material was prepared in the same manner as in Example 8, except that an emulsion was obtained using the coupler (10) instead of the coupler (6) used in Example 8. ,evaluated

Example 11 A thermosensitive recording material was prepared in the same manner as in Example 8, except that an emulsion was obtained using the coupler (11) instead of the coupler (6) used in Example 8. ,evaluated.

Example 12 A thermosensitive recording material was prepared in the same manner as in Example 8, except that an emulsion was obtained using the coupler (12) instead of the coupler (6) used in Example 8. ,evaluated.

Example 13 A thermosensitive recording material was prepared in the same manner as in Example 8, except that an emulsion was obtained using the coupler (18) instead of the coupler (6) used in Example 8. ,evaluated.

(Example 14) A thermosensitive recording material was produced in the same manner as in Example 8, except that an emulsion was obtained using the coupler (26) instead of the coupler (6) used in Example 8. ,evaluated.

(Example 15) A thermosensitive recording material was produced in the same manner as in Example 8, except that an emulsion was obtained using the coupler (49) instead of the coupler (6) used in Example 8. ,evaluated.

Example 16 A microcapsule solution was prepared using Exemplified Compound (4) -2 (maximum absorption wavelength: 370 nm) instead of the diazonium salt (Exemplified Compound (4) -1) used in Example 13. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 13 except for the above.

Comparative Example 1 An emulsion was obtained using 2-hydroxy-3-naphthoic acid [3- (2-ethylhexyloxy)] anilide instead of the coupler (6) used in Example 8. In the same manner as in Example 8, a thermosensitive recording material was prepared and evaluated.

Table 8 shows λ _{max of} the image portion, the results of the image light fastness test and the image fixability test, and Table 9 shows the absorbance (wavelength region of 400 to 475 nm) of the image portion.

[0133]

[Table 8]

[0134]

[Table 9]

From these results, it can be seen that the thermosensitive recording material of the present invention using the pyrrolo [1,2-a] pyrimidine compound represented by the general formula (1) or (2) as a coupler has a high color density. I understand. It can be seen that the image portion has little yellow absorption and is good cyan. In addition, even after irradiation with light from a fluorescent lamp, the rate of decrease in the density of the image area was small, indicating that the image was excellent in light resistance. Furthermore, when the background portion of the sample after image fixing is heat-printed again, there is little color development,
It can be seen that the image fixability is excellent.

[0136]

According to the present invention, when coupled with a diazonium salt compound as a coupler, a novel pyrrolo [1,1] which can provide a cyan dye having excellent color development and low yellow absorption. 2-a] pyrimidine compounds can be provided. Further, according to the present invention, by combining the pyrrolo [1,2-a] pyrimidine compound with a diazonium salt compound, in addition to the above-described properties, the shelf life, image light fastness, and image fixability are excellent. A novel cyan coloring type diazo thermosensitive recording material can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C07D 207: 00 239: 00) (C07D 487/14 207: 00 239: 00) (C07D 513/14 209: 00 239: (00 285: 00) (72) Mitsuyuki Tsurumi, Fuji Photo Film Co., Ltd. 200, Onakasato, Fujinomiya City, Shizuoka Prefecture (72) Inventor Tetsunori Matsushita 200, Onakazato, Fujinomiya City, Fujinomiya City, Shizuoka Prefecture F Fuji Photo Film Co., Ltd. Terms (reference) 2H026 AA07 BB42 BB43 DD12 DD15 FF05 4C050 AA01 BB08 CC04 EE03 FF03 GG04 HH01 4C072 AA01 BB03 CC04 CC16 EE15 FF05 GG01 GG07 GG09 GG10 HH02 UU05

Claims (7)

[Claims] 1. A pyrrolo [1,2-a] pyrimidine compound represented by the following general formula (1). Embedded image (In the general formula (1), R ¹ and R ² are each a hydrogen atom, a halogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group Or R ³ represents an electron-withdrawing group having a Hammett's substituent constant σ _P value of 0.20 or more.) 2. A pyrrolo [1,2-a] pyrimidine compound represented by the following general formula (2). Embedded image (In the general formula (2), R ¹ and R ² are each a hydrogen atom, a halogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an alkylsulfonyl group. Or X represents an arylsulfonyl group, and X represents CO or SO _2. ) 3. A diazonium salt compound on a support,
2. A thermosensitive recording material provided with a thermosensitive recording layer containing the diazonium salt compound and a coupler which develops a color when reacted with heat, wherein the coupler is represented by the general formula (1) according to claim 1.
And at least one selected from pyrrolo [1,2-a] pyrimidine compounds represented by the general formula (2) according to claim 2. A heat-sensitive recording material characterized in that: 4. The heat-sensitive recording material according to claim 3, wherein the maximum absorption wavelength λ _max of the diazonium salt compound is 450 nm or less. 5. The heat-sensitive recording material according to claim 3, wherein the diazonium salt compound is at least one of the following general formulas (3) to (5). Embedded image In (general formula (3), Ar is a substituted or unsubstituted aryl group, R ¹¹ and R ^12, .R ¹¹ and each represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group R ¹² may be the same or different, and X ⁻ represents an acid anion.) In (formula ^{(4), R 14, R} 15 and R ¹⁶ are each a substituted or unsubstituted alkyl group, or .R ^14, R ¹⁵ and R ¹⁶ to represent a substituted or unsubstituted aryl group, in the same Y represents a hydrogen atom or an —OR ¹³ group, and R ¹³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
X ^- represents an acid anion. ) (In the general formula (5), R ¹⁷ and R ¹⁸ each represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ⁻ represents an acid anion.) 6. The method according to claim 3, wherein the diazonium salt compound is encapsulated in a microcapsule.
2. The heat-sensitive recording material according to item 1. 7. The capsule wall of the microcapsule,
The heat-sensitive recording material according to claim 6, which is a capsule wall containing polyurethane and / or polyurea as a constituent.