JP2001113840A - Heat-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new heat-sensitive recording material which shows reliable color development properties and superb light resistance after image formation. SOLUTION: This heat-sensitive recording material comprises a support and a heat-sensitive recording layer containing at least one kind selected from diazo compounds represented by formulae [I]-[IV] and a coupler which develops color in the diazo compound through a chemical reaction with the diazo compound, formed on the support. Preferably the heat-sensitive recording material is of such a type that the diazo compound is enveloped in a microcapsule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording material using a diazo compound and a coupler as a color-forming component, and more particularly to a novel heat-sensitive recording material having excellent light resistance in an image area.

[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. For this reason, diazo compounds have long been used as optical recording materials typified by diazo copy ("The Fundamentals of Photographic Engineering-Non-Silver Photography" edited by The Photographic Society of Japan, Corona (1982) 89-
117, 182-201). Furthermore, by utilizing the property of the diazo compound that decomposes by light and loses its activity, it has recently been applied to recording materials that require fixing of the image. As a typical example, the diazo compound and the coupler are heated according to the image signal. A photo-fixing type thermosensitive recording material has been proposed in which an image is formed by reacting and then irradiating light to fix the image (Koji Sato, et al., Journal of the Institute of Image Electronics Engineers of Japan Vol. 11, No. 4,
No. (1982) pp. 290-296). Further, in the light-fixing type thermosensitive recording material, for the purpose of prolonging the shell life, a method of enclosing a diazo compound in a microcapsule and isolating the diazo compound from components that promote the decomposition of the diazo compound such as water and base is proposed. Proposed. (Tomomasa Usami et al., Journal of the Society of Electrophotography, Vol. 26, No. 2 (198
7), 115-125).

[0003]

However, in a recording material using a diazo compound as a coloring element, the chemical activity of the diazo compound is extremely high, and the diazo compound gradually becomes hot during storage of the recording material. It may decompose or photodegrade and lose its reactivity. Therefore, when image recording is performed using the recording material after long-term storage, the color density of the image area tends to decrease. Furthermore, after forming an image, even when the recording material is stored in a light place, the color density of the image area decreases, and the color density of the non-image area tends to increase. Improvement of light resistance is desired.

An object of the present invention is to solve the above problems. That is, an object of the present invention is to provide a novel heat-sensitive recording material that has good color developability and excellent light fastness after image formation.

[0005]

Means for solving the above problems are as follows. <1> A support, and the following general formulas (1) to
A heat-sensitive recording material comprising: a heat-sensitive recording layer containing at least one of the diazo compounds represented by (4) and a coupler which reacts with the diazo compound to form a color of the diazo compound.

[0006]

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In the general formula (1), R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁵¹ , —SR ⁵¹ , —COOR ⁵¹ , and —CONR ^51.
R ⁵² , -SO ₂ R ⁵¹ , -SO ₂ NR ⁵¹ N ⁵² , -COR ⁵¹ ,
—NR ⁵¹ R ⁵² represents any group selected from the group consisting of a nitro group and a cyano group, R ¹⁶ represents an alkyl group or an aryl group, and R ^{17 to} R ²⁰ each independently represent a hydrogen atom , A halogen atom, an alkyl group, an aryl group, -O
R ⁵³ , -SR ⁵³ , -COOR ⁵³ , -CONR ⁵³ R ⁵⁴ ,-
_{^{SO 2 R 53, -SO 2 NR}} 53 N 54, -COR 53, -NR 53
R ⁵⁴ represents a group selected from the group consisting of a nitro group and a cyano group, and R ^{51 to} R ⁵⁴ each independently represent
Represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group, and X ¹ represents a divalent group having at least one group selected from the following divalent group 1 , T ¹ represents an alkylene group or an arylene group. Z ¹¹ and Z ¹² are each independently —SO ₂
-, - C (= O) -, an alkylene group, -SO ₂ Q ¹ -, and -C (= O) -Q ¹ - represents any group selected from the group consisting of, Q ¹ is an alkylene group Represent.

[0008]

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[0009]

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In the general formula (2), R ^{21 to} R ²³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁶¹ , —SR ⁶¹ , —COOR ⁶¹ , and —CONR ^61.
R ⁶² , —SO ₂ R ⁶¹ , —SO ₂ NR ⁶¹ N ⁶² , —COR ⁶¹ ,
—NR ⁶¹ R ⁶² represents a group selected from the group consisting of a nitro group and a cyano group, R ²⁴ represents an alkyl group or an aryl group, and R ^{25 to} R ²⁸ each independently represent a hydrogen atom , A halogen atom, an alkyl group, an aryl group, -O
R ⁶³ , -SR ⁶³ , -COOR ⁶³ , -CONR ⁶³ R ⁶⁴ ,-
_{^{SO 2 R 63, -SO 2 NR}} 63 N 64, -COR 63, -NR 63
R ⁶⁴ represents any group selected from the group consisting of a nitro group and a cyano group, and R ²⁹ represents a hydrogen atom, an alkyl group,
Aryl group, -COOR ⁶⁵ , -CONR ⁶⁵ R ⁶⁶ , -SO
₂ R ⁶⁵ , —SO ₂ NR ⁶⁵ N ⁶⁶ and —COR ⁶⁵ represent any group selected from the group consisting of: R ^{61 to} R ⁶⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, X ² represents a divalent group having at least one group selected from the following divalent group 2; and T ² represents an alkylene group or an arylene group. Represents Z ²¹ and Z ²² are each independently —SO ₂ —, —C (＝ O) —, an alkylene group,
Represents any group selected from the group consisting of SO ₂ Q ² — and —C (＝ O) —Q ² —, and Q ² represents an alkylene group.

[0011]

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[0012]

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In the general formula (3), R ^{30 to} R ³³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁷¹ , —SR ⁷¹ , —COOR ⁷¹ , and —CONR ^{71.
_{R 72, -SO 2 R 71,}} -SO 2 NR 71 N 72, -COR 71,
-NR ⁷¹ R ⁷² represents any one group selected from the group consisting of a nitro group and a cyano group,, R ³⁴ Oyo and R ³⁵ each independently represent an alkyl group or an aryl group, R ³⁶ ~
R ³⁸ is each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁷³ , —SR ⁷³ , —COOR
^{73, -CONR 73 R 74, -SO} 2 R 73, -SO 2 NR 73 N
^{74, -COR 73, -NR 73 R} 74, represents any one group selected from the group consisting of a nitro group and a cyano group,, R ⁷¹
To R ⁷⁴ each independently represents any group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group; and X ³ represents any one selected from the following divalent group 3 And Z ³¹ and Z ³² each independently represent -SO _2- , -C (= O)-,
Alkylene group, —SO ₂ Q ³ —, and —C (＝ O) —Q
³ - represents any group selected from the group consisting of, Q ³ represents an alkylene group.

[0014]

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[0015]

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In the general formula (4), R ^{39 to} R ⁴¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁸¹ , —SR ⁸¹ , —COOR ⁸¹ , and —CONR ^{81.
_{R 82, -SO 2 R 81,}} -SO 2 NR 81 N 82, -COR 81,
-NR ⁸¹ R ⁸² represents any one group selected from the group consisting of a nitro group and a cyano group,, R ⁴² Oyo R ⁴³ are each independently an alkyl group or an aryl group, R ⁴⁴ ~
R ⁴⁶ is each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁸³ , —SR ⁸³ , —COOR
^{83, -CONR 83 R 84, -SO} 2 R 83, -SO 2 NR 83 N
^{84, -COR 83, -NR 83 R} 84, represents any one group selected from the group consisting of a nitro group and a cyano group,, R ⁴⁷
Represents a hydrogen atom, an alkyl group, an aryl group, -COOR ⁸⁵ ,
-CONR ⁸⁵ R ⁸⁶ , -SO ₂ R ⁸⁵ , -SO ₂ NR ⁸⁵ N ⁸⁶ ,
And -COR ⁸⁵ represents any group selected from the group consisting of: R ^{81 to} R ⁸⁶ are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group. X ⁴ represents a divalent group having at least any group selected from the following divalent group 4; Z ⁴¹ and Z ⁴² each independently represent -SO _2- , -C
(＝ O) —, an alkylene group, —SO ₂ Q ⁴ —, and —C
Represents any group selected from the group consisting of (（O) —Q ⁴ —, and Q ⁴ represents an alkylene group.

[0017]

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<2> The heat-sensitive recording material according to <1>, wherein the coupler is a compound represented by formula (5).

[0019]

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In the general formula (5), E ¹ and E ² each independently represent an electron-withdrawing group, and E ¹ and E ² may combine with each other to form a ring.

<3> The heat-sensitive recording material according to <1> or <2>, wherein the diazo compound represented by any of formulas (1) to (4) is encapsulated in microcapsules. <4> The heat-sensitive recording material according to <3>, wherein the capsule wall of the microcapsule is a capsule wall containing polyurethane and / or polyurea as a constituent.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The heat-sensitive recording material of the present invention has, on a support, a heat-sensitive recording layer containing at least one of the compounds represented by formulas (1) to (4). The compounds represented by the general formulas (1) to (4) function as color-forming elements that form a dye constituting an image area by reacting with a coupler contained in the heat-sensitive recording layer.
In the present specification, the term “diazo compound” refers to “Diazo compound”.
azo Chemistry I Aromaticand Heteroaromatic comp
ounds "(Heinrich Zollinger, VCH Verlagsges
ellschaft, Weimheim, 1994). Hereinafter, the diazo compounds represented by the general formulas (1) to (4) will be described.

A diazo compound represented by the general formula (1) In the general formula (1), R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —O
R ⁵¹ , -SR ⁵¹ , -COOR ⁵¹ , -CONR ⁵¹ R ⁵² ,-
_{^{SO 2 R 51, -SO 2 NR}} 51 N 52, -COR 51, -NR 51
R ⁵² represents any group selected from the group consisting of a nitro group and a cyano group.

As the halogen atom represented by R ^{12 to} R ¹⁵ , fluorine, chlorine, bromine and iodine are preferred, and among them, fluorine and chlorine are preferred.

The alkyl group represented by R ^{12 to} R ¹⁵ includes an unsubstituted alkyl group and an alkyl group having a substituent. The alkyl group may be linear or branched and has an unsaturated bond. You may.

The alkyl group represented by R ^{12 to} R ¹⁵ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, methyl, ethyl, n-propyl, i-propyl, n
-Butyl, t-butyl, n-hexyl, n-octyl,
2-ethylhexyl, 3,5,5-trimethylhexyl, dodecyl, 2-chloroethyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-benzoyloxyethyl, N, N-dibutylcarbamoylmethyl, 2-ethoxycarbonylethyl, Butoxycarbonylmethyl,
2-isopropyloxyethyl, 2- (2,5-di-t
-Amylphenoxy) ethyl, 2-phenoxyethyl,
1- (4-methoxyphenoxy) -2-propyl, 1-
(2,5-Di-t-amylphenoxy) -2-propyl, benzyl, α-methylbenzyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and the like are preferred.

The aryl group represented by R ^{12 to} R ¹⁵ includes an unsubstituted aryl group and an aryl group having a substituent. The aryl group represented by R ^{12 to} R ¹⁵ is preferably an aryl group having 6 to 30 carbon atoms in total. Specifically, phenyl, 4-methylphenyl, 2-chlorophenyl and the like are preferable.

R¹²~ R^FifteenIs -OR⁵¹, -SR⁵¹, -CO
OR⁵¹, -CONR⁵¹R⁵², -SO _TwoR⁵¹, -SO_TwoNR
⁵¹N⁵², -COR⁵¹Or -NR⁵¹R⁵²When representing
R⁵¹And R⁵²Is independently a hydrogen atom, an alkyl
Group, an aryl group, and an acyl group.
Represents any group represented by R⁵¹And R⁵²Alkyl represented by
The group includes an unsubstituted alkyl group and an alkyl group having a substituent.
Includes kill groups. R ⁵¹And R⁵²And an alkyl group represented by
For example, an alkyl group having 1 to 30 carbon atoms is preferable.
And an alkyl group having 1 to 10 carbon atoms is more preferable.
No. Specifically, methyl, ethyl, i-propyl, s-
Butyl, t-butyl, t-amyl and the like are preferred.

The aryl group represented by R ⁵¹ and R ⁵² includes an unsubstituted aryl group and an aryl group having a substituent. The aryl group represented by R ⁵¹ and R ⁵² is preferably an aryl group having 6 to 30 carbon atoms in total. Specifically, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 2,
5-Di-t-amylphenyl and the like are preferred.

The acyl groups represented by R ⁵¹ and R ⁵² include an unsubstituted acyl group and an acyl group having a substituent. As the acyl group represented by R ⁵¹ and R ⁵² , an acyl group having a total number of carbon atoms of 1 to 30 is preferable.
More preferred is an acyl group of 10 to 10. Specific examples include acetyl, propanoyl, butanoyl, benzonoyl and the like.

In the general formula (1), R ¹⁶ represents an alkyl group or an aryl group. The alkyl group represented by R ¹⁶ includes an unsubstituted alkyl group and an alkyl group having a substituent. The alkyl group may be linear or branched, and may have an unsaturated bond. The alkyl group R ¹⁶ represents an alkyl group having a total carbon number of 1 to 30 is preferred. Specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, 3,5,5 -Trimethylhexyl, dodecyl, 2-
Chloroethyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-methoxypropyl, 2-benzoyloxyethyl, N, N-dibutylcarbamoylmethyl,
-Ethoxycarbonylethyl, butoxycarbonylmethyl, octyloxycarbonylmethyl, cyclohexyl, 2-isopropyloxyethyl, 2- (2,5-di-t-amylphenoxy) ethyl, 2-phenoxyethyl, 1- (4-methoxyphenoxy) ) -2-propyl,
1- (2,5-di-t-amylphenoxy) -2-propyl, benzyl, α-methylbenzyl, phenethyl, 3
-Phenylpropyl, allyl, methallyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and the like are preferred.

The aryl group represented by R ¹⁶ includes an unsubstituted aryl group and an aryl group having a substituent. R
^The aryl group represented by ¹⁶ has 6 to 30 carbon atoms in total.
Are preferred. Specifically, phenyl, 2-
Preferred are methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl and the like.

In the general formula (1), R ^{17 to} R ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁵³ , —SR ⁵³ , —COOR ⁵³ , and —CON.
_{^{R 53 R 54, -SO 2 R}} 53, -SO 2 NR 53 N 54, -COR
Represents any group selected from the group consisting of ⁵³ , —NR ⁵³ R ⁵⁴ , a nitro group, and a cyano group.

As the halogen atom represented by R ^{17 to} R ²⁰ , fluorine, chlorine, bromine and iodine are preferable, and among them, fluorine and chlorine are preferable.

The alkyl group represented by R ^{17 to} R ²⁰ includes an unsubstituted alkyl group and an alkyl group having a substituent. The alkyl group may be linear or branched and has an unsaturated bond. You may.

The alkyl group represented by R ^{17 to} R ²⁰ is preferably an alkyl group having 1 to 20 carbon atoms in total, and more preferably an alkyl group having 1 to 10 carbon atoms in total. Specifically, methyl, ethyl, n-propyl, i-propyl, n
-Butyl, t-butyl, n-hexyl, n-octyl,
2-ethylhexyl, 3,5,5-trimethylhexyl, dodecyl, 2-chloroethyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-benzoyloxyethyl, N, N-dibutylcarbamoylmethyl, 2-ethoxycarbonylethyl, Butoxycarbonylmethyl,
2-isopropyloxyethyl, 2- (2,5-di-t
-Amylphenoxy) ethyl, 2-phenoxyethyl,
1- (4-methoxyphenoxy) -2-propyl, 1-
(2,5-Di-t-amylphenoxy) -2-propyl, benzyl, α-methylbenzyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and the like are preferred.

The aryl group represented by R ^{17 to} R ²⁰ includes an unsubstituted aryl group and an aryl group having a substituent. The aryl group represented by R ¹⁷ to R ^20, the total number of carbon atoms an aryl group having from 6 to 30 is preferred. Specifically, phenyl, 4-methylphenyl, 2-chlorophenyl and the like are preferable.

R¹⁷~ R²⁰Is -OR⁵³, -SR⁵³, -CO
OR⁵³, -CONR⁵³R⁵⁴, -SO _TwoR⁵³, -SO_TwoNR
⁵³N⁵⁴, -COR⁵³Or -NR⁵³R⁵⁴When representing
R⁵³And R⁵⁴Is independently a hydrogen atom, an alkyl
Group, an aryl group, and an acyl group.
Represents any group represented by R⁵³And R⁵⁴Alkyl represented by
The group includes an unsubstituted alkyl group and an alkyl group having a substituent.
Includes kill groups. R ⁵³And R⁵⁴And an alkyl group represented by
For example, an alkyl group having 1 to 30 carbon atoms is preferable.
And an alkyl group having 1 to 10 carbon atoms is more preferable.
No. Specifically, methyl, ethyl, i-propyl, s-
Butyl, t-butyl, t-amyl and the like are preferred.

The aryl group represented by R ⁵³ and R ⁵⁴ includes an unsubstituted aryl group and an aryl group having a substituent. The aryl group represented by R ⁵³ and R ⁵⁴ is preferably an aryl group having 6 to 30 carbon atoms in total. Specifically, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 2,
5-Di-t-amylphenyl and the like are preferred.

The acyl groups represented by R ⁵³ and R ⁵⁴ include an unsubstituted acyl group and an acyl group having a substituent. As the acyl group represented by R ⁵¹ and R ⁵² , an acyl group having a total number of carbon atoms of 1 to 30 is preferable.
More preferred is an acyl group of 10 to 10. Specific examples include acetyl, propanoyl, butanoyl, benzonoyl and the like.

In the general formula (1), X¹Is the divalent group
Divalent having at least any group selected from group 1
Represents a group. In group 1 of the divalent group, Z¹¹And Z¹²Are each
Independently, -SO_Two-, -C (= O)-, alkylene
Group, -SO_TwoQ¹-, And -C (= O) -Q¹−
Represents any group selected from the group consisting of¹Is Alkyre
Represents a group. Z¹¹, Z¹², And Q¹Alkylene represented by
The group may have a substituent and may have 2 to 6 carbon atoms.
Alkylene groups are preferred. A linking hand in the divalent group 1
Means a chemical bond such as a single bond or a double bond. Said
In the general formula (1), X ¹Is -SO_Two-, -C (= O)-
A divalent group containing at least, or a connecting hand is preferable.
New Specifically, phenylenesulfonyl, 2-hexyl
Luoxyphenylenecarbonyl, phenylenesulfonyl
Methylene, oxycarbonylphenylsulfonyl, oki
Cicarbonylphenylcarbonyl and the like. Said
In the general formula (1), T¹Is an alkylene group or aryl
Represents a group. T¹Is an alkylene group having 1 to 6 carbon atoms
It is preferable to include at least. Specifically,
Len, methylene, hexamethylene, 2-methoxytrime
Tylene, 2-acetoxytrimethylene, propylene, etc.
No.

A diazonium compound represented by the general formula (2) In the general formula (2), R ^{21 to} R ²³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —O
R ⁶¹ , -SR ⁶¹ , -COOR ⁶¹ , -CONR ⁶¹ R ⁶² ,-
_{^{SO 2 R 61, -SO 2 NR}} 61 N 62, -COR 61, -NR 61
R ⁶² represents any group selected from the group consisting of a nitro group and a cyano group.

As the halogen atom represented by R ^{21 to} R ²³ ,
It has the same meaning as the halogen atom represented by R ^{12 to} R ¹⁵ in the general formula (1), and preferred examples are also the same. As the alkyl group represented by R ^{21 to} R ²³ , R ^{12 to} R in the above general formula (1)
^It has the same meaning as the alkyl group represented by ¹⁵ , and the preferred examples are also the same. The aryl group represented by R ^{21 to} R ²³ has the same meaning as the aryl group represented by R ^{12 to} R ^{15 in} formula (1),
Preferred examples are also the same.

R^{twenty one}~ R^{twenty three}Is -OR⁶¹, -SR⁶¹, -C
OOR⁶¹, -CONR⁶¹R⁶², -SO_TwoR⁶¹, -SO_TwoN
R⁶¹N⁶², -COR⁶¹Or -NR⁶¹R⁶²Place to represent
If R ⁶¹And R⁶²Is each independently a hydrogen atom,
Selected from the group consisting of a kill group, an aryl group, and an acyl group.
Represents any of the following groups: R⁶¹And R⁶²Al
As the kill group, in the general formula (1), R⁵¹And R⁵²
Has the same meaning as the alkyl group represented by
You. R⁶¹And R⁶²The aryl group represented by
In the general formula (1), R⁵¹And R⁵²Has the same meaning as the aryl group represented by
The same applies to preferred examples. R⁶¹And R⁶²Is a table
As the acyl group, in the general formula (1), R⁵¹and
R⁵²Has the same meaning as the acyl group represented by
is there.

In the general formula (2), R ²⁴ represents an alkyl group or an aryl group. The alkyl group represented by R ²⁴ has the same meaning as the alkyl group represented by R ^{16 in} Formula (1), and preferred examples are also the same. The aryl group represented by R ²⁴ has the same meaning as the aryl group represented by R ^{16 in} formula (1), and preferred examples are also the same.

In the general formula (2), R ^{25 to} R ²⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁶³ , —SR ⁶³ , —COOR ⁶³ , and —CON.
R ⁶³ R ⁶⁴ , -SO ₂ R ⁶³ , -SO ₂ NR ⁶³ N ⁶⁴ , -COR
⁶³ , —NR ⁶³ R ⁶⁴ , a nitro group, and a cyano group.

R^{twenty five}~ R²⁸As the alkyl group represented by
R of the general formula (1)¹⁷~ R²⁰Has the same meaning as the alkyl group represented by
Yes, the same applies to preferred examples. R^{twenty five}~ R²⁸Ants represented by
As the hydroxyl group, R 1 of the above general formula (1)¹⁷~ R²⁰Represents
It has the same meaning as the aryl group, and preferred examples are also the same. R
^{twenty five}~ R²⁸Is -OR⁶³, -SR⁶³, -COOR⁶³, -C
ONR⁶³R⁶⁴, -SO_TwoR⁶³, -SO_TwoNR⁶³N⁶⁴, -C
OR⁶³Or -NR ⁶³R⁶⁴When R represents⁶³Or R
⁶⁴Is independently a hydrogen atom, an alkyl group, an aryl
Any one selected from the group consisting of
Represents a group. R⁶³And R⁶⁴Examples of the alkyl group represented by
R of the general formula (1)⁵³And R⁵⁴And an alkyl group represented by
It has the same meaning, and the preferred example is also the same. R⁶³And R⁶⁴
Is an aryl group represented by the general formula (1)⁵³You
And R⁵⁴Has the same meaning as the aryl group represented by
The same is true. R⁶³And R⁶⁴As the acyl group represented by
R of the general formula (1)⁵³And R⁵⁴Same as the acyl group represented by
The same applies to the preferred examples.

In the general formula (2), R²⁹Is a hydrogen atom,
Alkyl group, aryl group, -COOR ⁶⁵, -CONR⁶⁵R
⁶⁶, -SO_TwoR⁶⁵, -SO_TwoNR⁶⁵N⁶⁶, And -COR
⁶⁵Represents any group selected from the group consisting of

The alkyl group represented by R ²⁹ includes an unsubstituted alkyl group and an alkyl group having a substituent. The alkyl group may be linear or branched, and may have an unsaturated bond. .

The alkyl group represented by R ²⁹ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, dodecyl, Chloroethyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-benzoyloxyethyl, N, N-dibutylcarbamoylmethyl, 2-ethoxycarbonylethyl, butoxycarbonylmethyl,
Isopropyloxyethyl, 2- (2,5-di-t-amylphenoxy) ethyl, 2-phenoxyethyl, 1-
(4-methoxyphenoxy) -2-propyl, 1-
(2,5-Di-t-amylphenoxy) -2-propyl, benzyl, α-methylbenzyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and the like are preferred.

The aryl group represented by R ²⁹ includes an unsubstituted aryl group and an aryl group having a substituent. R
^The aryl group represented by ²⁹ has 6 to 30 carbon atoms in total.
Are preferred. Specifically, phenyl, 4-
Methylphenyl, 2-chlorophenyl and the like are preferred.

R ²⁹ is —COOR ⁶⁵ , —CONR ⁶⁵ R ⁶⁶ ,
Any -SO ₂ R ^65, when a -SO ₂ NR ⁶⁵ N ^66, or -COR ^65, is, R ⁶⁵ and R ⁶⁶ are each independently a hydrogen atom, selected from the group consisting of alkyl groups and acyl group, Represents a group. The alkyl group represented by R ⁶⁵ and R ⁶⁶ includes an unsubstituted alkyl group and an alkyl group having a substituent. The alkyl group represented by R ⁶⁵ and R ⁶⁶ is preferably an alkyl group having 1 to 30 total carbon atoms, and more preferably an alkyl group having 1 to 10 total carbon atoms. Specifically, methyl, ethyl, i-propyl, s-
Butyl, t-butyl, t-amyl and the like are preferred.

The aryl group represented by R ⁶⁵ and R ⁶⁶ includes an unsubstituted aryl group and an aryl group having a substituent. The aryl group represented by R ⁶⁵ and R ⁶⁶ is preferably an aryl group having 6 to 30 carbon atoms in total. Specifically, specifically, phenyl, 2-methylphenyl, 3
-Methylphenyl, 4-methylphenyl, 2-chlorophenyl, 2,5-t-amylphenyl and the like are preferred.

The acyl groups represented by R ⁶⁵ and R ⁶⁶ include an unsubstituted acyl group and an acyl group having a substituent. As the acyl group represented by R ⁶⁵ and R ⁶⁶ , an acyl group having a total number of carbon atoms of 1 to 30 is preferable.
More preferred is an acyl group of 10 to 10. Specific examples include acetyl, propanoyl, butanoyl, benzonoyl and the like.

In the general formula (2), X ² represents a divalent group having at least one group selected from Group 2 of the divalent group, and T ² represents an alkylene group or an arylene group. Z ²¹ and Z ²² are each independently —SO ₂ —, —C
(＝ O) —, an alkylene group, —SO ₂ Q ² —, and —C
(= O) -Q ² - represents any group selected from the group consisting of, Q ² represents an alkylene group. X ² and T ² have the same meanings as X ¹ and T ¹ in the general formula (1), and preferred examples are also the same. Z ²¹ , Z ²² ,
And as the alkylene group Q ² represents, Z ^11, Z ^{1 2} in the general formula (1), and Q ¹ has the same meaning as the alkylene group represented by, and preferred examples are also the same.

A diazo compound represented by the general formula (3) In the general formula (3), R ^{30 to} R ³³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —O
R ⁷¹ , -SR ⁷¹ , -COOR ⁷¹ , -CONR ⁷¹ R ⁷² ,-
_{^{SO 2 R 71, -SO 2 NR}} 71 N 72, -COR 71, -NR 71
R ⁷² represents any group selected from the group consisting of a nitro group and a cyano group.

As the halogen atom represented by R ^{30 to} R ³³ ,
It has the same meaning as the halogen atom represented by R ^{12 to} R ^{15 in} the general formula (1), and preferred examples are also the same. The alkyl group represented by R ^{30 to} R ³³ has the same meaning as the alkyl group represented by R ^{12 to} R ^{15 in} Formula (1), and preferred examples are also the same. The aryl group represented by R ^{30 to} R ³³ has the same meaning as the aryl group represented by R ^{12 to} R ^{15 in} formula (1), and preferred examples are also the same.

R³⁰~ R³³Is -OR⁷¹, -SR⁷¹, -C
OOR⁷¹, -CONR⁷¹R⁷², -SO_TwoR⁷¹, -SO_TwoN
R⁷¹N⁷², -COR⁷¹Or -NR⁷¹R⁷²Place to represent
If R ⁷¹And R⁷²Is each independently a hydrogen atom,
Selected from the group consisting of a kill group, an aryl group, and an acyl group.
Represents any of the following groups: R⁷¹And R⁷²Al
As the kill group, in the general formula (1), R⁵¹And R⁵²
Has the same meaning as the alkyl group represented by
You. R⁷¹And R⁷²The aryl group represented by
In the general formula (1), R⁵¹And R⁵²Has the same meaning as the aryl group represented by
The same applies to preferred examples. R⁷¹And R⁷²Is a table
As the acyl group, in the general formula (1), R⁵¹and
R⁵²Has the same meaning as the acyl group represented by
is there.

In the general formula (3), R ³⁴ and R ³⁵ are
Each independently represents an alkyl group or an aryl group. R
^The alkyl group represented by ³⁴ and R ³⁵ has the same meaning as the alkyl group represented by R ^{16 in} formula (1), and preferred examples are also the same. The aryl group represented by R ³⁴ and R ³⁵ has the same meaning as the aryl group represented by R ^{16 in} formula (1), and preferred examples are also the same.

In the general formula (3), R ^{36 to} R ³⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁷³ , —SR ⁷³ , —COOR ⁷³ , and —CON.
R ⁷³ R ⁷⁴ , -SO ₂ R ⁷³ , -SO ₂ NR ⁷³ N ⁷⁴ , -COR
⁷³ , —NR ⁷³ R ⁷⁴ , represents a group selected from the group consisting of a nitro group and a cyano group.

R³⁶~ R³⁸As the alkyl group represented by
R of the general formula (1)¹⁷~ R²⁰Has the same meaning as the alkyl group represented by
Yes, the same applies to preferred examples. R³⁶~ R³⁸Ants represented by
As the hydroxyl group, R 1 of the above general formula (1)¹⁷~ R²⁰Represents
It has the same meaning as the aryl group, and preferred examples are also the same. R
³⁶~ R³⁸Is -OR⁷³, -SR⁷³, -COOR⁷³, -C
ONR⁷³R⁷⁴, -SO_TwoR⁷³, -SO_TwoNR⁷³N⁷⁴, -C
OR⁷³Or -NR ⁷³R⁷⁴When R represents⁷³Or R
⁷⁴Is independently a hydrogen atom, an alkyl group, an aryl
Any one selected from the group consisting of
Represents a group. R⁷³And R⁷⁴Examples of the alkyl group represented by
R of the general formula (1)⁵³And R⁵⁴And an alkyl group represented by
It has the same meaning, and the preferred example is also the same. R⁷³And R⁷⁴
Is an aryl group represented by the general formula (1)⁵³You
And R⁵⁴Has the same meaning as the aryl group represented by
The same is true. R⁷³And R⁷⁴As the acyl group represented by
R of the general formula (1)⁵³And R⁵⁴Same as the acyl group represented by
The same applies to the preferred examples.

In the general formula (3), X ³ represents a divalent group having at least one group selected from Group 3 of the divalent group, and Z ³¹ and Z ³² each independently represent -SO
_{2 -, - C (= O} ) -, an alkylene group, -SO ₂ Q ³ -,
And -C (= O) -Q ³ - represents any group selected from the group consisting of, Q ³ represents an alkylene group. X ³ has the same meaning as X ¹ in the general formula (1),
Preferred examples are also the same. As the alkylene group represented by Z ³¹ , Z ³² and Q ³ , Z ¹¹ , Z
It has the same meaning as the alkylene group represented by ¹² and Q ¹ , and preferred examples are also the same.

A diazo compound represented by the general formula (4) In the general formula (4), R ^{39 to} R ⁴¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —O
R ⁸¹ , -SR ⁸¹ , -COOR ⁸¹ , -CONR ⁸¹ R ⁸² ,-
_{^{SO 2 R 81, -SO 2 NR}} 81 N 82, -COR 81, -NR 81
Represents any group selected from the group consisting of R ⁸² , a nitro group, and a cyano group.

As the halogen atom represented by R ^{39 to} R ⁴¹ ,
It has the same meaning as the halogen atom represented by R ^{12 to} R ¹⁵ in the general formula (1), and preferred examples are also the same. As the alkyl group represented by R ^{39 to} R ⁴¹ , R ¹² to R ⁴¹ in the above general formula (1)
It has the same meaning as the alkyl group R ¹⁵ is represented, and preferred examples are also the same. The aryl group represented by R ^{39 to} R ⁴¹ has the same meaning as the aryl group represented by R ^{12 to} R ^{15 in} Formula (1), and preferred examples are also the same.

R³⁹~ R⁴¹Is -OR⁸¹, -SR⁸¹, -C
OOR⁸¹, -CONR⁸¹R⁸², -SO_TwoR⁸¹, -SO_TwoN
R⁸¹N⁸², -COR⁸¹Or -NR⁸¹R⁸²Place to represent
If R ⁸¹And R⁸²Is each independently a hydrogen atom,
Selected from the group consisting of a kill group, an aryl group, and an acyl group.
Represents any of the following groups: R⁸¹And R⁸²Al
As the kill group, in the general formula (1), R⁵¹And R⁵²
Has the same meaning as the alkyl group represented by
You. R⁸¹And R⁸²The aryl group represented by
In the general formula (1), R⁵¹And R⁵²Has the same meaning as the aryl group represented by
The same applies to preferred examples. R⁸¹And R⁸²Is a table
As the acyl group, in the general formula (1), R⁵¹and
R⁵²Has the same meaning as the acyl group represented by
is there.

In the general formula (4), R ⁴² and R ⁴³ are
Each independently represents an alkyl group or an aryl group. R
^The alkyl group represented by ⁴² and R ⁴³ has the same meaning as the alkyl group represented by R ^{16 in} formula (1), and preferred examples are also the same. The aryl group represented by R ⁴² and R ⁴³ has the same meaning as the aryl group represented by R ^{16 in} formula (1), and preferred examples are also the same.

In the general formula (4), R ^{44 to} R ⁴⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR ⁸³ , —SR ⁸³ , —COOR ⁸³ , and —CON.
_{^{R 83 R 84, -SO 2 R}} 83, -SO 2 NR 83 N 84, -COR
⁸³ , —NR ⁸³ R ⁸⁴ , a group selected from the group consisting of a nitro group and a cyano group.

R⁴⁴~ R⁴⁶As the alkyl group represented by
R of the general formula (1)¹⁷~ R²⁰Has the same meaning as the alkyl group represented by
Yes, the same applies to preferred examples. R⁴⁴~ R⁴⁶Ants represented by
As the hydroxyl group, R 1 of the above general formula (1)¹⁷~ R²⁰Represents
It has the same meaning as the aryl group, and preferred examples are also the same. R
⁴⁴~ R⁴⁶Is -OR⁸³, -SR⁸³, -COOR⁸³, -C
ONR⁸³R⁸⁴, -SO_TwoR⁸³, -SO_TwoNR⁸³N⁸⁴, -C
OR⁸³Or -NR ⁸³R⁸⁴When R represents⁸³Or R
⁸⁴Is independently a hydrogen atom, an alkyl group, an aryl
Any one selected from the group consisting of
Represents a group. R⁸³Or R⁸⁴Examples of the alkyl group represented by
R of the general formula (1)⁵³And R⁵⁴And an alkyl group represented by
It has the same meaning, and the preferred example is also the same. R⁸³Or R⁸⁴
Is an aryl group represented by the general formula (1)⁵³You
And R⁵⁴Has the same meaning as the aryl group represented by
The same is true. R⁸³Or R⁸⁴As the acyl group represented by
R of the general formula (1)⁸³Or R⁸⁴Same as the acyl group represented by
The same applies to the preferred examples.

In the general formula (4), R⁴⁷Is a hydrogen atom,
Alkyl group, aryl group, -COOR ⁸⁵, -CONR⁸⁵R
⁸⁶, -SO_TwoR⁸⁵, -SO_TwoNR⁸⁵N⁸⁶, And -COR
⁸⁵Represents any group selected from the group consisting of R⁴⁷But
Examples of the alkyl group represented by R 1 in the general formula (2)²⁹Is a table
This is synonymous with the alkyl group, and preferred examples are also the same.
R⁴⁷Is an aryl group represented by the general formula (2)
²⁹Has the same meaning as the aryl group represented by
is there.

R⁴⁷Is -COOR⁸⁵, -CONR⁸⁵R⁸⁶,
-SO_TwoR⁸⁵, -SO_TwoNR⁸⁵N⁸⁶Or -COR⁸⁵To
When represented, R⁸⁵And R⁸⁶Are each independently a hydrogen source
, Alkyl, aryl, and acyl groups
Represents any group selected from the group; R⁸⁵And R⁸⁶But
As the alkyl group represented by the general formula (2),⁶⁵And R
⁶⁶Has the same meaning as the alkyl group represented by
is there. R⁸⁵And R⁸⁶As the aryl group represented by
R of the formula (2)⁶⁵And R⁶⁶Has the same meaning as the aryl group represented by
The same applies to preferred examples. R⁸⁵And R⁸⁶Represents
As the sil group, R represented by the general formula (2)⁶⁵And R⁶⁶Represents
It has the same meaning as the acyl group, and preferred examples are also the same.

In the general formula (4), X ⁴ represents a divalent group having at least one group selected from the group 4 of the divalent groups, and Z ⁴¹ and Z ⁴² each independently represent -SO
_{2 -, - C (= O} ) -, an alkylene group, -SO ₂ Q ⁴ -,
And —C (＝ O) —Q ⁴ —, and represents any group selected from the group consisting of: and Q ⁴ represents an alkylene group. X ⁴ has the same meaning as X ^{1 in the} general formula (1), and preferred examples are also the same. The Z ^41, Z ^42, and alkylene groups Q ⁴ represents, Z ^41, Z ⁴² in the general formula (1), and Q ⁴ have the same meaning as the alkylene group represented by, and preferred examples are also the same.

The following formulas (1) to (4)
Specific examples of the diazo compound represented by the following (A-1 to
A-32), but the diazo compound used in the present invention is not limited to the following compounds.

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Each of the diazo compounds represented by the general formulas (1) to (4) is described in JP-A-9-286782, Japanese Patent Application No. 11-43178, and US Pat.
No. 16262, and US Pat. No. 5,424,268.
It can be synthesized according to the method described in the specification.

The heat-sensitive recording layer is formed of the general formula (1)
It contains at least one diazo compound represented by (4). Two or more kinds may be used in combination, or may be used in combination with another diazo compound. The diazo compounds represented by the general formulas (1) to (4) are contained in the heat-sensitive recording layer in an amount of 0.02.
To 3 g / m ^2, preferably 0.1 to ² g / m ^2.
More preferably, m ^{2 is} contained. Content is 0.02g
/ M is less than ² in terms of color development property, in terms of the coating suitability exceeds 3 g / m ^2, both undesirable.

The heat-sensitive recording layer contains a coupler which reacts with the diazo compound represented by the general formulas (1) to (4) contained therein to form a color of the diazo compound.
One type of coupler may be used alone, or two or more types may be used in combination according to various purposes such as hue adjustment. Examples of the coupler include a so-called active methylene compound having a methylene group next to a carbonyl group, a phenol derivative, a naphthol derivative, and the like.

Specific examples include resorcin, phloroglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, sodium 2-hydroxy-3-naphthalenesulfonate, 2-hydroxy-3-naphthalenesulfonic acid anilide, Hydroxy-2-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthalenesulfonic acid morpholinopropylamide, 2-hydroxy-3-naphthalenesulfonic acid-2-ethylhexyloxypropylamide, 2-hydroxy-3-naphthalenesulfonic acid- 2-ethylhexylamide, 5-acetamido-1-naphthol, 1-hydroxy-8-acetamidonaphthalene-3,6-disulfonate sodium,
1-hydroxy-8-acetamidonaphthalene-3,6
-Disulfonic acid dianilide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-
Hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid anilide, 5,5-dimethyl-
1,3-cyclohexanedione, 1,3-cyclopentanedione, 5- (2-n-tetradecyloxyphenyl) -1,3-cyclohexanedione, 5-phenyl-
4-methoxycarbonyl-1,3-cyclohexanedione,

5- (2,5-di-n-octyloxyphenyl) -1,3-cyclohexanedione, 1,3-dicyclohexyl barbituric acid, 1,3-di-n-dodecyl barbituric acid, 1- n-octyl-3-n-octadecylbarbituric acid, 1-phenyl-3- (2,5
-Di-n-octyloxyphenyl) barbituric acid,
1,3-bis (octadecyloxycarbonylmethyl)
Barbituric acid, 1-phenyl-3-methyl-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3
-Anilino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-benzamido-5-pyrazolone, 6-hydroxy-4-methyl-3-cyano-1-
(2-ethylhexyl) -2-pyridone, 2- [3-
[Α- (2,4-di-tert-aluminophenoxy) butanamide] benzamide] phenol, 2,4-bis- (benzoylacetoamino) toluene, 1,3-bis- (pivaloylacetoaminomethyl) benzene, Benzoylacetonitrile, tenoylacetonitrile, acetoacetanilide, benzoylacetanilide, pivaloylacetanilide, 2-chloro-5- (Nn-butylsulfamoyl) -1-pivaloylacetamidebenzene, 1- (2-ethylhexyloxy) Propyl) -3-
Cyano-4-methyl-6-hydroxy-1,2-dihydropyridin-2-one, 1- (dodecyloxypropyl) -3-acetyl-4-methyl-6-hydroxy-
1,2-dihydropyridin-2-one, 1- (4-n-
Octyloxyphenyl) -3-tert-butyl-5
-Aminopyrazole and the like. For details of these couplers, see JP-A-4-201483 and JP-A-7-2014.
JP-A-125446, JP-A-7-96671, JP-A-7-223267, JP-A-7-223368
No., etc.

In particular, it is preferable to use the compound represented by formula (5) or a resonance isomer of the compound as a coupler.

In the general formula (5), E ¹ and E ² represent electron-withdrawing groups. As the electron withdrawing group, Hamme
tt means a substituent having a positive σ value, which may be the same or different, and may be an acetyl group, a propionyl group, a pivaloyl group, a chloroacetyl group, a trifluoroacetyl group, a 1-methylcyclopropyl group. Carbonyl group,
1-ethylcyclopropylcarbonyl group, 1-benzylcyclopropylcarbonyl group, benzoyl group, 4-methoxybenzoyl group, acyl group such as tenoyl group, methoxycarbonyl group, ethoxycarbonyl group, 2-methoxyethoxycarbonyl group, 4-methoxy Oxycarbonyl group such as phenoxycarbonyl group, carbamoyl group, N, N
-Dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group, N-2,4-bis (pentyloxy) phenylcarbamoyl group, N-
Carbamoyl groups such as 2,4-bis (octyloxy) phenylcarbamoyl group and morpholinocarbonyl group, cyano groups, methanesulfonyl groups, benzenesulfonyl groups, sulfonyl groups such as toluenesulfonyl groups, phosphono groups such as diethylphosphono groups, Oxazol-2-yl,
Heterocyclic groups such as a benzothiazol-2-yl group, a 3,4-dihydroquinazolin-4-one-2-yl group and a 3,4-dihydroquinazolin-4-sulfon-2-yl group are preferred.

In addition, E ¹ and E ² may combine to form a ring. The ring formed by E ¹ and E ² is preferably a 5- or 6-membered carbon ring or heterocyclic ring.

Specific examples of the compound represented by formula (5) are shown below. Specific examples of the couplers (C-1 to C-24) used in the present invention are not limited thereto. is not.

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The coupler is used in the heat-sensitive recording layer in an amount of 0.1.
The content is preferably from 0.4 to 9 g / m ² ,
g / m ² is more preferable. Content 0.0
If it is less than 4 g / m ^2, it is not preferable from the viewpoint of color development, and if it exceeds 9 g / m ² , it is not preferable from the viewpoint of applicability.

In the heat-sensitive recording layer, tertiary amines, piperidines, piperazines, amidines, tertiary amines, for the purpose of accelerating the coupling reaction between the coupler and the diazo compound.
It is preferable to use an organic base such as formamidines, pyridines, guanidines, and morpholines.

Specific examples of these organic bases include N,
N′-bis (3-phenoxy-2-hydroxypropyl) piperazine, N, N′-bis [3- (p-methylphenoxy) -2-hydroxypropyl] piperazine,
N, N'-bis [3- (p-methoxyphenoxy) -2
-Hydroxypropyl] piperazine, N, N'-bis (3-phenylthio-2-hydroxypropyl) piperazine, N, N'-bis [3- (β-naphthoxy) -2-
Hydroxypropyl] piperazine, N-3- (β-naphthoxy) -2-hydroxypropyl-N′-methylpiperazine, 1,4-bis {[3- (N-methylpiperazino) -2-hydroxy] propyloxy} benzene Piperazines, N- [3- (β-naphthoxy) -2-hydroxy] propylmorpholine, 1,4-bis [(3-
Morpholines such as morpholino-2-hydroxy) propyloxy] benzene and 1,3-bis [(3-morpholino-2-hydroxy) propyloxy] benzene;
(3-phenoxy-2-hydroxypropyl) piperidines such as piperidine and N-dodecylpiperidine, triphenylguanidine, tricyclohexylguanidine, dicyclohexylphenylguanidine, 2-hydroxybenzoic acid 2-N-methyl-N-benzylaminoethyl ester 4-hydroxybenzoic acid 2-N, N-di-n-butylaminoethyl ester, 4- (3-N, N-dibutylaminopropoxy) benzenesulfonamide, 4-
(2-N, N-dibutylaminoethoxycarbonyl) phenoxyacetic acid amide and the like.

The details of the organic base are described in
JP-A-7-123086, JP-A-60-49991, JP-A-60-94381, and JP-A-09-07.
No. 7,737, JP-A-09-077729, JP-A-09-071048, and the like.

These organic bases may be used alone or in combination of two or more. The amount of the organic base is preferably 1 to 30 mol per 1 mol of the diazo compound. The organic base may be contained in the heat-sensitive recording layer or may be contained in a layer other than the heat-sensitive recording layer.

The heat-sensitive recording layer may contain a coloring aid. As the color development aid, a phenol derivative,
Examples include naphthol derivatives, alkoxy-substituted benzenes, alkoxy-substituted naphthalenes, hydroxy compounds, carboxylic acid amide compounds, and sulfonamide compounds.
Further, the heat-sensitive recording layer may further contain a reducing agent.

The heat-sensitive recording layer preferably further contains a binder for forming the layer. As the binder, conventionally known binders such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, and styrene-acrylic acid copolymer can be used. Details are described in JP-A-2-141279.

In addition, various kinds of organic or inorganic pigments, various stabilizers, antioxidants and the like can be added to the heat-sensitive recording layer as needed.

In the heat-sensitive recording layer, the general formulas (1) to (1)
It is preferable that the diazo compound represented by (4) be encapsulated in microcapsules, because the raw storage stability of the heat-sensitive recording material is improved. As a method of forming microcapsules,
A conventionally known method can be adopted. The microcapsules are preferably formed of a polymer that is impermeable to substances at normal temperature and becomes permeable when heated. In particular, it is preferably formed from a polymer having a glass transition temperature of 60 to 200 ° C. Examples thereof include polyurethane, polyurea, polyamide, polyester, urea / formaldehyde resin, melamine resin, polystyrene, styrene / methacrylate copolymer, styrene / acrylate copolymer, and a mixture thereof. In particular, it is preferable that the microcapsules are formed from a polymer containing urethane and / or urea as a component (for example, polyurethane, polyurea, or the like).

As a method for forming microcapsules, an interfacial polymerization method and an internal polymerization method are suitable. For details of the capsule forming method and specific examples of the reactants, see U.S. Patent Nos. 3,726,804 and 3,796,663.
No. 9 and the like. For example, when polyurea or polyurethane is used as a capsule wall material, a polyisocyanate and a second substance (for example, polyol or polyamine) which reacts with the polyisocyanate to form a capsule wall are mixed in an aqueous medium or an oil medium to be encapsulated, and then mixed with water. These are emulsified and dispersed, and then heated to cause a polymer forming reaction at the oil droplet interface to form microcapsule walls. Note that polyurea is also generated when the addition of the second substance is omitted.

An example of a method for producing a diazo compound-encapsulated microcapsule (polyurea / polyurethane wall) will be described below. First, a diazo compound is dissolved or dispersed in a hydrophobic organic solvent serving as a core of a capsule. As the organic solvent in this case, an organic solvent having a boiling point of 100 to 300 ° C is preferable. 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 books (Polyurethane Handbook, edited by Keiji Iwata, Nikkan Kogyo Shimbun (198)
7)).

As the 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, adducts of polyols such as trimethylolpropane and bifunctional isocyanates such as xylylene diisocyanate are polyfunctional, and adducts of polyols such as trimethylolpropane and bifunctional isocyanates such as xylylene diisocyanate are used as polyadducts. Examples include compounds into which a high molecular weight compound such as polyether having active hydrogen such as ethylene oxide is introduced, and formalin condensate of benzene isocyanate. JP-A-62-212190, JP-A-4-26189, JP-A-5-317
No. 694, Japanese Patent Application No. 8-268721, and the like are preferred.

Further, a polyol or a 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 hydrophobic organic solvent used for dissolving the diazo compound and forming the core of the microcapsule has a boiling point of 1
Organic solvents of 00 to 300 ° C. are preferred, and specific examples thereof include alkylnaphthalene, alkyldiphenylethane, alkyldiphenylmethane, alkylbiphenyl, alkylterphenyl, chlorinated paraffin, phosphates, maleates, and adipic esters. Phthalates, benzoates, carbonates, ethers, sulfates, sulfonates, and the like. These may be used as a mixture of two or more.

When the solubility of the diazo compound encapsulated in the capsule in the solvent is poor, a low-boiling solvent having high solubility in the diazo compound may be used in combination. Specific examples include ethyl acetate, butyl acetate, methylene chloride, tetrahydrofuran, acetonitrile, acetone and the like. For this reason, the diazo compound preferably has an appropriate solubility in these high-boiling hydrophobic organic solvents and low-boiling auxiliary solvents, and specifically, has a solubility of 5% or more in the solvent. preferable. The solubility in water is preferably 1% or less.

On the other hand, as the water-soluble polymer used in the water-soluble polymer aqueous solution used as the water phase (water phase in which the prepared oil phase is dispersed), the solubility in water at the temperature to be emulsified is 5% or more. Are preferred. Specific examples thereof include polyvinyl alcohol and modified products thereof, polyacrylamide and derivatives thereof, ethylene-vinyl acetate copolymer, styrene-maleic anhydride copolymer, and ethylene-maleic anhydride. Acid copolymer, isobutylene-maleic anhydride copolymer, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, vinyl acetate-acrylic acid copolymer, carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivative, arabic gum, sodium alginate And the like.

It is preferable that these water-soluble polymers have no reactivity 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 is preferably 0.1% to 5%, particularly preferably 0.5% to 2%, based on the weight of the oil phase.

The emulsification is performed by using a homogenizer, a Menton-Gawley, an ultrasonic disperser, a dissolver, a Keddy mill, or the like.
A known emulsifying apparatus can be used. After the emulsification, the emulsified product is 30 to 70 to promote the capsule wall forming reaction.
Warming to ° C is performed. 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.

During the reaction, a dispersion for preventing aggregation may be added again. 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 diazo compound-encapsulated microcapsules can be obtained.

On the other hand, in the heat-sensitive recording layer, the coupler can be used in a solid dispersion state together with a water-soluble polymer by a sand mill or the like, if desired, together with an organic base, other coloring aids, and the like. Alternatively, after dissolving in an organic solvent that is hardly soluble or insoluble in water, this may be mixed with an aqueous phase having a surfactant and / or a water-soluble polymer as a protective colloid to obtain an emulsified dispersion. When used as an emulsified dispersion, a surfactant is preferably used from the viewpoint of facilitating emulsified dispersion. The solid dispersion method and the emulsification method are not particularly limited, and conventionally known methods can be used. Details of these methods are described in JP-A-59-190886, JP-A-2-141279, and JP-A-7-171.
No. 45, it is described.

The organic solvent used when the coupler is used as an emulsified dispersion is described, for example, in JP-A-2-141279.
Can be appropriately selected from the high-boiling oils described in Japanese Patent Application Publication No. Among these, the use of esters is preferred from the viewpoint of the emulsion stability of the emulsified dispersion, and tricresyl phosphate is particularly preferred. The above oils can be used together or with other oils.

An auxiliary solvent may be further added to the above organic solvent as a low boiling point dissolution aid. As such co-solvents, for example, ethyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like can be mentioned as particularly preferable ones. In some cases, only a low-boiling auxiliary solvent without a high-boiling oil can be used.

The water-soluble polymer to be contained as a protective colloid in the aqueous phase mixed with the oil phase containing these components is as follows:
It can be appropriately selected from known anionic polymers, nonionic polymers, and amphoteric polymers. Preferred water-soluble polymers include, for example, polyvinyl alcohol, gelatin, cellulose derivatives and the like.

As the surfactant to be contained in the aqueous phase, one which does not cause precipitation or aggregation by acting on the protective colloid described above is appropriately selected from anionic or nonionic surfactants. Can be. Preferred surfactants include sodium alkylbenzenesulfonate, sodium alkylsulfate, dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonyl phenyl ether), and the like.

The heat-sensitive recording material of the present invention is prepared, for example, by preparing a coating solution containing a diazo compound (the microcapsule when encapsulated in a microcapsule), a coupler and, if desired, an organic base and other additives. Then, it is coated and dried on a support such as paper or synthetic resin film by a coating method such as bar coating, blade coating, air knife coating, gravure coating, roll coating coating, spray coating, dip coating, curtain coating or the like. be able to. It is preferable to apply the coating so that the coating amount is 2.5 to 30 g / m ² in solid content.

As the support of the heat-sensitive recording material of the present invention,
Neutral paper, acidic paper, recycled paper, polyolefin resin laminated paper, synthetic paper, cellulose film such as polyester film and cellulose triacetate film, polystyrene film, polyolefin film such as polypropylene film and polyethylene film, and the like. Or bonded together.
The thickness of the support is preferably from 20 to 200 μm.

In the heat-sensitive recording material of the present invention, the diazo compound, the coupler and, if desired, the organic base may be contained in the same layer, or may be contained in another layer. That is, the heat-sensitive recording layer may have a laminated structure. In addition, a Japanese Patent Application No. Sho 59-1
After providing the intermediate layer as described in the specification of 77669, the heat-sensitive recording layer can be applied.

The heat-sensitive recording material of the present invention may optionally contain
A protective layer may be provided on the heat-sensitive recording layer. Two or more protective layers may be laminated as necessary. Materials used for the protective layer include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch,
Methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, gelatins, gum arabic,
Casein, styrene-maleic acid copolymer hydrolyzate,
Styrene-maleic acid copolymer half ester hydrolysate, isobutylene-maleic anhydride copolymer hydrolysate, polyacrylamide derivative, polyvinylpyrrolidone, polystyrene sodium sulfonate, water-soluble polymer compounds such as sodium alginate, and styrene- Latexes such as butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion are used. The water-soluble polymer compound in the protective layer can be cross-linked to further improve the storage stability, and a known cross-linking agent can be used as the cross-linking agent. Specifically, N-
Examples include water-soluble initial condensates such as methylol urea, N-methylol melamine, and urea-formalin; dialdehyde compounds such as glyoxal and glutaraldehyde; inorganic cross-linking agents such as boric acid and borax; and polyamide epichlorohydrin. The protective layer may further contain known pigments, metal soaps, waxes, surfactants, ultraviolet absorbers and precursors thereof. The protective layer can be formed by preparing a coating solution containing the above components, and applying and drying the coating solution. The coating amount of the protective layer coating solution is preferably 0.2 to 5 g / m ² , more preferably 0.5 to 5 g / m ^2.
2 g / m ² is preferred. The thickness of the protective layer is 0.2 to
5 μm is preferable, and particularly preferably 0.5 to 2 μm.

In order to correct the curl balance of the support,
Alternatively, for the purpose of improving the chemical resistance from the back surface, a back coat layer may be provided, or a label may be formed by combining release paper with an adhesive layer on the back surface. This back coat layer can be provided in the same manner as the protective layer.

The heat-sensitive recording material of the present invention can be used for multicolor heat-sensitive recording materials. The multicolor heat-sensitive recording material (heat-sensitive recording material) is disclosed in Japanese Patent Application Laid-Open No. 4-135787.
JP-A-4,144,784 and JP-A-4-144478
No. 5, No. 4-194842, No. 4-2474
Nos. 47, 4-247448, 4-340
Nos. 540, 4-340541 and 5-34
860 and the like. Specifically, it can be obtained by laminating thermosensitive recording layers which develop colors of different hues. Although the layer configuration is not particularly limited, as an example, two types of diazo compounds having different photosensitive wavelengths (at least one is a diazo compound represented by the above general formulas (1) to (4)) and Two layers (B layer and C layer) of a thermosensitive recording layer in which a diazo compound and a coupler which reacts with heat and develop a different hue are used, and a thermosensitive recording layer in which a colorless electron-donating dye and an electron-accepting compound are combined. (A
Layer) and a multicolor heat-sensitive recording material.

Specifically, a first heat-sensitive recording layer (A) containing a colorless electron-donating dye and an electron-accepting compound on a support is provided.
Layer), a second thermosensitive recording layer (layer B) containing a diazo compound having a maximum absorption wavelength of 355 nm ± 25 nm and a coupler which reacts with the diazo compound when heated to form a color, and has a maximum absorption wavelength of 405 ± 25 nm. The third heat-sensitive recording layer (C layer) contains a diazo compound and a coupler which reacts with the diazo compound when heated to give a color. In this example,
If the color hue of each heat-sensitive recording layer is selected so as to be three primary colors, yellow, magenta, and cyan in subtractive color mixing,
Full-color image recording becomes possible.

In the recording method of the multicolor heat-sensitive recording material, first, the third heat-sensitive recording layer (C layer) is heated so that the diazo compound and the coupler contained in the layer are colored. Next, 405 ± 2
After irradiating 5 nm light to decompose the unreacted diazo compound contained in the C layer and fix it by light, sufficient heat is applied to the second heat-sensitive recording layer (B layer) to develop a color. The diazo compound and the coupler contained in the layer are colored. At this time, the C layer is also heated strongly, but the diazo compound has already been decomposed (fixed by light) and the color forming ability has been lost, so that no color is formed. Further, the diazo compound contained in the B layer is decomposed by irradiating light of 355 ± 25 nm, and finally, the first heat-sensitive recording layer (A layer) is given a sufficient heat to develop a color to develop a color. At this time, the thermosensitive recording layers C and B are also heated strongly at the same time, but the diazo compound has already been decomposed and has lost the color-forming ability, so that no color is formed.

Further, all the heat-sensitive recording layers (A layer, B layer, and C layer in order from the upper layer) are heated to react with three kinds of diazo compounds having different photosensitive wavelengths to each of the diazo compounds to obtain different hues. It can also be composed of a heat-sensitive recording layer in which a coupler that develops color is combined. In particular, such a layer configuration is necessary when the yellow layer having low visibility is used as the lowermost layer to improve the image quality by reducing the influence on the image quality due to the roughness on the surface of the support. . When all the heat-sensitive recording layers (A layer, B layer, and C layer) are diazo-based heat-sensitive recording layers, it is necessary to fix the layers A and B after color development. For the layer C, it is not necessary to perform light fixing.

The heat-sensitive recording material of the present invention comprises:
An image can be formed by imagewise providing sufficient heat for the coupling reaction between the diazo compound and the coupler contained in the heat-sensitive recording layer to proceed. After the image is formed, light may be irradiated to decompose the diazo compound in the non-image area to fix the image. In order to provide imagewise heat to the heat-sensitive recording layer, a thermal head or the like can be used. Various fluorescent lamps, xenon lamps, mercury lamps, and the like are used as a fixing light source used for light fixing. It is preferable that this emission spectrum substantially coincides with the absorption spectrum of the diazo compound used in the heat-sensitive recording material, because light can be efficiently fixed.

In recording on the heat-sensitive recording material of the present invention, the heat-sensitive recording material is exposed through a manuscript to decompose diazo compounds other than the image forming portion to form a latent image. It can also be used as a heat-developable photosensitive material such as developing to obtain an image.

[0132]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited by these examples. In the following, “parts” and “%” in Examples are
The parts by weight and% by weight are shown. [Example 1] (Preparation of microcapsule liquid A containing diazonium salt compound) In 13.7 parts of ethyl acetate, 4.6 parts of a diazonium salt compound (exemplified compound a-12) as a core substance, and 10 parts of diphenyl phthalate. 4 parts were added and mixed homogeneously. Then, Takenate D1 was added to this mixture as a wall material.
5.5 parts of 10N (manufactured by Takeda Pharmaceutical Co., Ltd.), Millionate MR200 (manufactured by Nippon Polyurethane Industry Co., Ltd.)
2.8 parts were added to obtain a liquid X. Next, phthalated gelatin 8
% Aqueous solution, 67.4 parts of water, 17.4 parts of water, sucrapA
The above-mentioned solution X was added to a mixed solution of 0.4 parts of G-8 (manufactured by Nippon Seika Co., Ltd.), and emulsified and dispersed at 40 ° C. and 8,000 rpm for 10 minutes using a homogenizer. After adding 50 parts of water and 0.26 parts of diethylenetriamine to the obtained emulsion and homogenizing it, a microencapsulation reaction was performed at 60 ° C. for 3 hours with stirring to obtain a diazonium salt compound-containing microcapsule liquid A. . The average particle size of the microcapsules was 0.3 to 0.4 μm.

(Preparation of Coupling Component Emulsion B) A coupling component (Example Compound C-
12) 3.5 parts, 1.9 parts of triphenylguanidine and 3.3 parts of tricresyl phosphate were dissolved to obtain a liquid Y. Next, 50 parts of a 15% aqueous solution of lime-processed gelatin and 0.5% of a 10% aqueous solution of sodium dodecylbenzenesulfonate were used.
Part of water and 50 parts of water were uniformly mixed at 40 ° C., and the solution Y was added thereto.
The mixture was emulsified and dispersed at 0000 rpm for 10 minutes. The obtained emulsion was stirred at 40 ° C. for 2 minutes to remove ethyl acetate, and water was added to obtain a coupling component emulsion B.

(Preparation of Coating Solution C for Thermosensitive Recording Layer) 10 parts of the microcapsule solution A containing the diazonium salt compound and 30 parts of the emulsion B for the coupling component were mixed, and the coating solution C for the thermosensitive recording layer was mixed.
I got

(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 16 parts of water.

(Coating) Coating solution C for the heat-sensitive recording layer and coating solution D for the protective layer were applied in this order on a photographic paper support obtained by laminating polyethylene on a high-quality paper, and then dried at 50 ° C. for the desired heat-sensitive recording. The material was obtained. The coating amounts of the heat-sensitive recording layer and the protective layer as solids were 3.5 g / m ² and 1, respectively.
It was ² g / m ² .

The following evaluation was performed on the obtained heat-sensitive recording material. Table 1 shows the evaluation results. <Light resistance evaluation 1> Using the obtained heat-sensitive recording material, KST
The power applied to the thermal head and the pulse width are determined by using a thermal head (manufactured by Kyocera Corporation) so that the recording energy per unit area is 50 mJ / mm ^{2. After} performing thermal printing, the color density of the image area is determined. The measurement was performed using a Macbeth densitometer (reflection densitometer RD918, manufactured by Macbeth). Apply 32,000 fluorescent light to the sample after printing.
After irradiating with lux illuminance for 72 hours, measure the concentration,
The ratio of the density after irradiation to the color density before irradiation with the fluorescent lamp was evaluated as a residual rate. The higher the residual ratio, the better the light resistance. <Light resistance evaluation 2> Light 320 of the fluorescent lamp of the light resistance evaluation 1
The xenon light was changed to 4 hours instead of the condition of 00 lux for 72 hours.
The remaining rate was calculated in the same manner as in the light resistance evaluation 1 except that the irradiation was performed for 8 hours. <Evaluation of storability of scalp raw material>
It was forcibly stored for 72 hours under the condition of 90% RH. afterwards,
The density of the background was measured, and the increase in the background density due to the compulsory test was calculated.

Example 2 A thermosensitive recording material was prepared in the same manner as in Example 1, except that Exemplified Compound A-20 was used instead of Exemplified Compound A-12 used in Example 1. evaluated. Table 1 shows the evaluation results. Example 3 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1, except that Exemplified Compound A-5 was used instead of Exemplified Compound A-12 used in Example 1. Table 1 shows the evaluation results. Example 4 A thermosensitive recording material was prepared and evaluated in the same manner as in Example 1, except that Exemplified Compound C-9 was used instead of Exemplified Compound C-11 used in Example 1. Table 1 shows the evaluation results. Comparative Example 1 A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 1 except that the following compound was used instead of Exemplified Compound A-12 used in Example 1. Table 1 shows the evaluation results.

[0139]

Embedded image

[0140]

[Table 1]

[0141]

According to the present invention, it is possible to provide a heat-sensitive recording material which has good color developability and excellent light fastness after image formation.

Claims (4)

[Claims] 1. A support and, on the support, at least one of diazo compounds represented by the following general formulas (1) to (4) and reacting with the diazo compound to form a color of the diazo compound. And a heat-sensitive recording layer containing a coupler. Embedded image (In the general formula (1), R ^{12 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR
⁵¹ , -SR ⁵¹ , -COOR ⁵¹ , -CONR ⁵¹ R ⁵² , -S
_{^{O 2 R 51, -SO 2 NR}} 51 N 52, -COR 51, -NR 51 R
⁵² , a nitro group, and a cyano group; R ¹⁶ represents an alkyl group or an aryl group; R ^{17 to} R ²⁰ each independently represent a hydrogen atom, a halogen atom, Alkyl group, aryl group, -OR ⁵³ , -S
R ⁵³ , -COOR ⁵³ , -CONR ⁵³ R ⁵⁴ , -SO
_{^{2 R 53, -SO 2 NR 53}} N 54, -COR 53, -NR
⁵³ represents any group selected from the group consisting of R ⁵⁴ , a nitro group, and a cyano group, and R ^{51 to} R ⁵⁴ each independently represent a group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group. X ¹ represents a divalent group having at least one group selected from the following divalent group group 1, and T ¹ represents an alkylene group or an arylene group. Z ¹¹ and Z ¹² are each independently —S
O ₂ —, —C (＝ O) —, an alkylene group, —SO ₂ Q
¹ -, and -C (= O) -Q ¹ - represents any group selected from the group consisting of, Q ¹ represents an alkylene group. ) Embedded image (In the general formula (2), R ^{21 to} R ²³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR
⁶¹ , -SR ⁶¹ , -COOR ⁶¹ , -CONR ⁶¹ R ⁶² , -S
_{^{O 2 R 61, -SO 2 NR}} 61 N 62, -COR 61, -NR 61 R
⁶² , a nitro group, and a cyano group; R ²⁴ represents an alkyl group or an aryl group; R ^{25 to} R ²⁸ each independently represent a hydrogen atom, a halogen atom, Alkyl group, aryl group, -OR ⁶³ , -S
R ⁶³ , -COOR ⁶³ , -CONR ⁶³ R ⁶⁴ , -SO
₂ R ⁶³ , -SO ₂ NR ⁶³ N ⁶⁴ , -COR ⁶³ , -NR
⁶³ represents any group selected from the group consisting of R ⁶⁴ , a nitro group, and a cyano group, and R ²⁹ represents a hydrogen atom, an alkyl group, an aryl group, —COOR ⁶⁵ , —CONR ⁶⁵ R ⁶⁶ ,
SO ₂ R ^65, represents any one group selected from the group consisting of -SO ₂ NR ⁶⁵ N ^66, and -COR ^65, R ⁶¹ ~R
⁶⁶ independently represents any group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group; and X ² represents any group selected from the following divalent group 2 And T ² represents an alkylene group or an arylene group. Z ²¹ and Z ²² are each independently selected from the group consisting of —SO ₂ —, —C (＝ O) —, an alkylene group, —SO ₂ Q ² —, and —C (＝ O) —Q ² —. Q ² represents an alkylene group. ) Embedded image (In the general formula (3), R ^{30 to} R ³³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR
⁷¹ , -SR ⁷¹ , -COOR ⁷¹ , -CONR ⁷¹ R ⁷² , -S
_{^{O 2 R 71, -SO 2 NR}} 71 N 72, -COR 71, -NR 71 R
⁷² , a nitro group, and a cyano group; and R ³⁴ and R ³⁵ each independently represent
Represents an alkyl group or an aryl group, and R ^{36 to} R ³⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, -OR ⁷³ , -SR ⁷³ , -COOR ⁷³ , -CO
NR ⁷³ R ⁷⁴ , -SO ₂ R ⁷³ , -SO ₂ NR ⁷³ N ⁷⁴ , -CO
R ⁷³ , —NR ⁷³ R ⁷⁴ , represents a group selected from the group consisting of a nitro group and a cyano group, and R ^{71 to} R ⁷⁴ are
Each independently represents any group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group, and X ³ has at least any group selected from the following divalent group 3 Represents a divalent group, and Z ³¹ and Z ³² are each independently —SO ₂ —, —C (＝ O) —, an alkylene group, —SO ₂ Q ³ —, and —C (＝ O) —Q ³ - represents any group selected from the group consisting of, Q ³ represents an alkylene group. ) Embedded image (In the general formula (4), R ^{39 to} R ⁴¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, —OR
^{81, -SR 81, -COOR 81,} -CONR 81 R 82, -S
_{^{O 2 R 81, -SO 2 NR}} 81 N 82, -COR 81, -NR 81 R
⁸² , a nitro group, and a cyano group; and R ⁴² and R ⁴³ each independently represent
Represents an alkyl group or an aryl group, R ⁴⁴ to R ⁴⁶ are independently a hydrogen atom, a halogen atom, an alkyl group, an aryl ^{group, -OR 83, -SR 83, -COOR} 83, -CO
NR ⁸³ R ⁸⁴ , -SO ₂ R ⁸³ , -SO ₂ NR ⁸³ N ⁸⁴ , -CO
R ⁸³ , —NR ⁸³ R ⁸⁴ , represents a group selected from the group consisting of a nitro group and a cyano group, and R ⁴⁷ represents a hydrogen atom, an alkyl group, an aryl group, —COOR ⁸⁵ , —CON
_{^{R 85 R 86, -SO 2 R}} 85, and -SO ₂ NR ⁸⁵ N ^86, -
Represents any group selected from the group consisting of COR ⁸⁵ ,
R ^{81 to} R ⁸⁶ each independently represent a hydrogen atom, an alkyl group,
It represents any one group selected from the group consisting of aryl and acyl groups,, X ⁴ represents a divalent group having at least one group selected from the following divalent groups of 4, Z ⁴¹
And Z ⁴² are each independently —SO ₂ —, —C (＝ O)
—, An alkylene group, —SO ₂ Q ⁴ —, and —C (＝ O)
-Q ^4- represents any group selected from the group consisting of
Q ⁴ represents an alkylene group. ) 2. The heat-sensitive recording material according to claim 1, wherein the coupler is a compound represented by the general formula (5). Embedded image (In the general formula (5), E ¹ and E ² each independently represent an electron-withdrawing group, and E ¹ and E ² may be bonded to each other to form a ring.) 3. The heat-sensitive recording material according to claim 1, wherein the diazo compounds represented by the general formulas (1) to (4) are encapsulated in microcapsules. 4. The heat-sensitive recording material according to claim 3, wherein the capsule wall of the microcapsule is a capsule wall containing polyurethane and / or polyurea as a constituent.