JP2002241370A - Barbituric acid derivative and diazo thermosensitive recording material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a barbituric acid derivative having a specific substituent useful for a thermosensitive recording material and a diazo thermosensitive recording material containing the barbituric acid derivative and having excellent unsensitized preservability and image preservability. SOLUTION: This barbituric acid derivative is represented by the general formula (1)(R1 and R2 each denote mutually different substituents and are each an alkyl which may have a substituent or an aralkyl which may have a substituent; and L denotes H or a substituent capable of being removed when subjected to a coupling with a diazo compound). The diazo thermosensitive recording material contains the barbituric acid derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barbituric acid derivative and a diazo thermosensitive recording material containing the same, and more particularly to a barbituric acid derivative useful for a diazo thermosensitive recording material, and a barbituric acid derivative containing the barbituric acid derivative. The present invention relates to a diazo thermosensitive recording material having excellent raw storability before recording and image storability after recording.

[0002]

2. Description of the Related Art A diazo compound is a compound having a very high chemical activity, and easily reacts with a compound called a coupler, such as a phenol derivative or a compound having an active methylene group, to easily form an azo dye and enhance photosensitivity. It decomposes by light irradiation and loses its activity. Therefore, diazo compounds have been used for a long time as optical recording materials typified by diazo copy ("Photographic Engineering Fundamentals-Non-silver salt photography-" edited by The Photographic Society of Japan, Corona (1982) p.89-
P117, P182 to P201).

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 diazo compound and a coupler are heated in accordance with an image signal. A photo-fixing type thermosensitive recording material has been proposed in which an image is formed by reacting 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, No. 4 (1982) P290-296). Such).

However, in these recording materials using a diazo compound as a color-forming element, the activity of the diazo compound is extremely high, and even in a dark place, the diazo compound gradually decomposes and loses its reactivity. There is a drawback that the shelf life as a material is short. Various methods have been proposed as means for improving the instability of the diazo compound described above. One of the most effective means is a method of encapsulating the diazo compound in microcapsules.

As described above, by microencapsulating the diazo compound, the diazonium salt is isolated from water or base which promotes decomposition, so that the decomposition is remarkably suppressed. (Masamasa Usami et al., Journal of the Institute of Electrophotography, Vol. 26, No. 2, (1987) P115-12)
5).

As a general method for encapsulating a diazo compound in microcapsules, a diazonium salt is dissolved in a hydrophobic solvent (oil phase), and this is added to an aqueous solution (water phase) in which a water-soluble polymer is dissolved. By emulsifying and dispersing with a homogenizer, etc., and adding a monomer or prepolymer as a wall material for the microcapsules to either or both of the oil phase and the aqueous phase to polymerize at the interface between the oil phase and the aqueous phase. In some cases, a polymer wall is formed by causing a reaction or by precipitating a polymer to form a microcapsule.

These methods are described, for example, by Asashi Kondo, "Microcapsule", Nikkan Kogyo Shimbun (published in 1970),
Tamotsu Kondo et al., "Microcapsule" Sankyo Publishing (197
7 years). As the microcapsule wall to be formed, various materials such as crosslinked gelatin, alginate, celluloses, urea resin, urethane resin, melamine resin and nylon resin can be used.

In the case of a microcapsule having a glass transition temperature such as a urea resin or a urethane resin and having a glass transition temperature slightly higher than room temperature, the capsule wall at room temperature shows material impermeability, Since it shows a substance permeability above the glass transition temperature, it is called a thermoresponsive microcapsule and is useful for a heat-sensitive recording material.

That is, a diazonium salt is stably retained for a long period of time by preparing a recording material on which a thermoresponsive microcapsule containing a diazonium salt and a thermosensitive recording layer containing a coupler and a base are coated on a support. In addition to being able to form a color image easily by heating, it is also possible to fix the image by light irradiation. As described above, the stability of the diazo compound can be dramatically improved by microencapsulation.

On the other hand, a 4-substituted amino-2-alkoxybenzenediazonium salt exhibits particularly excellent performance as a coloring material for thermal recording (Japanese Patent Application Laid-Open No. 4-59288). In
It is known that a reddish dye having an extremely good hue is produced (JP-A-4-197778).

[0011]

SUMMARY OF THE INVENTION
A recording material containing a substituted amino-2-alkoxybenzenediazonium salt has the drawback that its raw preservability (background coloring during pre-copy preservation) and the preservability of a color image (light fastness) are not sufficient. Was. Thus, the present inventors have conducted intensive studies to solve the above-described drawbacks, and as a result, when a diazo compound having a specific substituent and a barbituric acid derivative having a specific substituent as a coupling component are used in combination. Have found that very good results can be obtained, and have reached the present invention.

Accordingly, the present invention provides a barbituric acid derivative having a specific substituent useful for a heat-sensitive recording material, and a diazo heat-sensitive recording material containing the barbituric acid derivative and having excellent raw preservability and image preservability. The purpose is to provide.

[0013]

The means for achieving the above object are as follows. <1> A barbituric acid derivative represented by the following general formula (1).

Embedded image In the formula, R ¹ and R ² each represent a different substituent, and each represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent. L represents a hydrogen atom or a substituent capable of leaving upon coupling with a diazo compound. <2> The barbituric acid derivative according to <1>, represented by the following general formula (2).

Embedded image In the formula, R ³ and R ⁴ are each independently, R ³ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁴ is a substituent And an aralkyl group which may have a substituent.

<3><2> represented by the following general formula (3)
2. The barbituric acid derivative according to item 1.

Embedded image In the formula, R ⁵ and R ⁶ are each independently, R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁶ is a substituent And an aralkyl group which may have a substituent. <4> On a support, a diazo compound, a coupling component,
And a thermosensitive recording material provided with a thermosensitive recording layer containing an organic base, wherein the coupling component contains at least one compound represented by the general formula (1). .

Embedded image In the formula, R ¹ and R ² each represent a different substituent, and each represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent. L represents a hydrogen atom or a substituent capable of leaving upon coupling with a diazo compound.

<5> In a diazo thermosensitive recording material in which a thermosensitive recording layer containing a diazo compound, a coupling component and an organic base is provided on a support, the coupling component is represented by the general formula (2). Thermosensitive recording material comprising at least one compound selected from the group consisting of:

Embedded image In the formula, R ³ and R ⁴ are each independently, R ³ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁴ is a substituent And an aralkyl group which may have a substituent. <6> On a support, a diazo compound, a coupling component,
And a thermosensitive recording material provided with a thermosensitive recording layer containing an organic base, wherein the coupling component contains at least one compound represented by the general formula (3). .

Embedded image In the formula, R ⁵ and R ⁶ are each independently, R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁶ is a substituent And an aralkyl group which may have a substituent.

<7> The diazo thermosensitive recording material according to <4> to <6>, wherein the diazo compound contains at least one compound represented by the following general formula (4).

Embedded image In the formula, R ⁷ , R ⁸ and R ⁹ are each independently and represent an alkyl group which may have a substituent or an aryl group which may have a substituent. X ^- represents an anion. <8> The diazo thermosensitive recording material according to <4> to <7>, wherein the diazo compound is encapsulated in microcapsules.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail. In the barbituric acid derivative represented by the general formula (1), R ¹ and R ² each represent a different substituent. That is, the barbituric acid derivative is asymmetric. R ¹ and R ² represent an alkyl group which may have a substituent or an aralkyl group which may have a substituent. The total carbon number of the alkyl group is 1 to 25
Is preferred, more preferably 5 to 25, and even more preferably 10 to 25. The total carbon number of the aralkyl group is preferably from 7 to 30,
It is more preferably from 10 to 30, and further preferably from 15 to 30.

When R ¹ and R ² have a substituent, examples of the substituent include an alkyl group having 1 to 18 carbon atoms and 6 to 20 carbon atoms.
Aryl group, hydroxyl group, alkyloxy group having 1 to 18 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkylthio group having 1 to 18 carbon atoms, arylthio group having 6 to 20 carbon atoms, 2 to 25 carbon atoms An alkylcarbonyl group of
Arylcarbonyl group having 7 to 35 carbon atoms, 2 to 2 carbon atoms
An alkoxycarbonyl group having 5 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 37 carbon atoms,
To 35 acylamino groups, alkylsulfonyl groups having 2 to 20 carbon atoms, arylsulfonyl groups having 7 to 20 carbon atoms,
An alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, a heterocyclic residue, a halogen atom, a cyano group, and a nitro group are preferable. In particular, an alkyl group having 1 to 18 carbon atoms and 1 carbon atom Preferred are an alkyloxy group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 25 carbon atoms, an alkoxycarbonyl group having 2 to 25 carbon atoms, and an acyloxy group having 2 to 20 carbon atoms. These substituents may further have a substituent.

L represents a hydrogen atom or a substituent capable of leaving upon coupling with a diazo compound (hereinafter referred to as a leaving group). Only one leaving group may be introduced as a substituent into the compound (barbituric acid derivative) represented by the general formula (1), or two or more leaving groups may be introduced.

Examples of the leaving group include a halogen atom, an aromatic azo group, an alkyl group, an aryl group or a heterocyclic group having a coupling position via an oxygen / nitrogen / sulfur or carbon atom, an alkyl or arylsulfonyl group, an aryl Examples include a sulfinyl group, an alkyl aryl or a heterocyclic carbonyl group, or a heterocyclic group bonded to a coupling site with a nitrogen atom.Specifically, for example,
Halogen atom, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylaryl or heterocyclic thio group A carbamoylamino group, an arylsulfinyl group, an arylsulfonyl group, a 5- or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group, and the like. The alkyl group or the heterocyclic group included in these leaving groups is It may be further substituted with a substituent such as an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, an alkylcarbonyloxy group.
Examples of the leaving group include an amino group, an ether group, and a thioether group that are bonded to a coupling site via a carbon atom. Specific examples include a dimethylaminomethyl group, a hydroxymethyl group, an ethoxymethyl group, and a phenoxymethyl group. , A methylthioxymethyl group, a phenylthioxymethyl group and the like.

When two or more substituents are introduced, they may be the same or different, and these substituents may further have the above-mentioned substituents. Also, the leaving group may form a ring with the coupler mother nucleus.

The leaving group is more specifically a halogen atom (fluorine, bromine, chlorine, iodine), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy). An aryloxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl A sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino, heptafluorobutyrylamino), an alkyl or arylsulfonamide group (eg, methanesulfonamide, trifluoromethanesulfonamino, p-toluenesulfonylamino), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), alkyl Aryl or heterocyclic thio group. (E.g., ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-t-octylphenylthio,
Tetrazolylthio), arylsulfonyl group (for example,
2-butoxy-t-octylphenylsulfonyl), arylsulfinyl group (eg, 2-butoxy-t-octylphenylsulfinyl), galvamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5-membered Alternatively, a 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, Phenylazo, 4-methoxyphenylazo) and the like. These groups may be further substituted.

Hereinafter, a method for synthesizing the barbituric acid derivative (barbituric acid compound) represented by the general formula (1) will be described. The barbituric acid compound represented by the general formula (1) has an N, N′-2 substituted urea (substituent is different) 1 m
ol, about 1.1 mol of malonic acid, 3 m of acetic anhydride
ol and 1 L of ethyl acetate, and reflux for 3 hours. Thereafter, for example, a poor solvent such as methanol is added,
The precipitated crystal is collected by filtration to obtain the target compound, a barbituric acid compound represented by the general formula (1). Further, as a method for introducing the leaving group L, a method for introducing a barbitur compound after synthesizing it by the above method (for example, NCS (N-Chl
(oro-Succinimide). ) And a method of synthesizing and introducing a barbituric acid compound by the above method using malonic acid having a leaving group L introduced.

Among the compounds represented by the general formula (1), the compound represented by the general formula (2) is particularly preferable. In the general formula (2), R ³ and R ⁴ are each independently, and R ³ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent; ⁴ represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent. Since the compound represented by the general formula (2) is asymmetric, the substituents on the nitrogen are different.

Among the compounds represented by the general formula (1), the compound represented by the general formula (3) is more preferable. In the general formula (3), R ⁵ and R ⁶ are each independently, and R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent; ⁶ represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent. Since the compound represented by the general formula (3) is asymmetric, the substituent on the nitrogen is different.

Here, when R ³ , R ⁴ , R ⁵ and R ⁶ are an alkyl group which may have a substituent or an aralkyl group which may have a substituent, The total carbon number of the alkyl group is preferably 1 to 25,
It is more preferably 5 and further preferably 10 to 25. The carbon number of the aralkyl group which may have a substituent is preferably 7 to 30, but is preferably 10 to 30.
Is more preferable, and 15 to 30 is further preferable.

When R ³ , R ⁴ , R ⁵ and R ⁶ have a substituent, the substituent may be an alkyl group having 1 to 18 carbon atoms;
An aryl group having 6 to 20 carbon atoms, a hydroxyl group, an alkyloxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an arylthio group having 6 to 20 carbon atoms, An alkylcarbonyl group having 2 to 25 carbon atoms, an arylcarbonyl group having 7 to 35 carbon atoms, an alkoxycarbonyl group having 2 to 25 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 37 carbon atoms, and a carbon number 2 to 35 acylamino groups, having 2 to 2 carbon atoms
An alkylsulfonyl group having 20 carbon atoms, an arylsulfonyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms,
An arylamino group having 6 to 20 carbon atoms, a heterocyclic residue, a halogen atom, a cyano group, and a nitro group are preferable. In particular, an alkyl group having 1 to 18 carbon atoms, an alkyloxy group having 1 to 18 carbon atoms, and 2 carbon atoms Alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, 2 to 2 carbon atoms
An acyloxy group of 0 is preferred. These substituents may further have a substituent.

Here, specific examples of the barbituric acid derivatives represented by the general formulas (1) to (3) are shown, but the present invention is not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The compound (barbituric acid derivative) represented by the general formula (1) is a compound of a diazo thermosensitive recording material in which a thermosensitive recording layer containing a diazo compound, a coupling component and an organic base is provided on a support. It can be used as a ring component. Further, it is more preferable to use a compound represented by the general formula (2) as a coupling component,
It is more preferable to use the compound represented by the general formula (3).

In the present invention, the general formulas (1) to (3)
A known coupling component that forms a dye by coupling with a diazo compound in a basic atmosphere can be used together with a coupling component represented by for the purpose of adjusting hue and the like, if necessary. It is preferable that 50% by mass or more of all the coupling components are the coupling components represented by the general formulas (1) to (3).

Known coupling components which can be used in combination with the coupling components represented by the general formulas (1) to (3) include, for example, a so-called active methylene compound having a methylene group next to a carbonyl group, and phenol. Derivatives, naphthol derivatives and the like.

Specifically, resorcin, phloroglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene,
2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfo-naphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-
3-naphthoic acid octylamide, 2-hydroxy-3-
Naphthoic acid anilide, benzoylacetonilide, 1-phenyl-3-methyl-5-pyrazolone, 1- (2,4,
6-trichlorophenyl) -3-anilino-5-pyrazolone, 2- {3- [α- (2,4-di-tert-amylphenoxy) -butanamido] ben {amide} phenol, 2,4-bis- (benzoylaceto Amino) toluene, 1,3-bis- (pivaloylacetoaminomethyl) benzene, and the like.

In the above diazo thermosensitive recording material, it is preferable to use a compound represented by the general formula (4) as the diazo compound. In the formula, R ⁷ , R ⁸ and R ⁹ are each independently and represent an alkyl group which may have a substituent or an aryl group which may have a substituent. X ^- represents an anion.

The alkyl group which may have a substituent represented by R ⁷ and R ⁸ preferably has a total carbon number of 1 to 30, but more preferably 5 to 25. For example,
Methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl, 2-pentyl, 3-pentyl, isopentyl, normal hexyl, normal octyl, 2-ethylhexyl, 3,5,5,-
Trimethylhexyl, normal dodecyl, cyclohexyl, benzyl, allyl, 2-methoxyethyl, 2-ethoxyethyl, 2-phenoxyethyl, 2- (2,5-di-tert-amylphenoxy) ethyl, 2-benzoyloxyethyl, methoxy Carbonylmethyl, methoxycarbonylethyl, butoxycarbonylethyl, 2-isopropyloxyethyl, 2- (4-methoxyphenoxy) ethyl, 3- (4-methoxyphenoxy) propan-2-yl, N, N-di (butyl)- Carbamoylmethyl,
N, N-di (hexyl) -carbamoylmethyl, N, N-di (ethyl) -carbamoylmethyl, piperidinocarbonylmethyl, 2- {N, N-di (butyl) -carbamoyl} ethyl, 1- {N , N-di (butyl) -carbamoyldiethyl,
Pyrrolidinocarbonylmethyl is preferred.

The aryl group which may have a substituent represented by R ⁷ and R ⁸ preferably has a total carbon number of 6 to 30, and more preferably 10 to 30.

The anion represented by X ⁻ is preferably an inorganic anion such as hexafluorophosphate ion, borofluoride ion, chloride ion, hydrogen sulfate ion or sulfate ion. Preferred are a fluoroalkyl carboxylate ion, a polyfluoroalkyl sulfonate ion, an aromatic carboxylate ion, an aromatic sulfonate ion, and a tetraaryl borate ion.
Particularly, hexafluorophosphate ion and borofluoride ion are preferable.

In the general formula (4), the optionally substituted alkyl group represented by R ⁹ has a total carbon number of 1 to 30.
Is preferred, and more preferably 5 to 25. For example, methyl, ethyl, normal propyl, isopropyl, normal butyl, tertiary butyl, secondary butyl, isobutyl, normal pentyl, 2-pentyl, 3-pentyl, isopentyl, normal hexyl, normal octyl, 2-ethylhexyl, 3,5, 5, -trimethylhexyl, normal dodecyl,
Cyclohexyl, benzyl, allyl, 2-chloroethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-phenoxyethyl, 2- (2,5-di-tert-amylphenoxy) ethyl, 2-benzoyloxyethyl, methoxycarbonylmethyl , Methoxycarbonylethyl, butoxycarbonylethyl and 2-isopropyloxyethyl are preferred.

The aryl group which may have a substituent represented by R ⁹ preferably has 6 to 30 carbon atoms, more preferably 10 to 30 carbon atoms. For example, phenyl, 4-methylphenyl, 3-methylphenyl, 2
-Methylphenyl, 4-chlorophenyl, 2-chlorophenyl are preferred.

Next, specific examples of the diazo compound of the general formula (4) are shown, but the present invention is not limited to these.

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[0046]

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The diazo compounds represented by the general formula (4) may be used alone or in combination of two or more. Further, according to various purposes such as hue adjustment, the general formula (4)
And a known diazo compound can be used in combination. However, the diazo compound (diazonium salt) represented by the general formula (4) can
It is preferably at least 0% by mass.

The diazo compound used in combination is 4-diazo-1-dimethylaminobenzene, 4-diazo-2-butoxy-5-chloro-1-dimethylaminobenzene,
-Diazo-1-methylbenzylaminobenzene, 4-diazo-1-ethylhydroxyethylaminobenzene, 4
-Diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2, 5-dibutoxybenzene, 4-
Diazo-1-toluylmercapto-2,5-diethoxybenzene, 4-diazo-1-piperazino-2-methoxy-5-chlorobenzene, 4-diazo-1- (N, N-dioctylaminocarbonyl) benzene, -Diazo-1
-(4-tert-octylphenoxy) benzene, 4
-Diazo-1- (2-ethylhexanoylpiperidino)
-2,5-dibutoxybenzene, 4-diazo-1- [α
-(2,4-ditert-amylphenoxy) butyrylpiperidino] benzene, 4-diazo-1- (4-methoxy) phenylthio-2,5-diethoxybenzene, 4-
Diazo-1- (4-methoxy) benzamide-2,5-
Diethoxybenzene, 4-diazo-1-pyrrolidino-2
-Methoxybenzene and the like are preferred.

Further, in the diazo thermosensitive recording material of the present invention, in order to improve the raw preservability of the thermosensitive recording material before use, a diazo compound is encapsulated in microcapsules as described later in detail. Is preferable, in that case,
For use by dissolving in an appropriate solvent, the diazo compound is
It is preferable to have appropriate solubility in these solvents and low water solubility. Specifically, it is preferable that the organic solvent used has a solubility of 5% or more and the solubility in water is 1% or less.

In the diazo thermosensitive recording material of the present invention,
It is preferable that a diazo compound is contained in the heat-sensitive recording layer in a range of 0.02 to 3 g / m ² .
In particular, it is preferable to contain it in the range of 0.1 to ² g / m ² .

The diazo thermosensitive recording material of the present invention preferably contains a diazo compound in microcapsules in order to improve the raw preservability before use. The microcapsules used in this case are a non-aqueous solvent having a boiling point of 40 to 95 ° C. at normal pressure, and a solution in which a diazonium salt and a same or different compound which reacts with each other to produce a polymer substance are dissolved. After emulsifying and dispersing in a hydrophilic protective colloid solution, the system is heated while the pressure in the reaction vessel is reduced to evaporate the solvent, and the wall forming substance is transferred to the oil droplet surface while distilling off the solvent. It is produced by advancing a polymer formation reaction by polycondensation to form a wall film.

In the diazo thermosensitive recording material of the present invention,
In particular, it is preferable to use microcapsules substantially free of a solvent, which will be described later, from the viewpoint of obtaining a good shelf life. Further, the polymer substance forming the microcapsule wall is preferably at least one selected from polyurethane and polyurea.

Hereinafter, a method for producing a diazonium salt-containing microcapsule (polyurea / polyurethane wall) in the diazo thermosensitive recording material of the present invention will be described. First,
The diazonium salt is dissolved in a hydrophobic organic solvent serving as the core of the capsule. In this case, the organic solvent is preferably at least one solvent selected from halogenated hydrocarbons, carboxylic esters, phosphoric esters, ketones, and ethers. In the core solvent, polyvalent isocyanate is further added as a wall material (oil phase).

On the other hand, as the aqueous phase, an aqueous solution in which a water-soluble polymer such as polyvinyl alcohol or gelatin is dissolved is prepared, and then the oil phase is charged and emulsified and dispersed by means such as a homogenizer. At this time, the water-soluble polymer acts as a stabilizer for emulsification and dispersion. A surfactant may be added to at least one of the oil phase and the aqueous phase in order to perform the emulsification and dispersion more stably.

The amount of the polyvalent isocyanate used is determined so that the microcapsules have an average particle size of 0.3 to 12 μm and a wall thickness of 0.01 to 0.3 μm. The dispersed particle diameter is generally about 0.2 to 10 μm. In the emulsified dispersion, a polymerization reaction of the polyvalent isocyanate occurs at the interface between the oil phase and the aqueous phase to form a polyurea wall.

If a polyol is added to the aqueous phase, the polyvalent isocyanate can react with the polyol to form a polyurethane wall. It is preferable to keep the reaction temperature high or to add an appropriate polymerization catalyst in order to increase the reaction rate. Details of polyvalent isocyanates, polyols, reaction catalysts, and polyamines for forming a part of the wall material are described in detail in Polygraphs (Polyurethane Handbook, edited by Keiji Iwata, Nikkan Kogyo Shimbun (1987)).

As the hydrophobic organic solvent for dissolving the diazonium salt and forming the core of the microcapsule, an organic solvent having a boiling point of 100 to 300 ° C. is preferable. Specifically, alkylnaphthalene, alkyldiphenylethane, alkyldiphenylmethane, Alkyl biphenyl, chlorinated paraffin, tricresyl phosphate, maleic acid ester, adipic acid ester, sulfate ester, sulfonate ester and the like can be mentioned. These may be used as a mixture of two or more.

When the solubility of the diazonium salt to be encapsulated in these solvents is poor, a low-boiling solvent having high solubility of the dizonium salt to be used can be used in combination. Specific examples include ethyl acetate, butyl acetate, methylene chloride, tetrahydrofuran, acetone and the like. When only a low boiling point solvent is used for the core of the capsule, the solvent evaporates during the encapsulation reaction to form a so-called coreless capsule in which the capsule wall and the diazo compound are present integrally.

As a polyvalent isocyanate compound used as a raw material for the microcapsule wall, a compound having a trifunctional or more isocyanate group is preferable, but a bifunctional isocyanate compound may be used in combination. Specifically, diisocyanates such as xylene diisocyanate and its hydrogenated product, hexamethylene diisocyanate, tolylene diisocyanate and its hydrogenated product, and isophorone diisocyanate are used as main raw materials, and dimers or trimers (buret or isocyanurate) thereof are used. In addition, polyfunctional adducts with polyols such as trimethylolpropane, and formalin condensates of benzene isocyanate may be mentioned.

Further, a polyol or polyamine may be added to a hydrophobic solvent serving as a core or a water-soluble polymer solution serving as a dispersion medium, and used as one of the raw materials for the microcapsule wall. Specific examples of these polyols or polyamines include propylene glycol, glycerin, trimethylolpropane, triethanolamine, sorbitol, hexamethylenediamine, and the like. When a polyol is added, a polyurethane wall is formed.

The water-soluble polymer used in the water-soluble polymer aqueous solution in which the oil phase of the capsule thus prepared is dispersed is preferably a water-soluble polymer having a solubility in water of 5 or more at the temperature to be emulsified. Specific examples thereof include polyvinyl alcohol and modified products thereof, polyacrylamide and derivatives thereof, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, and isobutylene-anhydride. Maleic acid copolymer, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer,
Examples include carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivatives, gum arabic, sodium alginate and the like.

It is preferable that these water-soluble polymers have no or low reactivity with the isocyanate compound. For example, those having a reactive amino group in the molecular chain such as gelatin are modified beforehand. It is necessary to eliminate reactivity. When a surfactant is added, the amount of the surfactant added is 0.1 to the mass of the oil phase.
It is preferably from 1% to 5%, particularly preferably from 0.5% to 2%.

For the emulsification, a known emulsifying apparatus such as a homogenizer, a Manton-Gawley, an ultrasonic disperser, and a Keddy mill can be used. After the emulsification, the emulsion is heated to 30 to 70 ° C. in order to promote the capsule wall forming reaction. During the reaction, in order to prevent the capsules from agglomerating, it is necessary to reduce the collision probability between the capsules by adding water or to perform sufficient stirring.

Further, a dispersant for preventing aggregation may be added again during the reaction. Generation of carbon dioxide gas is observed with the progress of the polymerization reaction, and the end thereof can be regarded as an approximate end point of the capsule wall forming reaction. Usually, by reacting for several hours, the desired diazonium salt-containing microcapsules can be obtained.

In the diazo thermosensitive recording material of the present invention,
An organic base is added for the purpose of promoting the coupling reaction between the diazo compound and the coupler. These organic bases can be used alone or in combination of two or more. Examples of the basic substance include nitrogen-containing compounds such as tertiary amines, piperidines, piperazines, amidines, formamidines, pyridines, guanidines, and morpholines.

Of these, N, N'-bis (3-phenoxy-2-hydroxypropyl) piperazine and 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 N'-
Bis [3- (β-naphthoxy) -2-hydroxypropyl] piperazine, N-3- (β-naphthoxy) -2-hydroxypropyl-N′-methylpiperazine, 1,4-
Piperazines such as bis {[3- (N-methylpiperazino) -2-hydroxy] propyloxy} benzene;
[3- (β-naphthoxy) -2-hydroxy] propylmorpholine, 1,4-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, 1,3-bis [(3-morpholino-2-hydroxy) ) Propyloxy] morpholines such as benzene, piperidines such as N- (3-phenoxy-2-hydroxypropyl) piperidine and N-dodecylpiperidine, guanidines such as triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenyl guanidine, etc. Is preferred.

In the diazo thermosensitive recording material of the present invention, the amount of the coupling component and the basic substance used is preferably 0.1 to 30 parts by mass with respect to 1 part by mass of the diazo compound. In the present invention, in addition to the above-mentioned organic base, a color-forming aid can be added for the purpose of accelerating the color-forming reaction. Color development aids include substances that increase the color density during heating recording or lower the minimum color development temperature, lower the melting point of couplers, basic substances, diazo compounds, etc., and reduce the softening point of the capsule wall. This is for creating a situation in which the diazo compound, the basic substance, the coupler, and the like easily react due to the action of decreasing the activity.

Examples of the color-forming aid used in the diazo thermosensitive recording material of the present invention include phenol derivatives, naphthol derivatives, alkoxy-substituted benzenes, Substituted naphthalenes, hydroxy compounds, amide compounds, sulfonamide compounds and the like can be added. It is considered that these compounds reduce the melting point of the coupling component or the basic substance or improve the heat permeability of the microcapsule wall, thereby enabling a high color density.

The coloring aid used in the diazo thermosensitive recording material of the present invention may be a heat-fusible substance. The heat-meltable substance is
Melting point 50 ° C which is solid at room temperature and melts by heating
A substance at a temperature of up to 150 ° C. that dissolves a diazo compound, a coupling component, or a basic substance. Specific examples of these compounds include carboxylic amides, N-substituted carboxylic amides, ketone compounds, urea compounds, esters and the like. In the recording material of the present invention,
It is preferable to use the following known antioxidants for the purpose of improving the fastness of the thermochromic image to light and heat or reducing yellowing of unprinted portions after fixing by light.

The above antioxidants are described, for example, in European Patent Publication Nos. 2,223,939 and 3,094.
Nos. 01, 309402 and 31055
No. 1, No. 310552, No. 559416
No. 3,435,443, JP-A-54-48535, JP-A-62-262047, JP-A-63-113536, and JP-A-63-16335.
No. 1, JP-A-2-262654, JP-A-2-262654
No. 71262, JP-A-3-121449, JP-A-5-61166, JP-A-5-119449, U.S. Pat. No. 4,814,262, U.S. Pat. No. 4,980,275, and the like.

Further, it is also effective to use various known additives already used in heat-sensitive recording materials and pressure-sensitive recording materials. Specific examples of these antioxidants include JP-A-60-107384 and JP-A-60-107383.
JP-A-60-125470, JP-A-60-125
Nos. 471, 60-125472, 60-
Nos. 287485, 60-287486, 60-287487, 60-287488, 61-160287, and 61-18548.
No. 3, No. 61-211079, No. 62-14
Nos. 6678, 62-146680, 62
-146679, 62-282885,
JP-A-63-051174, JP-A-63-89877, JP-A-63-88380, and JP-A-63-088381
JP-A-63-203372 and JP-A-63-224.
Nos. 989 and 63-251282, 63-251
267594, 63-182484, JP-A-01-239282 and 04-291885
JP, JP-A-04-291684, JP-A-05-188
Nos. 687, 05-188686 and 05-188.
No. 110490, No. 05-1108437,
05-170361, JP-B-48-04329
No. 4, JP-A-48-033212 and the like.

Specifically, 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2 -Dihydroquinoline, 6-ethoxy-1-
Phenyl-2,2,4-trimethyl-1,2,3,4-
Tetrahydroquinoline, 6-ethoxy-1-octyl-
2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, nickel cyclohexanoate, 2,2-bis-4-hydroxyphenylpropane, 1,1-bis-4
-Hydroxyphenyl-2-ethylhexane, 2-methyl-4-methoxy-diphenylamine, 1-methyl-2
-Phenylindole and the like.

The addition amount of these antioxidants is preferably from 0.05 to 100 parts by mass, more preferably from 0.2 to 30 parts by mass, per 1 part by mass of the diazo compound. The above-mentioned known antioxidants may be used in a microcapsule together with the diazo compound, or may be used together with a coupling component, a basic substance, and other color-forming aids, as a solid dispersion, or with a suitable emulsifying aid. It can be used in the form of an emulsion or both. Of course, antioxidants can be used alone or in combination. Further, it can be added to or present in the protective layer.

These antioxidants need not be added to the same layer. Further, when a plurality of these antioxidants are used in combination, they are structurally classified like anilines, alkoxybenzenes, hindered phenols, hindered amines, hydroquinone derivatives, phosphorus compounds, sulfur compounds, and have different structures from each other. May be combined, or a plurality of the same may be combined.

In the present invention, L in the general formula (1)
Is a substituent other than a hydrogen atom, and represents a substituent which can be eliminated upon coupling with a diazonium salt compound, it is preferable to use a reducing agent or a hydrogen donor together. As the reducing agent and the hydrogen donor, general ones can be used, and examples thereof include the following compounds.

Embedded image

The coupling component used in the present invention comprises:
It can be used as a solid dispersion with a water-soluble polymer by a sand mill or the like together with a basic substance, other color-forming auxiliary, etc., but it is particularly preferable to use it as an emulsion with a suitable emulsifying auxiliary. Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (for example, see JP-A-59-190886). In this case, the coupling component, the basic substance, and the coloring aid are added to the water-soluble polymer solution in an amount of 5 to 40% by mass. The dispersed or emulsified particle size is preferably 10 μm or less.

The diazo thermosensitive recording material of the present invention contains a free radical generator (a compound capable of generating free radicals upon irradiation with light) for use in a photopolymerizable composition for the purpose of reducing yellowing of the background after fixing. ) Can be added. Such free radical generators include aromatic ketones, quinones, benzoin, benzoin ethers, azo compounds, organic disulfides, acyl oxime esters, and the like.
The amount to be added is preferably 0.01 to 5 parts by mass of the free radical generator per 1 part by mass of the diazo compound.

Similarly, for the purpose of reducing yellowing, a polymerizable compound having an ethylenically unsaturated bond (hereinafter, referred to as a vinyl monomer) may be used. The vinyl monomer is a compound having at least one ethylenically unsaturated bond (vinyl group, vinylidene group, etc.) in its chemical structure, and has a chemical form of a monomer or prepolymer. Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohols, and amide compounds of unsaturated carboxylic acids and aliphatic polyamines.

The vinyl monomer is preferably used in a ratio of 0.2 to 20 parts by mass with respect to 1 part by mass of the diazo compound. The free radical generator and the vinyl monomer may be used in a microcapsule together with a diazo compound. In the present invention, in addition to the above-mentioned materials, citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid and the like can be added as an acid stabilizer.

The diazo thermosensitive recording material of the present invention comprises a microcapsule containing a diazo compound, a coupling component,
And a coating solution containing an organic base and other additives is prepared and coated with a bar on a support such as paper or a synthetic resin film,
1. Coating and drying by a coating method such as blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, curtain coating, etc.
It is preferable to provide a heat-sensitive layer of 5 to 30 g / m2.

In the diazo thermosensitive recording material of the present invention,
The microcapsules, the coupling component, the base, and the like may be contained in the same layer, but may have a laminated structure in which they are contained in different layers. Further, after providing an intermediate layer as described in Japanese Patent Application No. 59-177669 on a support, a heat-sensitive layer can be applied.

As the support used in the diazo thermosensitive recording material of the present invention, any paper support used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copy paper, etc. can be used. Neutral paper having a pH of 5 to 9 sized with a neutral sizing agent such as alkyl ketene dimer (described in Japanese Patent Application No. 55-14281);
No. 7-116687, satisfying the relationship between the Stöckicht sizing degree and the metric basis weight, and having a Beck smoothness of 90.
Seconds or more, the optical surface roughness described in JP-A-58-136492 is 8 μm or less, and the thickness is 30 to 15 μm.
Paper having a density of 0.9 g / cm @ 3 or less and an optical contact ratio of 15% as described in JP-A-58-69091.
The above-mentioned paper, a paper which is prepared from pulp beaten to 400 cc or more at a Canadian standard freeness (JIS P8121) described in JP-A-58-69097 to prevent the penetration of a coating solution, 58. A paper improved in color density and resolution by using a glossy surface of a base paper made by a Yankee machine described in JP-A-58-65695 as a coated surface. JP-A-59-
Paper obtained by subjecting a base paper described in JP-A-35985 to corona discharge treatment to improve coating suitability can also be used.

The synthetic resin film used as the support does not deform even by heating during the development process and can be arbitrarily selected from known materials having dimensional stability. Examples of such a film include polyester films such as polyethylene terephthalate and polybutylene terephthalate, cellulose derivative films such as cellulose triacetate film, polystyrene films, polypropylene films, and polyolefin films such as polyethylene. These can be used alone or bonded together. As the thickness of the support,
Those having a thickness of 20 to 200 μm are used.

In the diazo thermosensitive recording material of the present invention,
If necessary, when printing with a thermal head on the heat-sensitive recording layer, polyvinyl alcohol or the like is used as a main component on the heat-sensitive recording layer for the purpose of preventing sticking, head contamination, etc., and imparting water resistance to the recording material. It is preferable to further provide a protective layer (hereinafter, simply referred to as a protective layer) to which various pigments and release agents are added.

When the recording surface of the thus obtained diazo thermosensitive recording material of the present invention is heated by a thermal head or the like,
The capsule wall of polyurea or polyurethane is softened, and the coupler and the base compound outside the capsule enter the capsule and develop color. After recording, irradiation with light having an absorption wavelength of the diazo compound causes the diazo compound to decompose and lose reactivity with the coupler, so that the image is fixed.

As the fixing light source, various fluorescent lamps, xenon lamps, mercury lamps and the like are used. It is preferable that this emission spectrum substantially coincides with the absorption spectrum of the diazo compound used in the recording material, since light can be fixed efficiently. Further, the heat-sensitive recording material of the present invention may be exposed using a manuscript to decompose a diazo compound other than the image forming portion to form a latent image, and then heat and develop the recording material to obtain an image. it can.

[0087]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. [Synthesis of Barbituric Acid Derivative] <Synthesis Example of Exemplified Compound B-1>N-dodecyl-N'-octadecylurea 20 g (37.1 mmol), malonic acid 4.2 g (40.8 mmol), acetic anhydride 11.3 g
(111.8 mmol) and 60 ml of ethyl acetate were mixed and refluxed for 3 hours. Then, methanol 120ml
And the resulting crystals are collected by filtration to give Exemplified Compound B-11.
1.8 g (52%) were obtained. The identification result of the obtained compound B-1 is shown below. ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.88
(T, 6H), 1.2-1.4 (m, 48H), 1.5
-1.7 (m, 4H), 3.65 (s, 2H), 3.8
4 (t, 4H)

<Synthesis Example of Exemplified Compound B-2> 15 g (31.2 mmol) of N-dodecyl-N'-octadecyloxycarbonylmethylurea and 3.6 g of malonic acid (3
4.3 mmol), 9.5 g of acetic anhydride (93.6 mmol)
l) and 40 ml of ethyl acetate were mixed and refluxed for 3 hours. Thereafter, 50 ml of methanol was added, and the resulting crystals were collected by filtration to obtain 11.8 g (69%) of Exemplified Compound B-2. The identification result of the obtained compound B-2 is shown below. ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.88
(T, 6H), 1.2-1.4 (m, 48H), 1.5
-1.7 (m, 4H), 3.7 (s, 2H), 3.85
(T, 2H), 4.15 (t, 2H), 4.6 (s, 2
H)

<Synthesis Example of Exemplified Compound B-3> 28.4 g (50 mmol) of N-decyloxycarbonylmethyl-N'-octadecyloxycarbonylmethylurea, 5.7 g (55 mmol) of malonic acid, 11.2 g of acetic anhydride
(110 mmol) and 50 ml of ethyl acetate were mixed and refluxed for 3 hours. Thereafter, 100 ml of methanol was added, and the resulting crystals were collected by filtration, and 20 g of Exemplified Compound B-3 was obtained.
(63%). The results of identifying the obtained compound B-3 are shown below. ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.88
(T, 6H), 1.2-1.4 (m, 44H), 1.6
-1.8 (m, 4H), 3.8 (s, 2H), 4.2
(T, 4H), 4.6 (s, 4H)

[Preparation and evaluation of diazo thermosensitive recording material] <Example 1> (Preparation of capsule liquid A) The diazo compound (A-1) 2.8 described as a specific example in the specification was used in 19 parts of ethyl acetate.
And 10 parts of tricresyl phosphate were added and mixed uniformly. Next, 7.6 parts of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) was added to this mixed solution as a wall agent, and the mixture was uniformly mixed to obtain Liquid I.

The obtained working solution was added to an aqueous phase consisting of 46.1 parts of an 8% by mass aqueous solution of phthalated gelatin, 17.5 parts of water, and 2 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate. 10,000r. p. m for 10 minutes. After adding 20 parts of water to the obtained emulsion and homogenizing, an encapsulation reaction was carried out at 40 ° C. for 3 hours with further stirring to obtain a capsule liquid A. The particle size of the capsule is 0.
It was 35 μm.

(Preparation of (Copper / Base Emulsion) B) In 8 parts of ethyl acetate, 4 parts of the coupler compound (B-3) described as a specific example in the specification, and triphenylguanidine 2
Part, tricresyl phosphate (0.64 part) and maleic acid diethyl ester (0.32 part) were dissolved to obtain solution II. Solution II was added to an aqueous phase obtained by uniformly mixing 32 parts of a 15% by mass aqueous solution of lime-processed gelatin, 5 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate, and 30 parts of water at 40 ° C. Then, using a homogenizer, at 40 ° C., 10,000 r. p. m. For 10 minutes. The obtained emulsion was stirred at 40 ° C. for 2 hours, and after removing ethyl acetate, the masses of the volatilized ethyl acetate and water were supplemented with water to obtain (coupler / base emulsion) B.

(Preparation of Coating Liquid C) After uniformly mixing 6 parts of capsule liquid A, 4.4 parts of water, and 1.9 parts of a 15% by mass aqueous solution of lime-processed gelatin at 40 ° C., (coupler / base emulsification) Liquid) B8.3 parts was added and uniformly mixed to obtain a thermosensitive recording layer coating liquid C.

(Preparation of Protective Layer Coating Solution D) A protective layer coating solution D was obtained by uniformly mixing 32 parts of a 10% aqueous solution of polyvinyl alcohol (degree of polymerization 1700, saponification degree 88%) and 36 parts of water.

(Coating) On a photographic paper support obtained by laminating polyethylene on a high-quality paper, a thermosensitive recording layer coating solution C and a protective layer coating solution D were sequentially coated with a wire bar and dried at 50 ° C. The desired diazo thermosensitive recording material was obtained. The coating amounts as solids were 6.4 g / m ² and 1.05 g, respectively.
/ M ² .

(Coloring and Fixing Test) Using a thermal head (KST type) manufactured by Kyocera Corporation, the applied power and pulse width to the thermal head were determined so that the recording energy per unit area was 0 to 40 mJ / mm ^2. ,
After an image was obtained by thermal printing on the diazo thermosensitive recording layer, the entire surface was irradiated with an ultraviolet lamp having an emission center wavelength of 365 nm and an output of 40 W for 15 seconds. About the obtained sample, the density of the color-developed portion and the background portion was measured using a Macbeth densitometer.

(Comparative test of raw preservability) The test of raw preservability was performed by comparing a diazo thermosensitive recording sheet stored at room temperature with a sheet at 60 ° C.
The difference between the color density and the background density of the diazo thermosensitive recording sheet forcibly stored for 72 hours under the condition of 0% RH was measured and compared. The change in coloring density was measured by a Macbeth reflection densitometer.

(Light fastness test)
The fixed sample was subjected to 32,000 Lux. Was used for continuous light irradiation for 24 hours using a fluorescent light fastness tester, and an image portion and a background portion were subjected to a discoloration test. In the measurement, a change in density at an initial reflection density of about 1.1 using a Macbeth densitometer was examined.

Example 2 The compound (A) used in Example 1
A recording material was prepared and an image was formed by performing the same operation as in Example 1 except that a capsule liquid was obtained using compound (A-2) instead of -1). Using a Macbeth densitometer, the density of the color-developed portion and the background was measured. Example 3 A recording material was prepared in the same manner as in Example 1 except that a capsule liquid was obtained using the compound (A-3) instead of the compound (A-1) used in Example 1. Fabricated to form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured.

Example 4 The compound (A) used in Example 1
A recording material was prepared and an image was formed by performing the same operation as in Example 1 except that a capsule liquid was obtained using compound (A-4) instead of -1). Using a Macbeth densitometer, the density of the color-developed portion and the background was measured. <Example 5> A recording material was prepared in the same manner as in Example 1 except that a capsule liquid was obtained using the compound (A-5) instead of the compound (A-1) used in Example 1. Fabricated to form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured.

Comparative Example 1 Compound (A) used in Example 1
-1) is replaced by 4-N, N-dihexylamino-2
Example 1 except that a capsule liquid was obtained using hexyloxybenzenediazonium hexafluorophosphate
By performing the same operation as described above, a recording material was prepared to form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured. <Comparative Example 2> Instead of the compound (A-1) used in Example 1, 4- [N- (4-methoxyphenoxyethyl),
[N-Hexyl] amino-2-hexyloxybenzenediazonium hexafluorophosphate, except that a capsule solution was obtained, and the same operation as in Example 1 was carried out to produce a recording material and form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background portion was measured.

<Comparative Example 3> Compound (A) used in Example 1
Example 1 was repeated except that a capsule solution was obtained using 4- [N- (4-methoxyphenoxypropyl), N-hexyl] amino-2-hexyloxybenzenediazonium hexafluorophosphate instead of -1). The same operation was performed to prepare a recording material and form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured.

The test results of the raw preservability (the coloring density of the image portion and the background portion before and after forced storage) of the recording materials prepared in Examples 1 to 5 and Comparative Examples 1 to 3 are shown below.

[0104]

[Table 1]

The test results of the storability (light fastness) of the color-developed portions of the recording materials prepared in Examples 1 to 5 and Comparative Examples 1 to 3 (color density of the image portion and the background portion before and after light irradiation) are shown below. Show.

[0106]

[Table 2]

Example 6 The compound (B) used in Example 1
The same operation as in Example 1 was performed except that a coupler / base emulsion was obtained using compound (B-1) instead of -3),
A recording material was prepared to form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured. <Example 7> The same operation as in Example 1 was performed except that a coupler / base emulsion was obtained using compound (B-2) instead of compound (B-3) used in Example 1, A recording material was prepared to form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured.

Example 8 The compound (B) used in Example 1
In the same manner as in Example 1 except that a compound (B-43) was used instead of -3) and 2 parts of a phenol compound (R-1) as a reducing agent was added to obtain a coupler / base emulsion. The operation was performed to prepare a recording material and form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured. <Example 9> The same operation as in Example 1 was performed except that a coupler / base emulsion was obtained using compound (B-44) instead of compound (B-3) used in Example 1, A recording material was prepared to form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured.

<Example 10> The same operation as in Example 1 was carried out except that a coupler / base emulsion was obtained using compound (B-37) instead of compound (B-3) used in Example 1. And a recording material was prepared to form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured. <Comparative Example 4> A coupler / base emulsion was prepared using 5- (2-tetradecyloxyphenyl) -cyclohexane-1,3-dione instead of the compound (B-3) used in Example 1. Other than that, the same operation as in Example 1 was performed to prepare a recording material and form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured.

<Comparative Example 5> Compound (B) used in Example 1
A recording material was prepared in the same manner as in Example 1 except that a coupler / base emulsion was obtained using 1-phenyl-3-octyloxycarbonylpyrazoli-5-one instead of -3). To form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured. <Comparative Example 6> Instead of the compound (B-3) used in Example 1, N- (2 ', 5'-dibutyloxy-4'-chlorophenyl) -4,4-dimethyl-3-oxopentamide was used. Was used to obtain a coupler / base emulsion, and the same operation as in Example 1 was carried out to prepare a recording material and form an image. Using a Macbeth densitometer, the density of the color-developed portion and the background was measured.

The raw storage test results (the color density of the image area and the background area before and after forced storage) of the recording materials prepared in Examples 6 to 10 and Comparative Examples 4 to 6 are shown below.

[0112]

[Table 3]

The test results of the storability (light fastness) of the colored portions of the recording materials prepared in Examples 6 to 10 and Comparative Examples 4 to 6 (color density of the image portion and the background portion before and after light irradiation) are shown below. Show.

[0114]

[Table 4]

From the results shown in Tables 1 to 4, it was proved that the diazo thermosensitive recording material containing the barbituric acid derivative of the present invention was excellent in raw storability and image storability.

[0116]

As described above, according to the present invention,
A barbituric acid derivative useful for a diazo thermosensitive recording material can be provided, and a diazo thermosensitive recording material having excellent raw storability and image storability can be provided by using the same.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yosuke Takeuchi 200 Fujinaka Film Co., Ltd., Fujinomiya City, Shizuoka Prefecture (72) Inventor Daisuke Arioka 200 Onakazato Fujinaka City, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd. 72) Inventor Takami Ikeda 200, Onakazato, Fujinomiya City, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. (72) Inventor Sachiko 200, Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H026 BB42 BB43

Claims (8)

[Claims] 1. A barbituric acid derivative represented by the following general formula (1). Embedded image In the formula, R ¹ and R ² each represent a different substituent, and each represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent. L represents a hydrogen atom or a substituent capable of leaving upon coupling with a diazo compound. 2. The barbituric acid derivative according to claim 1, represented by the following general formula (2). Embedded image In the formula, R ³ and R ⁴ are each independently, R ³ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁴ is a substituent And an aralkyl group which may have a substituent. 3. The barbituric acid derivative according to claim 2, represented by the following general formula (3). Embedded image In the formula, R ⁵ and R ⁶ are each independently, R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁶ is a substituent And an aralkyl group which may have a substituent. 4. A diazo thermosensitive recording material having a thermosensitive recording layer containing a diazo compound, a coupling component and an organic base on a support, wherein the coupling component is
A diazo thermosensitive recording material comprising at least one compound represented by the general formula (1). Embedded image In the formula, R ¹ and R ² each represent a different substituent, and each represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent. L represents a hydrogen atom or a substituent capable of leaving upon coupling with a diazo compound. 5. A diazo thermosensitive recording material having a thermosensitive recording layer containing a diazo compound, a coupling component, and an organic base on a support, wherein the coupling component is:
A diazo thermosensitive recording material comprising at least one compound represented by the general formula (2). Embedded image In the formula, R ³ and R ⁴ are each independently, R ³ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁴ is a substituent And an aralkyl group which may have a substituent. 6. A diazo thermosensitive recording material in which a thermosensitive recording layer containing a diazo compound, a coupling component and an organic base is provided on a support, wherein the coupling component is:
A diazo thermosensitive recording material comprising at least one compound represented by the general formula (3). Embedded image In the formula, R ⁵ and R ⁶ are each independently, R ⁵ represents a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group which may have a substituent, and R ⁶ is a substituent And an aralkyl group which may have a substituent. 7. The diazo compound represented by the following general formula (4)
The diazo heat-sensitive recording material according to any one of claims 4 to 6, comprising at least one compound represented by the following formula: Embedded image In the formula, R ⁷ , R ⁸ and R ⁹ are each independently and represent an alkyl group which may have a substituent or an aryl group which may have a substituent. X ^- represents an anion. 8. The thermal recording material according to claim 4, wherein the diazo compound is encapsulated in microcapsules.