JP2005298445A - Heterocyclic compound and recording material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a recording material having excellent image light resistance with time and excellent color purity of a recording part. <P>SOLUTION: The recording material has a recording layer containing a compound represented by formula (1) (X is an oxygen atom or a sulfur atom; R<SP>1</SP>and R<SP>2</SP>are each a substituent group; R<SP>3</SP>is an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group; m is an integer of 0-4; n is an integer of 0-3; when m or n is an integer of ≥2, a plurality of R<SP>1</SP>or R<SP>2</SP>may be mutually the same or different and may be mutually bonded to form a ring; o and p are each independently 0 or 1; o+p is 1 or 2; when n≥1, R<SP>2</SP>and R<SP>3</SP>may be mutually bonded to form a ring) on a substrate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel compound useful as a color forming component to be combined with a diazo compound or the like, and a yellow color recording material using the same, particularly excellent in image light resistance with time and having good color purity.

  The diazo compound reacts with a compound called “coupler” such as a phenol derivative or a compound having an active methylene group to form an azo dye. In addition, diazo compounds have the property of decomposing by light irradiation and losing their activity. Conventionally, diazo compounds have been used for a long time as optical recording materials typified by diazocopy by utilizing this property (for example, see Non-Patent Document 1).

  In addition, diazo compounds have recently been applied to recording materials that require image fixing. As a typical example, diazo compounds and coupler compounds are heated in accordance with an image signal and reacted to form an image. A light-fixing type heat-sensitive recording material that fixes an image by light irradiation has been proposed (see, for example, Non-Patent Document 2).

  However, these recording materials have a drawback that the shell life as a recording material is short because the active diazo compound gradually decomposes by heat and loses reactivity even in a dark place. In order to remedy this drawback, a method has been proposed in which a diazo compound is encapsulated in a microcapsule and the diazo compound is isolated from a component that promotes decomposition such as water or base. By this method, the shell life of the recording material can be dramatically improved (for example, see Non-Patent Document 3).

  On the other hand, a microcapsule having a glass transition temperature higher than room temperature exhibits a substance non-permeable property at the room temperature, whereas the microcapsule exhibits a material permeability above the glass transition temperature. It can be preferably used. That is, a thermosensitive recording material in which a thermoresponsive microcapsule containing a diazo compound and a thermosensitive recording layer containing a coupler compound and a base are coated on a support, (1) Improved long-term stable storage of the diazo compound; 2) Colored image formation by heating and (3) Image fixing by light irradiation are possible.

In recent years, such a heat-sensitive recording material has been improved in function as a recording material for forming a multicolor image (see Patent Documents 1 and 2). Therefore, it is desired to improve the light resistance of the image area and non-image area after recording.
For example, a method of using an acetoacetanilide coupler compound as a coupler for obtaining a yellow image has been proposed (see, for example, Patent Document 3). However, the acetoacetanilide coupler compound has a drawback that the light resistance of the image area is low.
Japanese Patent Laid-Open No. 04-135787 Japanese Patent Laid-Open No. 04-144784 Japanese Patent Laid-Open No. 04-201483 The Photographic Society of Japan “Basics of Photographic Engineering: Non-Silver Salt Photography”, Corona, 1982, pages 89-117, 182-101 Koji Sato, “Journal of the Institute of Image Electronics Engineers”, Vol. 11, No. 4, 1982, pp. 290-296 Tomomasa Usami, “Journal of the Electrophotographic Society” Vol. 26, No. 2, 1987, 115-125

  Accordingly, an object of the present invention is to provide a recording material having good image light resistance and color purity over time after recording.

In view of such circumstances, the present inventor has conducted intensive research, and as a result, has found a novel compound in which a group having a 1,3-dicarbonyl structure is introduced into the substituent of the anilide moiety. It has been found that a yellow color-forming recording material having good image light resistance and color purity can be obtained, and the present invention has been completed.
That is, the present invention provides the following.

  <1> A compound represented by the following general formula (1) or a tautomer thereof.

[In general formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² represent a substituent, R ³ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. M represents an integer of 0 to 4, n represents an integer of 0 to 3, and when m or n represents an integer of 2 or more, a plurality of R ^{1 s} or R ^{2 s} are the same or different from each other. They may be linked to each other to form a ring. o and p each independently represent 0 or 1, and o + p is 1 or 2. When n ≧ 1, R ² and R ³ may be connected to each other to form a ring. ]

  <2> A recording material having a recording layer containing a compound represented by the following general formula (1) or a tautomer thereof on a support.

[In general formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² represent a substituent, R ³ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. M represents an integer of 0 to 4, n represents an integer of 0 to 3, and when m or n represents an integer of 2 or more, a plurality of R ^{1 s} or R ^{2 s} are the same or different from each other. They may be linked to each other to form a ring. o and p each independently represent 0 or 1, and o + p is 1 or 2. When n ≧ 1, R ² and R ³ may be connected to each other to form a ring. ]

  <3> A recording material having a recording layer containing a compound represented by the following general formula (1) or a tautomer thereof and a diazo compound on a support.

[In general formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² represent a substituent, R ³ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. M represents an integer of 0 to 4, n represents an integer of 0 to 3, and when m or n represents an integer of 2 or more, a plurality of R ^{1 s} or R ^{2 s} are the same or different from each other. They may be linked to each other to form a ring. o and p each independently represent 0 or 1, and o + p is 1 or 2. When n ≧ 1, R ² and R ³ may be connected to each other to form a ring. ]

  <4> The recording material according to <3>, wherein the diazo compound is a diazonium salt represented by the following general formula (2).

[In General Formula (2), R ²⁴ and R ²⁶ each independently represents an alkyl, aryl, heterocyclic ring or acyl group which may have a substituent. R ²⁵ represents an alkyl, aryl, alkylsulfonyl, arylsulfonyl, acyl or heterocyclic group which may have a substituent. Y ²¹ represents an oxygen atom, sulfur atom or nitrogen atom, Y ²² represents an oxygen atom, sulfur atom or single bond, and Y ²³ represents an oxygen atom, sulfur atom or hydrogen atom. However, R ²⁶ does not exist when Y ²³ is a hydrogen atom. R ²⁴ and R ²⁶ may be bonded to each other to form a ring. X ⁻ represents an anion. ]

<5> The recording material according to <3> or <4>, wherein the diazo compound is encapsulated in microcapsules.
<6> The recording material according to <5>, wherein the capsule wall forming the microcapsule contains polyurethane and / or polyurea as a constituent component.

  When the compound of the present invention is used as a coupler in a recording material, a yellow color-type heat-sensitive recording material having excellent image light resistance with time and good color purity of a recording portion can be obtained.

Hereinafter, the present invention will be described in detail.
<< Compound Represented by Formula (1) or Tautomer thereof >>
First, the compound of the present invention or a tautomer thereof will be described.
The present invention is a compound represented by the following general formula (1) or a tautomer thereof.

[In general formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² represent a substituent, R ³ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. M represents an integer of 0 to 4, n represents an integer of 0 to 3, and when m or n represents an integer of 2 or more, a plurality of R ^{1 s} or R ^{2 s} are the same or different from each other. They may be linked to each other to form a ring. o and p each independently represent 0 or 1, and o + p is 1 or 2. When n ≧ 1, R ² and R ³ may be connected to each other to form a ring. ]

In general formula (1), X represents an oxygen atom or a sulfur atom, and a sulfur atom is preferred.
In the general formula (1), examples of the substituent represented by R ¹ and R ² include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and carbon. Aryloxy group having 6 to 30 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, aryloxycarbonyl group having 7 to 30 carbon atoms, acyloxy group having 2 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, carbon number An amide group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfamoyl group having 1 to 30 carbon atoms, a sulfonamido group having 1 to 20 carbon atoms, a halogen atom, an alkylthio group having 1 to 20 carbon atoms, and 6 carbon atoms To 30 arylthio groups, C1 to C20 alkylsulfonyl groups, C6 to C30 arylsulfonyl groups, amino groups, cyano groups, hydrazino groups , Hydroxyamino group, ureido group, thioureido group and the like.

  Among these, examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl, sec-butyl group, t-butyl group, and n-pentyl. Group, isopentyl group, 3-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, t-octyl group, nonyl group, 3,5,5-trimethylhexyl group, decyl group , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, n-hexadecyl group, 2-hexyldecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, cyclohexyl group, cyclopentyl group and the like.

Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group and a naphthyl group.
Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, t-butyloxy group, n-hexyloxy group, and n-octyloxy group. , 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-dodecyloxy group, cyclohexyloxy group, among which an alkyloxy group having 1 to 10 carbon atoms is particularly preferable. A methoxy group, an ethoxy group, and an n-hexyloxy group are more preferable.

  Examples of the aryloxy group having 6 to 30 carbon atoms include a phenyloxy group and a naphthyloxy group. Among them, an aryloxy group having 6 to 15 carbon atoms is more preferable.

  Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group And octadecyloxycarbonyl group.

  Examples of the aryloxycarbonyl group having 7 to 30 carbon atoms include 2-methylphenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2,6-dimethylphenyloxycarbonyl group, and 2,4,6-trimethylphenyloxycarbonyl. Group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 4-chlorophenyloxycarbonyl group, 4-butoxyphenyloxycarbonyl group and the like.

  Examples of the acyloxy group having 2 to 20 carbon atoms include acetyloxy group, propanoyloxy group, butanoyloxy group, hexanoyloxy group, octanoyloxy group, 2-ethylhexanoyloxy group, dodecanoyloxy group, Examples include benzoyloxy group, 4-methoxybenzoyloxy group, 2-methoxybenzoyloxy group, 4-chlorobenzoyloxy group, 2-chlorobenzoyloxy group, 4-methylbenzoyloxy group and 2-methylbenzoyloxy group. Of these, an acyloxy group having 1 to 10 carbon atoms is preferable, and a propanoyloxy group, a butanoyloxy group, and a hexanoyloxy group are particularly preferable.

  The acyl group having 2 to 20 carbon atoms is particularly preferably one having 2 to 10 carbon atoms. The portion other than the carbonyl group of the acyl group may be any of an aliphatic group, an aromatic group, and a heterocyclic group. As the acyl group, in particular, acetyl group, propanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzoyl group, phenoxyacetyl group, 2-ethylhexanoyl group, 2,5-dibutoxybenzoyl Group, 2-naphthoyl group, butoxyethanoyl group, trichloroethanoyl group, 4-nitrobenzoyl group, 4-phenoxybenzoyl group, 4-cyanobenzoyl group, more preferably ethanoyl group, propanoyl group, butanoyl group, hexanoyl Group, 2-ethylhexanoyl group, octanoyl group, decanoyl group, benzoyl group, 4-chlorobenzoyl group, 4-nitrobenzoyl group, and particularly preferably ethanoyl group, propanoyl group, butanoyl group, hexanoyl group, 2-ethyl Kisanoiru group, and a benzoyl group.

  As the carbamoyl group, those having 1 to 20 carbon atoms are preferable, and those having 1 to 10 carbon atoms are particularly preferable. As the carbamoyl group, in particular, ethylcarbamoyl group, butylcarbamoyl group, hexylcarbamoyl group, diethylcarbamoyl group, ethoxyethylcarbamoyl group, phenylcarbamoyl group, tolylcarbamoyl group, benzylcarbamoyl group, dimethylcarbamoyl group, dibutylcarbamoyl group, cyclohexylcarbamoyl group Group, 2-ethylhexylcarbamoyl group, decylcarbamoyl group, methylethylcarbamoyl group, methoxyethylcarbamoyl group, naphthylcarbamoyl group, 4-cyanophenylcarbamoyl group, 4-nitrophenylcarbamoyl group, more preferably dimethylcarbamoyl group, Ethylcarbamoyl group, dibutylcarbamoyl machine, cyclohexylcarbamoyl group, phenylcarbamoyl group, 2-ethyl Examples include a silcarbamoyl group, a decylcarbamoyl group, a methylethylcarbamoyl group, a benzylcarbamoyl group, a methoxyethylcarbamoyl group, and a naphthylcarbamoyl group, and particularly preferably a dimethylcarbamoyl group, an ethylcarbamoyl group, a dibutylcarbamoyl group, a cyclohexylcarbamoyl group, a phenyl group. A carbamoyl group, a 2-ethylhexylcarbamoyl group, and a decylcarbamoyl group may be mentioned.

  The sulfamoyl group preferably has 0 to 30 carbon atoms, and particularly preferably has 1 to 10 carbon atoms. As the sulfamoyl group, a diethylsulfamoyl group, an octylsulfamoyl group, a methyldodecylsulfamoyl group, a phenylsulfamoyl group, a methoxyphenylsulfamoyl group, and a tolylsulfamoyl group are particularly preferable.

  The sulfonamide group may be either an aliphatic or aromatic sulfonamide group, and the carbon number thereof is preferably 1-20, particularly 1-10. Examples of the sulfonamide group include methanesulfonamide group, butanesulfonamide group, octanesulfonamide group, decanesulfonamide group, 2-ethylhexylsulfonamide group, phenylsulfonamide group, 2-butoxyphenylsulfonamide group, and 4chlorophenylsulfone. An amide group, 2,5-diethoxysulfonamide group, and 4-hexyloxyphenylsulfonamide group are preferable.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom is preferable.

  Examples of the alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-butylthio group, t-butylthio group, n-hexylthio group, n-octylthio group, 2-ethylhexylthio group, n-dodecylthio group, cyclohexylthio group. Groups. In particular, a methylthio group, an ethylthio group, a t-butylthio group, an n-octylthio group, a 2-ethylhexylthio group, an n-dodecylthio group, and the like are preferable. Further, an alkylthio group having 1 to 6 carbon atoms is more preferable.

  Examples of the arylthio group having 6 to 30 carbon atoms include phenylthio and naphthylthio. Further, an arylthio group having 6 to 15 carbon atoms is more preferable.

  Examples of the alkylsulfonyl group having 1 to 20 carbon atoms include a methylsulfonyl group, an ethylsulfonyl group, an n-butylsulfonyl group, an n-hexylsulfonyl group, an n-octylsulfonyl group, a 2-ethylhexylsulfonyl group, and an n-dodecylsulfonyl group. Group, a cyclohexylsulfonyl group, and a methylsulfonyl group, an n-hexylsulfonyl group, an n-octylsulfonyl group, a 2-ethylhexylsulfonyl group, an n-dodecylsulfonyl group, and the like are particularly preferable. Further, an alkylsulfonyl group having 1 to 10 carbon atoms is more preferable.

  The arylsulfonyl group having 6 to 30 carbon atoms is particularly preferably an arylsulfonyl group having 6 to 10 carbon atoms. Particularly preferable examples of the arylsulfonyl group include a phenylsulfonyl group, a naphthylsulfonyl group, a 4-chlorobenzenesulfonyl group, and a 4-methylbenzenesulfonyl group.

The substituent represented by R ¹ is preferably a hydrogen atom, alkyl group, aryl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group or carbamoyl group, and the substituent represented by R ² is a hydrogen atom, halogen atom or alkyl group. , Aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acyl group, carbamoyl group, amide group, sulfamoyl group, sulfone Amide group, amino group, cyano group, hydrazino group, hydroxyamino group, ureido group and thioureido group are preferred.

The above substituents represented by R ¹ and R ² may further have a substituent, and examples of such a substituent include the following.

A linear or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, isopropyl group, cyclohexyl group), aryl group having 6 to 18 carbon atoms (for example, phenyl group, chlorophenyl group, 2,4- Di-t-amylphenyl group, 1-naphthyl group), aralkyl group having 7 to 18 carbon atoms (for example, benzyl group, anisyl group), alkenyl group having 2 to 20 carbon atoms (for example, vinyl group, 2-methyl) Vinyl group), alkynyl group having 2 to 20 carbon atoms (for example, ethynyl group, 2-methylethynyl group, 2-phenylethynyl group), halogen atom (for example, F, Cl, Br, I), cyano group, hydroxyl group A carboxyl group, an acyl group having 2 to 20 carbon atoms (for example, an acetyl group, a benzoyl group, a salicyloyl group, a pivaloyl group), an aryl group having 1 to 20 carbon atoms. Coxy group (for example, methoxy group, butoxy group, cyclohexyloxy group), C 6-20 aryloxy group (for example, phenoxy group, 1-naphthoxy group, toluoyl group), C 1-20 alkylthio group (for example, , Methylthio group, butylthio group, benzylthio group, 3-methoxypropylthio group), arylthio group having 6 to 20 carbon atoms (for example, phenylthio group, 4-chlorophenylthio group), alkylsulfonyl group having 1 to 20 carbon atoms (for example, , Methanesulfonyl group, butanesulfonyl group), arylsulfonyl group having 6 to 20 carbon atoms (for example, benzenesulfonyl group, paratoluenesulfonyl group), carbamoyl group having 1 to 17 carbon atoms (for example, unsubstituted carbamoyl group, methyl) Carbamoyl group, ethylcarbamoyl group, n-butylcarba Yl group, dimethylcarbamoyl group), amide group having 1 to 16 carbon atoms (for example, acetamido group, benzamide group), acyloxy group having 2 to 10 carbon atoms (for example, acetoxy group, benzoyloxy group), 2 to 10 carbon atoms. Alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group), 5- or 6-membered heterocyclic groups (for example, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, pyrazolyl group, etc.) , A pyrrolidine ring, a piperidine ring, a morpholine ring, a pyran ring, a thiopyran ring, a hetero ring such as a dioxane ring and a dithiolane ring), an amino group, an acylamino group, and the like.

In general formula (1), the substituent represented by R ³ is an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.

The acyl group represented by R ³ preferably has 2 to 20 carbon atoms, and particularly preferably has 2 to 10 carbon atoms. The portion other than the carbonyl group of the acyl group may be an aliphatic, aromatic or heterocyclic group, and may further have a substituent, and examples of the substituent include an alkoxy group, an aryloxy group, and a halogen atom. . As the acyl group, an acetyl group, a propanoyl group, a hexanoyl group, an octanoyl group, a 2-ethylhexanoyl group, and a benzoyl group are particularly preferable.

As the carbamoyl group represented by R ³ , those having 1 to 20 carbon atoms are preferable, and those having 1 to 10 carbon atoms are particularly preferable. The carbamoyl group may have a substituent or may be unsubstituted. Examples of the carbamoyl group include unsubstituted carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group. Groups are preferred.

The alkoxycarbonyl group represented by R ³ may have a substituent. An alkoxycarbonyl group having 2 to 20 carbon atoms is preferred. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, and an octadecyloxycarbonyl group. , Phenyloxyethyloxycarbonyl group, phenyloxypropyloxycarbonyl group, 2,4-di-t-amylphenyloxyethylcarbonyl group, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl group, isostearyl Preferred examples include an oxycarbonyl group.

The alkylsulfonyl group represented by R ³ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, A carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group or a heterocyclic group is preferred.

Examples of the alkylsulfonyl group represented by R ³ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, a benzylsulfonyl group, and a methoxybutylsulfonyl group.

The arylsulfonyl group represented by R ³ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, A carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group or a heterocyclic group is preferred.

Particularly preferred examples of the arylsulfonyl group represented by R ³ include a phenylsulfonyl group, a naphthylsulfonyl group, a 4-chlorobenzenesulfonyl group, and a 4-methylbenzenesulfonyl group.

Of these, R ³ is preferably an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.

  In addition, as a tautomer of the compound represented by the general formula (1), there is a so-called enol type structure in which a carbonyl group and a methylene part are isomerized. Similar isomers exist when the imine structure of the thiazolyl group and the methylene moiety are isomerized. The structures of these isomers are shown below.

[R represents a corresponding substituent]

  Specific examples of the compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (1) can be synthesized using a corresponding aminonitrophenol derivative as a raw material. An example of the synthesis method is shown below.

  That is, using a nitrobenzene derivative in which a hydroxyl group and an amino group are introduced at respective desired positions as raw materials, the corresponding acylation, sulfonylation, urealation, and urethanization reactions are performed on the amino group in the first stage of the reaction. Subsequently, the target compound can be synthesized by reducing the nitro group to an amino group constructed by anilide into cyanoacetate, followed by coupling into a heterocycle.

<Recording material>
The recording material of the present invention is characterized in that it has at least one recording layer containing a coupler on a support, and the compound represented by the above general formula (1) is used as the coupler. Moreover, it is preferable to use a diazo compound with a coupler. As the recording material of the present invention, a heat-sensitive recording material having a heat-sensitive recording layer having a color-developing method, a pressure-sensitive recording material having a pressure-sensitive recording layer having a color-developing method, and a heat forming a latent image by light. Examples thereof include a heat-sensitive photothermographic recording material. Hereinafter, a recording material having a thermal recording layer (thermal recording material) will be described as an example of the recording material of the present invention, but the present invention is not limited to this.

<Recording layer>
The recording layer in the present invention contains at least the compound represented by the above general formula (1) and a diazo compound, and the diazo compound is preferably contained in a microcapsule. Moreover, you may contain various additives, such as an organic base and a coloring aid, as needed.

(coupler)
As described above, the recording layer in the present invention contains the compound represented by the general formula (1) as a coupler. The total content of couplers in the recording layer is preferably 0.2 to 8 mol, more preferably 0.5 to 4 mol, per 1 mol of the diazo compound. When the total coupler content is less than 0.2 mol per 1 mol of diazo compound, sufficient color development may not be obtained, and when it exceeds 8 mol per 1 mol of diazo compound, the coating suitability deteriorates. There is.

  In the present invention, together with the compound represented by the general formula (1), for the purpose of adjusting the hue, a known coupler that forms a dye by coupling with a diazo compound in a basic atmosphere as necessary. It can also be used together. When the compound represented by the general formula (1) and a known coupler are used in combination, 50% by mass or more of all the couplers contained in the recording layer is preferably the compound represented by the general formula (1). More preferably, it is 70 mass% or more.

  Examples of the known couplers include so-called active methylene compounds having a methylene group next to a carbonyl group, phenol derivatives, naphthol derivatives, and the like.

  Specific examples of the known coupler include 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, benzoyl Acetonilide, 1-phenyl-3-methyl-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-anilino-5-pyrazolone, 2- {3- [α- (2,4 − Di-tert-amylphenoxy) -butanamide] benzamide} phenol, Examples include 2,4-bis- (benzoylacetamino) toluene, 1,3-bis- (pivaloylacetaminomethyl) benzene, and the like.

(Diazo compound)
The diazo compound used in the recording layer in the invention is not particularly limited, but it is preferable to use a diazonium salt represented by the following general formula (2).

[In General Formula (2), R ²⁴ and R ²⁶ each independently represents an alkyl, aryl, heterocyclic ring or acyl group which may have a substituent. R ²⁵ represents an alkyl, aryl, alkylsulfonyl, arylsulfonyl, acyl or heterocyclic group which may have a substituent. Y ²¹ represents an oxygen atom, sulfur atom or nitrogen atom, Y ²² represents an oxygen atom, sulfur atom or single bond, and Y ²³ represents an oxygen atom, sulfur atom or hydrogen atom. However, R ²⁶ does not exist when Y ²³ is a hydrogen atom. R ²⁴ and R ²⁶ may be bonded to each other to form a ring. X ⁻ represents an anion. ]

In the general formula (2), as the R ²⁴ and R ^26, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an acyl group having 2 to 20 carbon atoms preferably.
The alkyl group represented by R ²⁴ and R ²⁶ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, An acylamino group, carbamoyl group, cyano group, carboxylic acid group, sulfonic acid group or heterocyclic group is preferred.

As the (substituted) alkyl group represented by R ²⁴ and R ²⁶ , in particular, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, pentyl group, 3-pentyl group, cyclopentyl group, hexyl Group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, 2-hydroxyethyl group, 2-benzoyloxyethyl group, 2- (4-butoxyphenoxy) ethyl group, benzyl Group, allyl group, methoxyethyl group, ethoxyethyl, dibutylaminocarbonylmethyl group are preferred.

The aryl group represented by R ²⁴ and R ²⁶ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, and an acyloxy group. An acylamino group, a carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group or a heterocyclic group is preferred.
As the (substituted) aryl group represented by R ²⁴ and R ²⁶ , a phenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-butoxyphenyl group, and a naphthyl group are particularly preferable.

When R ²⁴ and R ²⁶ are a heterocyclic group, the heterocyclic ring preferably has nitrogen, oxygen, or sulfur as a hetero atom, and any of saturated, unsaturated, monocyclic, and condensed rings Good. Specific examples include furyl, thienyl, oxazolyl, azozolyl, imidazolyl, pyrazolyl, pyridyl, pyrimidyl, morpholinyl, piperazinyl, indolyl, isoindolyl and the like. Furthermore, these heterocyclic groups may have a substituent. Examples of the substituent include the same ones as described above for the alkyl group.

The acyl group represented by R ²⁴ and R ²⁶ may be aliphatic, aromatic or heterocyclic, and may further have a substituent. As the substituent, an alkoxy group, an aryloxy group, and a halogen atom are preferable.
As the acyl group represented by R ²⁴ and R ²⁶ , an acetyl group, a propanoyl group, a hexanoyl group, a benzoyl group and the like are particularly preferable.

R ²⁴ and R ²⁶ may be bonded to each other to form a ring. Examples of the ring in which R ²⁴ and R ²⁶ are bonded include a thiazole ring, an oxazole ring, and an imidazole ring, and these may further have a substituent. Examples of the substituent include the same substituents as those described above for the alkyl group.

In General Formula (2), R ²⁵ is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms.
Examples of the alkyl group, aryl group, heterocyclic group, and acyl group for R ²⁵ include the same alkyl groups, aryl groups, heterocyclic groups, and acyl groups as those described above for R ²⁴ and R ²⁶ .

The alkylsulfonyl group represented by R ²⁵ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, and an acylamino group. , A carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group or a heterocyclic group is preferred.

Examples of the (substituted) alkylsulfonyl group represented by R ²⁵ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, a benzylsulfonyl group, and a methoxybutylsulfonyl group.

The arylsulfonyl group represented by R ²⁵ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, and an acylamino group. , A carbamoyl group, a cyano group, a carboxylic acid group, a sulfonic acid group or a heterocyclic group is preferred.

Particularly preferable examples of the (substituted) arylsulfonyl group represented by R ²⁵ include a phenylsulfonyl group, a naphthylsulfonyl group, a 4-chlorobenzenesulfonyl group, and a 4-methylbenzenesulfonyl group.

In the general formula (2), Y ²¹ is preferably a sulfur atom or an amino group, and when Y ²¹ is an amino group, it may further have a substituent. Examples of the substituent include an alkyl group and an aryl group.
Y ²¹ and R ²⁴ may form a ring. Examples of the ring formed by Y ²¹ and R ²⁴ include pyrrolidinyl, piperidinyl, piperazinyl, indolyl group and the like, and these may further have a substituent. Examples of the substituent include the same ones as described above for the alkyl group.

In the general formula (2), Y ²² is preferably a sulfur atom or an oxygen atom. Similarly, Y ²³ is preferably a sulfur atom or an oxygen atom.

Examples of the anion represented by X ⁻ in the general formula (2) include inorganic anions and organic anions. As the inorganic anion, hexafluorophosphate ion, borohydrofluoric acid ion, chloride ion, and sulfate ion are preferable, and hexafluorophosphate ion and borohydrofluoric acid ion are particularly preferable. As the organic anion, polyfluoroalkylcarboxylate ions, polyfluoroalkylsulfonate ions, tetraphenylborate ions, aromatic carboxylate ions, and aromatic sulfonate ions are particularly preferable.

  The diazonium salt represented by the general formula (2) is preferably a diazonium salt represented by the following general formula (3) or general formula (4).

[In General Formula (3), R ³¹ and R ³² each independently represents an alkyl or aryl group which may have a substituent, and R ³³ may have a hydrogen atom or a substituent. Represents an alkyl or aryl group, and X ⁻ represents an anion. ]

[In the general formula (4), R ⁴¹ , R ⁴² and R ⁴³ each independently represents an alkyl or aryl group which may have a substituent, or R ⁴² and R ⁴³ are bonded to each other. A ring may be formed. X ⁻ represents an anion. ]

As R <^31> , R ^<32> and R ^<33 > in General formula (3), a C1-C20 alkyl group and a C6-C30 aryl group are preferable.
The alkyl group represented by R ³¹ , R ³² and R ³³ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, An acyloxy group, acylamino group, carbamoyl group, cyano group, carboxylic acid group, sulfonic acid group or heterocyclic group is preferred.

As the (substituted) alkyl group represented by R ³¹ , R ³² and R ³³ , a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, Cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, octadecyl group, 2-hydroxyethyl group, 2-benzoyloxyethyl group, 2- (4-butoxyphenoxy) ethyl group, benzyl group, An allyl group, a methoxyethyl group, an ethoxyethyl group, and a dibutylaminocarbonylmethyl group are preferable.

In the general formula (3), the aryl group represented by R ³¹ , R ³² and R ³³ may further have a substituent. Examples of the substituent include a phenyl group, a halogen atom, an alkoxy group, An aryloxy group, alkoxycarbonyl group, acyloxy group, acylamino group, carbamoyl group, cyano group, carboxylic acid group, sulfonic acid group or heterocyclic group is preferred.
As the (substituted) aryl group represented by R ³¹ , R ³² and R ³³ , a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group and a 4-butoxyphenyl group are particularly preferable.

In the general formula (3), X ^- is, X in the general formula (2) ^- are the same meaning, include those similar. .

Preferred examples of the alkyl group, aryl group, and X ⁻ represented by R ⁴¹ , R ^42, and R ⁴³ in the general formula (4) are alkyl groups represented by R ^{31 to} R ³³ in the general formula (3). , an aryl group, and X ^- are the same as those for. R ⁴² and R ⁴³ may be bonded to each other to form a ring. Examples of the ring formed by R ⁴² and R ⁴³ include a morpholine ring, a piperidine ring, and a pyrrolidine ring.

  Specific examples of the diazonium salt compounds represented by the general formulas (2) to (4) (illustrated compounds (D-1) to (D-92)) are shown below, but the present invention is not limited thereto. .

Diazonium salt represented by the general formula (2)

Diazonium salt represented by general formula (3)

Diazonium salt represented by the general formula (4)

  The diazonium salts represented by the general formulas (2) to (4) may be used alone or in combination of two or more. Furthermore, depending on various purposes such as hue adjustment, the diazonium salt represented by the general formulas (2) to (4) and a known diazonium salt may be used in combination. When the diazonium salt represented by the general formulas (2) to (4) and the known diazonium salt are used in combination, the diazonium salt represented by the general formulas (2) to (4) is contained in the recording layer. It is preferable that it is 50 mass% or more of a diazonium salt, and it is preferable that it is 80 mass% or more.

  Examples of the known diazonium salts include 4-diazo-1-dimethylaminobenzene, 4-diazo-2-butoxy-5-chloro-1-dimethylaminobenzene, 4-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-Toluyl mercapto-2,5-diethoxybenzene, 4-diazo-1-piperazino-2-methoxy-5-chlorobenzene, 4-diazo-1- (N, N-dioctylaminocarbonyl) benzene, 4- Diazo-1- (4-tert-octylphenoxy) benzene, 4-diazo-1- (2-ethyl) Xanoylpiperidino) -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 preferable.

  Further, in the recording material of the present invention, it is preferable to encapsulate a diazonium salt in a microcapsule as described in detail later in order to improve the raw storage stability before use of the recording material. Therefore, the diazonium salt preferably has appropriate solubility in these solvents and low water solubility in order to be dissolved in an appropriate solvent. Specifically, it has a solubility of 5% or more with respect to the organic solvent to be used, and the solubility in water is preferably 1% or less.

In the recording material of the present invention, the diazonium salt is preferably contained in the recording layer in the range of 0.02 to 3 g / m ² , and particularly in the range of 0.1 to ² g / m ² from the viewpoint of color density. It is preferable to contain.

(Microcapsule)
In the recording material of the present invention, it is preferable to encapsulate a diazo compound in a microcapsule in order to improve the raw storage stability before use.
The microcapsule used in this case is a solution obtained by dissolving a diazo compound in a non-aqueous solvent having a boiling point of 40 to 95 ° C. at normal pressure and the same or different compound that reacts with each other to form a polymer substance. After emulsifying and dispersing in the hydrophilic protective colloid solution, the temperature of the solution is increased while the reaction vessel is decompressed to move the wall-forming substance to the surface of the oil droplet while distilling off the solvent, and polyaddition or It is produced by forming a wall film by advancing a polymer formation reaction by polycondensation.

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

A method for producing diazo compound-containing microcapsules (polyurea / polyurethane wall) in the recording material of the present invention will be described below.
First, the diazo compound is dissolved in a hydrophobic organic solvent that becomes the core of the capsule. As the hydrophobic organic solvent used in this case, an organic solvent having a boiling point of 100 ° C. to 300 ° C. is preferable. Aromatic hydrocarbons, halogenated hydrocarbons, carboxylic acid esters, phosphate esters, sulfate esters, Examples include sulfonic acid esters, ketones, and ethers. Specific examples of the organic solvent include alkyl naphthalene, alkyl diphenyl ethane, alkyl diphenyl methane, alkyl biphenyl, chlorinated paraffin, trixyl phosphate, tricresyl phosphate, maleic acid dioctyl ester, adipic acid dibutyl ester and the like. These may be used individually by 1 type and may use 2 or more types together.
Moreover, when the solubility of the diazo compound to be encapsulated in the organic solvent is poor, a low-boiling solvent having high solubility in the diazo compound can be used in combination. Specific examples of the low boiling point solvent include ethyl acetate, butyl acetate, methylene chloride, tetrahydrofuran, and acetone. Further, a polyvalent isocyanate is further added as a wall material (oil phase) in the hydrophobic organic solvent that becomes the core of the microcapsule.

  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 added and emulsified and dispersed by means such as a homogenizer. At this time, the water-soluble polymer acts as a stabilizer for emulsion dispersion. In order to carry out emulsification and dispersion more stably, a surfactant may be added to at least one of the oil phase and the aqueous phase.

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

  If a polyol is added to the aqueous phase, the polyvalent isocyanate and the polyol can react to form a polyurethane wall. In order to increase the reaction rate, it is preferable to keep the reaction temperature high or to add an appropriate polymerization catalyst. The polyisocyanate, polyol, reaction catalyst, polyamine for forming a part of the wall agent, etc. are well known in the book (Keiji Iwata, Polyurethane Handbook, Nikkan Kogyo Shimbun (1987)).

  The polyvalent isocyanate compound used as the raw material for the microcapsule wall is preferably a compound having a trifunctional or higher functional isocyanate group, but a bifunctional isocyanate compound may be used in combination. Specifically, xylene diisocyanate and its hydrogenated product, hexamethylene diisocyanate, tolylene diisocyanate and its hydrogenated product, and diisocyanates such as isophorone diisocyanate are used as the main raw materials, and these dimers or trimers (burette or isosinurate). In addition, polyfunctional adducts with polyols such as trimethylolpropane, formalin condensates of benzene isocyanate, and the like.

  Furthermore, a polyol or polyamine can 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 raw materials for a 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 for dispersing the oil phase of the capsule thus prepared is preferably a water-soluble polymer having a water solubility of 5 or more at the temperature to be emulsified. As polyvinyl alcohol and its modified products, polyacrylic acid amide and its derivatives, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer. Examples include polymers, polyvinylpyrrolidone, ethylene-acrylic acid copolymers, vinyl acetate-acrylic acid copolymers, carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivatives, arabic gum, and sodium alginate.

  These water-soluble polymers preferably have no or low reactivity with isocyanate compounds. For example, those having a reactive amino group in the molecular chain, such as gelatin, can be modified by modification beforehand. It is necessary to eliminate this. Moreover, when adding surfactant, it is preferable that the addition amount of surfactant is 0.1%-5% with respect to the mass of an oil phase, especially 0.5%-2%.

  For emulsification, a known emulsification apparatus such as a homogenizer, a manton gorey, an ultrasonic disperser, or a teddy mill can be used. After emulsification, the emulsion is heated to 30 to 70 ° C. in order to promote the capsule wall formation reaction. Further, during the reaction, in order to prevent aggregation between the capsules, it is necessary to add water to reduce the collision probability between the capsules or to perform sufficient stirring.

  Further, a dispersing agent for preventing aggregation may be added again during the reaction. As the polymerization reaction proceeds, the generation of carbon dioxide gas is observed, and its end can be regarded as the approximate end point of the capsule wall formation reaction. Usually, the target diazo compound-containing microcapsules can be obtained by reacting for several hours.

(Organic base)
In the recording material of the present invention, an organic base may be 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.

  Among these, in particular, 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] Piperazines such as propyloxy} benzene, N- [3- (β-naphthoxy) -2-hydroxy] propylmorpholine, 1,4-bis [(3-mol Morpholines such as lino-2-hydroxy) propyloxy] benzene, 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene, N- (3-phenoxy-2-hydroxypropyl) piperidine, N -Piperidines such as dodecylpiperidine, guanidines such as triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine and the like are preferable.

  In the recording material of the present invention, the amount of the organic base used relative to 1 part by mass of the diazo compound is preferably 0.1 to 30 parts by mass.

(Coloring aid)
In the present invention, in addition to the organic base described above, a coloring aid can be added for the purpose of promoting the coloring reaction. The color assistant is a substance that increases the color density during heat recording or lowers the minimum color development temperature, lowers the melting point of couplers, basic substances, diazo compounds, etc., or softens the capsule wall. This is intended to create a situation in which diazo compounds, basic substances, couplers, etc. are likely to react by the action of lowering the amount of water.

  As the color developing aid used in the recording material of the present invention, for example, a phenol derivative, a naphthol derivative, an alkoxy-substituted benzene, an alkoxy-substituted naphthalene, a hydroxy, and the like in the photosensitive layer so that rapid and complete thermal development is performed with low energy. Compounds, amide compounds, sulfonamide compounds and the like can be added. These compounds are considered to reduce the melting point of couplers and basic substances, or to improve the heat permeability of the microcapsule wall, thereby enabling a high color density.

  The coloring aid used in the recording material of the present invention may be a heat-meltable substance. The heat-melting substance is a substance having a melting point of 50 ° C. to 150 ° C. that is solid at normal temperature and melts by heating, and is a substance that dissolves a diazo compound, a coupler, a basic substance, or the like. Specific examples of these compounds include carboxylic acid amides, N-substituted carboxylic acid amides, ketone compounds, urea compounds, esters and the like.

(Other additives)
In the recording material of the present invention, the following known antioxidants are used for the purpose of improving fastness to light and heat of a thermochromic image or reducing yellowing due to light of an unprinted portion after fixing. Is preferably used.

  Examples of the antioxidant include, for example, European Patent Nos. 223739, 309401, 309402, 310551, 310552, 455416, German Patent No. No. 3435443, JP-A-54-48535, JP-A-62-262047, JP-A-63-113536, JP-A-63-163351, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275 and the like.

  Furthermore, 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, JP-A-60-107383, JP-A-60-125470, JP-A-60-125471, JP-A-60-125472, and JP-A-60. -287485, 60-287486, 60-287487, 60-287488, 61-160287, 61-185483, 61-2111079, 62- 146678, 62-146680, 62-146679, 62-28285, 63-051174, 63-89877, 63-88380, 63-088381 Gazette, 63-203372 gazette, 63-224989 gazette, 63-251 gazette. No. 82, No. 63-267594, No. 63-182484, JP-A-01-239282, No. 04-29185, No. 04-291684, No. 05-188687, No. 05- 188686, 05-110490, 05-1108437, 05-170361, Japanese Patent Publication No. 48-043294, 48-033212, and the like. it can.

  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 cyclohexaneate, 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 0.05 to 100 parts by mass, particularly preferably 0.2 to 30 parts by mass with respect to 1 part by mass of the diazo compound. The above-mentioned known antioxidants can be used in a microcapsule together with a diazo compound, or they can be used as a solid dispersion or with a suitable emulsification aid together with a coupling component, a basic substance, or other coloring aid. It can be used in the form of an emulsion or in both forms. Of course, one or more antioxidants can be used in combination. Further, a protective layer can be provided on the recording layer, and the protective layer can be added or exist.

  These antioxidants need not be added to the same layer. When these antioxidants are used in combination, they are structurally classified as anilines, alkoxybenzenes, hindered phenols, hindered amines, hydroquinone derivatives, phosphorus compounds, sulfur compounds, and different structures. These may be combined, or a plurality of the same may be combined.

  The coupler used in the present invention can be used in the form of a solid dispersion with a water-soluble polymer using a sand mill or the like together with a basic substance and other color forming aids. Is particularly preferred. Preferred water-soluble polymers include water-soluble polymers used when preparing microcapsules (see, for example, JP-A-59-190886). In this case, the coupler, 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.

  To the recording material of the present invention, for the purpose of reducing yellowing of the background after fixing, a free radical generator (compound that generates free radicals by light irradiation) used in a photopolymerizable composition or the like may be added. it can. Examples of 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 with respect to 1 part by mass of the diazo compound.

  Similarly, a polymerizable compound having an ethylenically unsaturated bond (hereinafter sometimes referred to as “vinyl monomer”) may be used for the purpose of reducing yellowing. 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 monomer or prepolymer. Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohols, amide compounds of unsaturated carboxylic acids and aliphatic polyvalent amines, and the like.

  The vinyl monomer is preferably used at 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 can be used in a microcapsule together with a diazo compound. In the present invention, in addition to the above materials, citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid and the like can be added as an acid stabilizer.

The recording material of the present invention is prepared by preparing a coating solution containing a microcapsule containing a diazo compound, a coupler, an organic base, and other additives, and coating a bar on a support such as paper or a synthetic resin film. It is preferable to provide a heat sensitive layer having a solid content of 2.5 to 30 g / m ² by coating and drying by a coating method such as coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating or curtain coating.

  In the recording material of the present invention, microcapsules, couplers, bases, and the like may be contained in the same layer, but it is also possible to adopt a laminated type constitution that is contained in another layer. Further, after providing an intermediate layer as described in Japanese Patent Application No. 59-177669 on the support, a heat-sensitive layer can be applied.

<Support>
As the support used in the recording material of the present invention, any of the paper supports used for ordinary pressure-sensitive paper, thermal paper, dry or wet diazo copy paper, etc. can be used, alkyl ketene dimer, etc. Sizing with a neutral sizing agent, neutral paper having a pH of 5 to 9 (as described in Japanese Patent Application No. 55-14281), Steiktite sizing degree and metric basis weight as described in Japanese Patent Application Laid-Open No. 57-116687 A paper having a Beck smoothness of 90 seconds or more, a paper having an optical surface roughness of 8 μm or less and a thickness of 30 to 150 μm described in JP-A-58-136492, Paper having a density of 0.9 g / cm ³ or less described in 58-69091 and an optical contact ratio of 15% or more, Canadian standard freeness described in JP-A-58-69097 (JIS P8121) 40 Colored with the coated surface of glossy surface of the paper made by Yankee machine described in JP-A-58-65695, which prevents the coating liquid made from pulp pulped to 0 ml (400 cc) or more. Paper with improved density and resolution. It is also possible to use paper that has been subjected to corona discharge treatment on the base paper described in Japanese Patent Application Laid-Open No. 59-35985 and whose coating suitability has been improved.

  Further, the synthetic resin film used as the support is not deformed 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, polyolefin films such as polyethylene, and the like. These can be used alone or in combination. The thickness of the support is 20 to 200 μm.

<Protective layer>
In the recording material of the present invention, if necessary, on the heat-sensitive recording layer for the purpose of preventing sticking or head contamination when printing on the heat-sensitive recording layer or imparting water resistance to the recording material. In addition, it is preferable to further provide a protective layer (hereinafter sometimes simply referred to as “protective layer”) containing polyvinyl alcohol or the like as a main component and added with various pigments, release agents and the like.

<Recording method>
When the recording surface of the recording material of the present invention thus obtained is heated with a thermal head or the like, the polyurea or polyurethane capsule wall is softened, and the coupler and the base compound outside the capsule enter the capsule to 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 a 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 because it can be efficiently photofixed. The recording material (heat-sensitive recording material) of the present invention is exposed using a manuscript, decomposes a diazo compound other than the image forming portion to form a latent image, and then develops the image by heating the recording material. You can also get

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the following description, “parts” means “parts by weight” unless otherwise specified.

Compound synthesis
[Example 1: Synthesis of exemplary compound A-1]
Exemplary Compound A-1 was synthesized according to the following formula.

[Synthesis of Z-1]
15.4 g of 2-amino-4-nitrophenol and 6.6 g of acetic acid marketed by Tokyo Chemical Industry Co., Ltd. were dissolved in 100 mL of acetonitrile. To this, 22.6 g of N, N′-dicyclohexylcarbodiimide was added dropwise. The produced crystals were filtered off and further washed with methanol. The mother liquor was concentrated to obtain a Z-1 crude product. This crude product was used in the next reaction without purification.

[Synthesis of Y-1]
25 g of iron powder and 1 g of ammonium chloride were added to a mixed solution of 25 mL of isopropanol and 25 mL of water, and heated to reflux for 1 hour. After confirming that the iron powder was activated, an isopropanol solution of the crude product of Z-1 was added dropwise. After confirming the disappearance of Z-1 by TLC, the iron powder was removed by Celite filtration, and the mother liquor was concentrated to obtain a crude product of Y-1. This crude product was used in the next reaction without purification.

[Synthesis of X-1]
8.5 g of cyanoacetic acid and the crude Y-1 product synthesized in the previous section were dissolved in 100 mL of acetonitrile. To this solution, 22.6 g of N, N′-dicyclohexylcarbodiimide was added dropwise. After confirming the completion of the reaction by TLC, 50 mL of methanol was added, and the crystals were separated by filtration. The mother liquor was concentrated and purified by column chromatography to obtain 16 g of X-1 (69% yield in 3 steps from Z-1).

[Synthesis of A-1]
In the above reaction formula, 16 g of compound X-1 and 5.32 g of aminoethanethiol were dissolved in 200 mL of ethanol and heated to reflux. After completion of the reaction, the reaction solution was quenched with saturated brine and ethyl acetate. The ethyl acetate phase was washed with saturated brine, dried over magnesium sulfate, filtered and evaporated under reduced pressure. 13.1 g of the target product A-1 was obtained by performing column chromatography. Yield 65%.
¹ H-NMR (300 MHz, CDCl 3) 2.10 (s, 3H), 3, 21 (s, 2H), 3.32 (t, 2H), 4.30 (t, 2H), 6.69 (d , 1H), 7.23 (d, 1H), 7.84 (d, 1H), 8.10 (bs, 1H)

[Example 2: Synthesis of exemplary compound A-4]
Illustrative compound A-4 was synthesized according to the following formula.

Compound X-4 (51.3 g) and aminoethanethiol (7.7 g) were dissolved in ethanol (1000 mL) and heated under reflux. After completion of the reaction, the reaction solution was quenched with saturated brine and ethyl acetate. The ethyl acetate phase was washed with saturated brine, dried over magnesium sulfate, filtered and evaporated under reduced pressure. 13.1 g of the target product A-4 was obtained by performing column chromatography. Yield 65%.
¹ H-NMR (300 MHz, CDCl 3) 0.90 (m, 6H), 1.35 (m, 6H), 1.42 (m, 6H), 1.60 (q, 2H), 1.95-2 .10 (m, 4H), 2.25 (t, 2H), 3, 22 (s, 2H), 3.31 (t, 2H), 4.30 (t, 2H), 6.45 (d, 1H), 6.63 (d, 1H), 6.81 (d, 1H), 7.20 (m, 2H), 8.05 (bs, 2H)

[Example 3: Synthesis of Exemplified Compound A-9]
Exemplified Compound A-9 was synthesized according to the following formula.

3.7 g of compound X-9 and 0.8 g of aminoethanethiol were dissolved in 50 mL of ethanol and heated to reflux. After completion of the reaction, the reaction solution was quenched with saturated brine and ethyl acetate. The ethyl acetate phase was washed with saturated brine, dried over magnesium sulfate, filtered and evaporated under reduced pressure. 1.1 g of the target product A-9 was obtained by performing column chromatography. Yield 25%.
¹ H-NMR (300 MHz, CDCl 3) 0.90 (t, 3H), 1.25-1.35 (m, 10H), 1.85 (m, 2H), 3.22 (s, 2H), 3 .41 (d, 2H), 3.31 (t, 2H), 4.00 (bs, 1H), 4.30 (t, 2H), 6.45 (d, 1H), 6.63 (d, 1H), 6.81 (d, 1H), 8.05 (bs, 2H)

[Example 4: Synthesis of Exemplified Compound A-11]
Exemplified Compound A-11 was synthesized according to the following formula.

4.1 g of compound X-11 and 0.8 g of aminoethanethiol were dissolved in 50 mL of ethanol and heated to reflux. After completion of the reaction, the reaction solution was quenched with saturated brine and ethyl acetate. The ethyl acetate phase was washed with saturated brine, dried over magnesium sulfate, filtered and evaporated under reduced pressure. 1.6 g of the target product A-11 was obtained by performing generation by column chromatography. Yield 35%.
¹ H-NMR (300 MHz, CDCl 3) 2.62 (m, 4H), 3, 21 (s, 2H), 3.33 (t, 2H), 4.34 (t, 2H), 6.60-6 .75 (m, 4H), 7.19-7.22 (m, 3H), 7.85 (s, 1H), 8.02 (bs, 2H)
Preparation of recording material [Example 5]
<Preparation of capsule liquid A>
To 19 parts of ethyl acetate, 2.8 parts of the diazonium salt (Exemplary Compound D-38) described as the above specific example and 10 parts of tricresyl phosphate were added and mixed uniformly. Next, 7.6 parts of Takenate D-110N (manufactured by Mitsui Takeda Chemical Co., Ltd.) was added to the mixed solution as a wall material and mixed uniformly to obtain a liquid I.

  The obtained liquid I was added to an aqueous phase composed of 46.1 parts of an 8% by weight aqueous solution of phthalated gelatin, 17.5 parts of water and 2 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate, and 40 ° C., 10,000 rotations / minute. Emulsification dispersion was performed for 10 minutes. After adding 10 parts of water to the obtained emulsion and homogenizing it, the capsule solution A was obtained by carrying out an encapsulation reaction at 40 ° C. for 3 hours with further stirring. The capsule particle size was 0.35 μm.

(Preparation of alkali-treated gelatin aqueous solution)
25.5 parts of alkali-treated gelatin (trade name: # 750 gelatin, Nitta Gelatin Co., Ltd.), 0.7286 parts of 1,2-benzothiazolin-3-one (3.5% methanol solution), calcium hydroxide 0.153 parts and 143.6 parts of ion-exchanged water were mixed and then dissolved at 50 ° C. to obtain an alkali-treated gelatin aqueous solution.

(Preparation of coupler liquid B)
13.1 parts of ethyl acetate, 5.7 parts of coupler (exemplary compound (A-4)), 4.0 parts of triphenylguanidine (manufactured by Hodogaya Chemical Co., Ltd.), 4,4 '-(m-phenyleneisopropylidene) ) Diphenol (trade name: Bisphenol M, manufactured by Mitsui Petrochemical Co., Ltd.) 8.4 parts 3,3-tetramethyl-5,5 ′, 6,6′-tetra (n-propoxy) -1,1 '-Spirodyne 1.3 g, 2.7 parts of 4- (2-ethylhexyloxy) benzenesulfonamide, calcium dodecylbenzenesulfonate (trade name: Pionein A-41-C 70% methanol solution, manufactured by Takemoto Yushi Co., Ltd.) 1.7 parts were dissolved to obtain a liquid II.
Separately, 43.8 parts of ion-exchanged water was mixed with 83.8 parts of the above alkali-treated gelatin, and the solution II was added thereto, and emulsified and dispersed using a homogenizer at 40 ° C., 10000 rpm for 10 minutes. The obtained emulsion was heated under reduced pressure to remove ethyl acetate, and the concentration was adjusted to a solid content concentration of 26.5%. The particle size of the obtained coupler emulsion was 0.22 μm in median diameter as a result of particle size measurement (LA-700, measured by HORIBA, Ltd.). To this, 3.7 parts of SBR latex (trade name: SN-307, 48% by mass solution, Sumika ABS Latex Co., Ltd.) adjusted to a concentration of 26.5% by mass was added, and the coupler emulsified. Product B was obtained.

(Preparation of coating solution C)
After 6 parts of capsule liquid A, 4.4 parts of water, and 1.9 parts of a 15% by weight aqueous solution of lime-processed gelatin are uniformly mixed at 40 ° C., 8.3 parts of coupler liquid B is added and mixed uniformly to produce heat. Recording layer coating solution C was obtained.

(Preparation of protective layer coating solution D)
Polyvinyl alcohol (polymerization degree 1700, saponification degree 88%) 10% aqueous solution 32 parts and water 36 parts were uniformly mixed to obtain protective layer coating solution D.

(Application)
The target diazo thermosensitive recording material is coated on a photographic paper support in which polyethylene is laminated on high-quality paper in order of the thermal recording layer coating liquid C and the protective layer coating liquid D in this order with a wire bar and dried at 50 ° C. Got. The coating amount as a solid content is 6.4 g / m ² and 1.05 g / m ² , respectively.

<Evaluation>
(Print test and color purity measurement)
The obtained diazo thermosensitive recording material sheet was stored at room temperature for 48 hours, and then applied power to the thermal head using a Kyocera thermal head (KST type) so that the recording energy per unit area was 0 to 40 mJ / mm ^2. The pulse width was selected, and thermal printing was performed on the diazo thermosensitive recording layer to obtain an image. Next, the diazo thermosensitive recording layer was fixed by photolyzing the diazonium salt for 15 seconds using an ultraviolet lamp having an emission center wavelength of 420 nm and an output of 40 w. Thereafter, the color purity of the obtained yellow image was measured visually with respect to the obtained sample. The results are shown in Table 1.

(Light fastness)
Using a weatherometer (Ci65 type, manufactured by Atlas), the sample that was colored and fixed as shown in the above section of the print test and color purity measurement was irradiated with artificial sunlight having an output at a wavelength of 420 nm of 0.9 W / cm ² for 48 hours. Thereafter, the density of the yellow part was measured using a Macbeth densitometer. The residual ratio was measured by comparing with the concentration before light irradiation. The results are shown in Table 1.

[Example 6]
A diazo thermosensitive recording material was prepared in the same manner as in Example 5 except that 5.5 parts of the coupler (Exemplary Compound A-5) was used instead of the coupler (Exemplary Compound A-4) used in Example 5. Similar evaluations were made. The results are shown in Table 1.

[Example 7]
A diazo thermosensitive recording material was prepared in the same manner as in Example 5 except that 4.7 parts of the coupler (Exemplary Compound A-9) was used instead of the coupler (Exemplary Compound A-4) used in Example 5. Similar evaluations were made. The results are shown in Table 1.

[Example 8]
A diazo thermosensitive recording material was prepared in the same manner as in Example 5 except that 4.7 parts of the coupler (Exemplary Compound A-11) was used instead of the coupler (Exemplary Compound A-4) used in Example 5. Similar evaluations were made. The results are shown in Table 1.

[Comparative Example 1]
A diazo thermosensitive recording material was prepared in the same manner as in Example 5 except that 4.1 parts of the coupler (Comparative Compound (1)) shown below was used instead of the coupler (Exemplary Compound A-4) used in Example 5. The same evaluation was performed. The results are shown in Table 1.

  According to the present invention, a novel compound useful as a coupler is obtained, and a recording material using the compound is particularly excellent in image light resistance over time, and the color purity of a recording portion is good.

Claims (6)

A compound represented by the following general formula (1) or a tautomer thereof.

[In general formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² represent a substituent, R ³ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. M represents an integer of 0 to 4, n represents an integer of 0 to 3, and when m or n represents an integer of 2 or more, a plurality of R ^{1 s} or R ^{2 s} are the same or different from each other. They may be linked to each other to form a ring. o and p each independently represent 0 or 1, and o + p is 1 or 2. When n ≧ 1, R ² and R ³ may be connected to each other to form a ring. ] A recording material having a recording layer containing a compound represented by the following general formula (1) or a tautomer thereof on a support.

[In general formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² represent a substituent, R ³ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. M represents an integer of 0 to 4, n represents an integer of 0 to 3, and when m or n represents an integer of 2 or more, a plurality of R ^{1 s} or R ^{2 s} are the same or different from each other. They may be linked to each other to form a ring. o and p each independently represent 0 or 1, and o + p is 1 or 2. When n ≧ 1, R ² and R ³ may be connected to each other to form a ring. ] A recording material having a recording layer containing a compound represented by the following general formula (1) or a tautomer thereof and a diazo compound on a support.

[In general formula (1), X represents an oxygen atom or a sulfur atom, R ¹ and R ² represent a substituent, R ³ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. M represents an integer of 0 to 4, n represents an integer of 0 to 3, and when m or n represents an integer of 2 or more, a plurality of R ^{1 s} or R ^{2 s} are the same or different from each other. They may be linked to each other to form a ring. o and p each independently represent 0 or 1, and o + p is 1 or 2. When n ≧ 1, R ² and R ³ may be connected to each other to form a ring. ] The recording material according to claim 3, wherein the diazo compound is a diazonium salt represented by the following general formula (2).

[In General Formula (2), R ²⁴ and R ²⁶ each independently represents an alkyl, aryl, heterocyclic ring or acyl group which may have a substituent. R ²⁵ represents an alkyl, aryl, alkylsulfonyl, arylsulfonyl, acyl or heterocyclic group which may have a substituent. Y ²¹ represents an oxygen atom, sulfur atom or nitrogen atom, Y ²² represents an oxygen atom, sulfur atom or single bond, and Y ²³ represents an oxygen atom, sulfur atom or hydrogen atom. However, R ²⁶ does not exist when Y ²³ is a hydrogen atom. R ²⁴ and R ²⁶ may be bonded to each other to form a ring. X ⁻ represents an anion. ] The recording material according to claim 3 or 4, wherein the diazo compound is encapsulated in a microcapsule. 6. The recording material according to claim 5, wherein the capsule wall forming the microcapsule contains polyurethane and / or polyurea as a constituent component.