JPH09230531A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material having satisfactory sharpness, causing no problem on coloring and ensuring light fastness by incorporating a specified dye and at least one kind of specified compd. as a fading inhibitor. SOLUTION: This photosensitive material contains a dye represented by formula I or II and at least one kinds of compd. represented by the formula Ln<1> Mm<2> (III), etc. IN the formula I, each of Z<1> and Z<2> is a group of nonmetallic atoms required to form an optionally condensed 5- or 6-membered N-contg. hetero ring, each or R<1> and R<2> is an alyl, alkenyl or aralkyl, L is a combining group formed by combining 5, 7 or 9 methine groups through conjugated double bonds, each of (a), (b) and (c) is 0 or 1 and Z is an anion. In the formula II, each of R<3> -R<10> is H, an alkyl, etc. In the formula III, L is a ligand, M is Ni, Co, Cu, Pt, Pd, Fe, Mn or Zn, n<1> is an integer of 1-10 and m1 is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a technique for imparting high sharpness, low coloring and high light fastness.

A photothermographic material for forming a photographic image using a photothermographic treatment is disclosed, for example, in US Pat. No. 3,152,904.
No. 3457075 and D. Morgan and B. Shely, "Thermally Processed Silver Systems" (Imaging Processes and Materials (Imag).
ing Processes and Materials) Neblette, 8th Edition, Sturge, V. Walworth, A. Shepp, ed., p. 2, 1969). In such a photothermographic material, a reducible silver source (eg organic silver salt), a catalytically active amount of a photocatalyst (eg silver halide), a toning agent for controlling the color tone of silver and a reducing agent are usually (organic) binders. It is contained in the matrix in a dispersed state. The photothermographic material is stable at room temperature,
When heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is generated through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver produced by the reaction of the organic silver salt in the exposed areas provides a black and white image, which contrasts with the unexposed areas and is imaged. In recent years, in the medical field, technology has advanced with the keywords of processing simplification, speedup, and environmental friendliness. An infrared laser (especially 750
A system is conceivable in which exposure is performed by an electromagnetic wave having a wavelength of nm or more) and thermal development is performed. In order to obtain an image with high sharpness in such a system, an infrared dye having an absorption suitable for an infrared laser used for exposure in order to prevent halation and irradiation is necessary. The infrared dye is required to have no absorption in the visible region or to be colored even if there is no problem. Japanese Patent Application No. 7-111
No. 84 or US Pat. No. 5,380,635 proposes a photothermographic material using a cyanine dye and a squarylium dye satisfying the required absorption characteristics, but these dyes have insufficient light fastness and are obtained. In addition, there are problems that the coloring (color) of the image changes and stains occur.

[0003]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a photothermographic material having good sharpness, no coloring problem, and lightfastness.

[0004]

The above-mentioned problems are solved by the dye of the following general formula (1a) or (2) and the following general formula (3a):
This can be achieved by a photothermographic material containing at least one of the compound (4) or (5) as an anti-fading agent.

[0005]

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In the formula, Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle which may be condensed, and R ¹ and R ² are each an alkyl group. , Alkenyl group or aralkyl group, L is 5, 7 or 9
Represents a linking group formed by linking methine groups with a conjugated double bond, a, b or c each represents 0 or 1, and X represents an anion. However, X is the general formula (3a)
When it is an anion containing M of general formula (3a),
The compound represented by (4) or (5) may not be contained.

[0007]

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In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R
⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom, an alkyl group,
Represents a cycloalkyl group, an aryl group or an aralkyl group, R ³ and R ⁴ and / or R ⁵ and R ⁶ and / or R ⁷ and R ⁸ and / or R ⁹ and R ¹⁰ or R ⁴ and R
⁵ and / or R ⁸ and R ⁹ may form a 5- or 6-membered ring.

[0009]

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In the formula, L represents a ligand, M represents Ni, C
represents a metal atom of o, Cu, Pt, Pd, Fe, Mn, or Zn, n ¹ represents an integer of ¹ to 10, and m ¹ represents 1 or 2.

[0011]

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In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom or an alkyl group, and X represents an anion.

[0013]

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In the formula, R ¹⁵ is hydrogen atom, halogen atom, C
ONHR ²² , SO ₂ NHR ²² , NHSO ₂ R ²² , NHC
OR ²² or NHCONHR ²² , R ²² represents an alkyl group or an aryl group, and R ¹⁶ and R ¹⁷ represent a hydrogen atom, an alkyl group, a halogen atom, NHCOR ²² ,
NHSO ₂ R ²² or a non-metal atom necessary for linking with each other to form an aromatic ring, R ²² represents an alkyl group or an aryl group, R ¹⁸ and R ¹⁹ are each a hydrogen atom,
Represents an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom, R ²⁰ and R ²¹ are each an alkyl group,
An aralkyl group or an atom necessary for forming a heterocycle by connecting to the substituent R ^{19 which} is connected to each other or adjacent to each other, and n ² is 0, 1 or 2.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (1a) will be described in detail.
The optionally condensed 5- or 6-membered nitrogen-containing heterocycle represented by Z ¹ and Z ² is an oxazole ring, an isoxazole ring,
Benzoxazole ring, naphthoxazole ring, thiazole ring, benzothiazole ring, naphthothiazole ring, indolenine ring, benzoindolenine ring, imidazole ring, benzimidazole ring, naphthimidazole ring, imidazoquinoxaline ring, quinoline ring, pyridine ring, pyrrolo Examples thereof include a pyridine ring and a furopyrrole ring. Preferred is a 5-membered nitrogen-containing heterocyclic ring in which a benzene ring or a naphthalene ring is condensed, and most preferred is an indolenine ring. These rings may be substituted. Examples of the substituent include an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy), a phenoxy group (eg, unsubstituted phenoxy, p-chlorophenoxy), a halogen atom (Cl, B).
r, F), an alkoxycarbonyl group (for example, ethoxycarbonyl), a cyano group, a nitro group and the like. More preferred is an indolenine ring substituted or unsubstituted with a chlorine atom, a methoxy group or a methyl group.

The alkyl group represented by R ¹ and R ² is an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl). . Further, it may be substituted with a halogen atom (F, Cl, Br), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl) or a hydroxy group. R ¹ and R ²
The aralkyl group represented by is preferably an aralkyl group having a carbon number of 7 to 12 (eg, benzyl, phenylethyl), and may have a substituent (eg, methyl, alkoxy, chloro atom). The alkenyl group represented by R ¹ and R ² is preferably an alkenyl group having 2 to 6 carbon atoms, for example, 2-pentenyl group, vinyl group, allyl group, 2-butenyl group, 1-propenyl group. A group can be mentioned.

In the formula (1a), L is 5, 7 or 9
It is a linking group in which individual methine groups are bonded so as to be conjugated with a double bond. The number of methine groups is preferably 7 (heptamethine compound). The methine group may have a substituent. However, the methine group having a substituent is preferably a central (meso-position) substituted methine group. Among the methine groups represented by L, preferred ones are
It is represented by the following formulas L5 (pentamethine), L7 (heptamethine) and L9 (nonamethine).

[0018]

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In the formula, R ³⁰ is a hydrogen atom, an alkyl group, a halogen atom, an aryl group, NR ³² R ³³ , SR ³⁴ or OR.
³⁴ (R ³² , R ³³ and R ³⁴ each represent an alkyl group or an aryl group). R ³² and R ³³ may combine to form a heterocycle (eg piperidine, morpholine). R ²⁹ and R ^31, represents an atomic group necessary for forming a hydrogen atom or a bond to 5-membered or 6-membered ring together, R ³⁹
And R ⁴⁰ are each a hydrogen atom or an alkyl group. It is preferable that R ²⁹ and R ³¹ are bonded to each other to form a 5- or 6-membered ring. Examples of the ring to be formed include a cyclopentene ring and a cyclohexene ring. The rings may have a substituent (for example, an alkyl group and an aryl group).

The above alkyl group has the same meaning as the alkyl group of R ¹ and R ² . The halogen atom is F, Cl, Br
It is. The aryl group preferably has 6 to 12 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
The aryl group may be substituted, and as the substituent,
An alkyl group having 10 or less, preferably 6 or less carbon atoms (eg, methyl, ethyl, butyl, hexyl), an alkoxy group having 10 or less, preferably 6 or less carbon atoms (eg,
Methoxy, ethoxy), aryloxy groups having 20 or less, preferably 12 or less carbon atoms (eg, phenoxy, p
-Chlorophenoxy), a halogen atom (Cl, Br,
F), alkoxycarbonyl groups having 10 or less, preferably 6 or less carbon atoms (eg, ethoxycarbonyl), cyano groups, nitro groups and carboxyl groups.

In the formula (1a), a, b and c are 0 or 1 respectively. a and b are preferably 0. c is generally 1. However, c becomes 0 when an anionic substituent such as carboxyl forms an intramolecular salt with N ⁺ .

Examples of the anion represented by X, a halogen ion (Cl, Br, I), p- toluenesulfonate ion, ethyl sulfate _{^{ion, PF 6 -, BF 4 -}} , ClO
₄ ^- and can be exemplified anion represented by the formula (6).

[0023]

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In the formula, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each a hydrogen atom, an alkyl group, an aryl group, a cyano group or R ³⁵ and R ³⁶ or R ³⁷ and R ³⁸ are connected to each other. Represents a non-metal atom necessary for forming an aromatic ring, Y ¹ and Y ²
Each represent O, S or NH, M represents Ni, C
represents a metal atom of o, Cu, Pt, Pd, Fe, Mn, or Zn.

The alkyl group and aryl group represented by R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ have the same meanings as the alkyl group described in R ¹ and R ² and the aryl group described in R ³⁰ , respectively.
Examples of the aromatic ring formed by R ³⁵ and R ³⁶ and R ³⁷ and R ³⁸ connected to each other include a phenyl group and a naphthyl group. It may be substituted with a methyl, t-butyl, methoxy, chlorine atom or the like. When the counterion of the dye of the general formula (1a) is the formula (6), the compound of the formula (3a), (4) or (5) may or may not be used. A more preferred heptamethine cyanine dye is of formula (1b).

[0026]

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In the formula, Z ³ and Z ⁴ each represent an atom required to form a benzo or naphtho condensed ring, and R ²³ and R 4
²⁴ represents an alkyl group, an aralkyl group or an alkenyl group, and R ²⁹ and R ³¹ each represent a hydrogen atom or an atomic group necessary for connecting with each other to form a 5- or 6-membered ring;
R ³⁰ represents a hydrogen atom, an alkyl group, a halogen atom, an aryl group, NR ³² R ³³ , SR ³⁴ or OR ³⁴ , and R ³² , R
³³ and R ³⁴ each represent an alkyl group or an aryl group, and R ³² and R ³³ may be connected to each other to form a 5- or 6-membered ring. R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each represent an alkyl group, and R ²⁵ and R ²⁶ and R ²⁷ and R ²⁸ may be linked to form a ring. X represents an anion, and c represents 0 or 1.

The general formula (1b) will be described in detail. Z ³ and Z ⁴
The benzo- or naphtho-condensed ring formed by may be substituted with the substituent described for Z ¹ or the like. R ²³ , R ²⁴ ,
The alkyl group represented by R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ , R ³² , R ³³ and R ³⁴ has the same meaning as the alkyl group in R ^{1 and the} like of the general formula (1). R ²⁵ and R ²⁶ and R ²⁷ and R ²⁸ may combine with each other to form a ring (eg, cyclohexane). The alkenyl group and aralkyl group represented by R ²³ and R ²⁴ have the same meaning as the alkenyl group and aralkyl group of R ¹ and R ² . The aryl group represented by R ³⁰ , R ³² , R ³³ and R ³⁴ has the same meaning as the aryl group described for R ³⁰ in formula (L5). The halogen atom of R ³⁰ has the formula (L
It has the same meaning as the halogen atom of R ³⁰ in 5). Ring formation by R ²⁹ and R ³¹ has the same meaning as the ring formed by R ²⁹ and R ³¹ of formula (L7). The ring formation by R ³² and R ^{33 is represented} by the general formula (L
It is synonymous with the ring formation by R ³² and R ^{33 in} 5). X has the same meaning as X in formula (1a). c is c in the general formula (1a)
Is synonymous with The most preferred heptamethine cyanine dye is of formula (1c).

[0029]

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In the formula, Z ³ and Z ⁴ each represent an atom necessary for forming a benzo or naphtho condensed ring, R ²³ and R ²⁴ each represent an alkyl group, an aralkyl group or an alkenyl group, and R ³² and R ³³ each represents an alkyl group or an aryl group, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each represent an alkyl group, and R ²⁵ and R ²⁶ and R ²⁷ and R ²⁸ may be linked to form a ring. Good. X represents an anion, and c is 0 or 1.
Represents

The formula (1c) will be described in detail. The benzo- or naphtho-condensed ring formed by Z ³ and Z ⁴ may be substituted with the substituent described for Z ^{1 and the} like. R ²³ , R ²⁴ , R ²⁵ , R
^The alkyl group represented by ²⁶ , R ²⁷ , R ²⁸ , R ³² and R ³³ has the same meaning as the alkyl group in R ^{1 and the} like described in the general formula (1a). R ²⁵ and R ²⁶ and R ²⁷ and R ²⁸ may combine with each other to form a ring (eg, cyclohexane). The alkenyl group and aralkyl group represented by R ²³ and R ²⁴ have the same meaning as the alkenyl group and aralkyl group of R ¹ and R ² in formula (1a). The aryl group represented by R ³² and R ³³ has the same meaning as the aryl group described for R ³⁰ in formula (L5). X has the same meaning as X in formula (1a). c has the same meaning as c in formula (1a).

The above-mentioned cyanine dye has the above general formula (3)
The present invention is achieved by adding the compound of any one of a), (4) and (5). However, when the compound of the formula (6) is contained as the counter ion of the cyanine dye, the compound of the general formula (3a), (4) or (5) may or may not be added.

The general formula (2) will be described in detail. The alkyl group and aralkyl group represented by R ³ to R ¹⁰ are each represented by the general formula (1
It has the same meaning as the alkyl group and aralkyl group represented by R ¹ in a). Examples of the cycloalkyl group represented by R ³ to R ¹⁰ include cyclopentyl and cyclohexyl. The aryl group represented by R ³ to R ¹⁰ has the same meaning as the aryl group of R ^{30 in} formula (L5).

The general formula (3a) will be described in detail. L represents a ligand that is a group or molecule bonded to a metal. As examples of the ligand, various groups or molecules described in “Organometallic Compound Synthesis and Utilization”, supervised by Akio Yamamoto, Tokyo Kagaku Dojin, page 25 can be used. M is Ni, C
represents a metal atom of o, Cu, Pt, Pd, Fe, Mn, or Zn, n ¹ is an integer of ¹ to 10, and m ¹ is 0 or 1.
Represents Roughly preferred are compounds of general formula (3b).

[0035]

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In the formula, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each a hydrogen atom, an alkyl group, an aryl group, a cyano group or R ³⁵ and R ³⁶ , or R ³⁷ and R ³⁸ are linked to each other. Represents a non-metal atom necessary for forming an aromatic ring, Y ¹ and Y ² each represent O, S or NH, M represents Ni,
Represents a metal atom of Co, Cu, Pt, Pd, Fe, Mn or Zn, A represents a quaternary ammonium salt or a quaternary phosphonium salt, m ² represents 0, -1 or -2, m
³ represents 0, 1 or 2.

An alkyl group represented by R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ of formula (3b), an aryl group, and R ³⁵ and R ³⁶ and R ³⁷ and R ³⁸ are formed by being connected to each other. The aromatic ring has the same meaning as R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ of the general formula (6).
Examples of the ammonium salt represented by A include tetramethylammonium, tetraethylammonium, tetrabutylammonium, octyltriethylammonium, phenyltrimethylammonium, phenyltriethylammonium, triphenylbutylammonium, triphenylbenzylammonium, tetraphenylammonium and the like. Can be done. Examples of the phosphonium salt represented by A include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, octyltriethylphosphonium, phenyltrimethylphosphonium, phenyltriethylphosphonium, triphenylbutylphosphonium, triphenylbenzylphosphonium, and tetraphenylphosphonium. Can be done. m ² represents 0, −1 or −2, m ³ is 0,
Represents 1 or 2. When m ² is 0, m ³ is 0, m ²
When m is 1, m ³ is 1, and when m ² is 2, m ³ is 2
become.

The general formula (4) will be described in detail. R ¹¹ , R ¹² , R
^The alkyl group represented by ¹³ and R ¹⁴ has the same meaning as the alkyl group represented by R ¹ and R ² in the general formula (1a). R ¹¹
And R ¹² and R ¹³ and R ¹⁴ may combine to form a heterocycle, for example, pyrrolidine or piperazine. X has the same meaning as X in formula (1).

The general formula (5) will be described in detail. R ²² , R ¹⁶ , R
^The alkyl group represented by ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ has the same meaning as the alkyl group of R ¹ and R ^{2 in} the general formula (1). The aryl group represented by R ²² is R ^{30 of the} formula (L5).
Is synonymous with the aryl group of. The halogen atom represented by R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ is represented by R ^{30 of the} general formula (L5).
Is synonymous with the halogen atom of. Examples of the alkoxy group represented by R ¹⁸ and R ¹⁹ include a methoxy group and an ethoxy group. The aralkyl group represented by R ²⁰ and R ²¹ is
It has the same meaning as the aralkyl group represented by R ^{1 in} formula (1a). R
²⁰ and R ²¹ may combine with each other to form piperidine or pyrrolidine. Further, it may combine with adjacent R ¹⁹ to form julolidine or the like.

General formula (1a) and general formulas (3a) and (4)
Or in the combination of (5), preferred is (1
It is a combination of a) and (3a). Furthermore, (1
The combination of b) and (3b) is preferable, and the combination of (1c) and (3b) is most preferable. Also, a dye having a compound represented by the general formula (6) as an anion of the general formula (1a) is preferable, and a combination of (1b) and an anion (6), particularly (1c) and an anion (6).
Is most preferred. Further, in the combination of the general formula (2) and the general formula (3a), (4) or (5),
The combination of (2) and (3a), and more preferably the combination of (2) and (3b). Examples of compounds used in the present invention are shown below.

[0041]

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[0042]

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[0043]

[Chemical 21]

[0044]

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[0050]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0070]

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The compounds (1a), (1b) and (1c) of the present invention can be prepared according to the methods described in US Pat. Nos. 3,671,648 and 2,
095,854, JP-A-6-43583 and the like, and the following synthesis examples can be used for synthesis. The compound of formula (2) is US Pat. No. 5,380,635, and the compound of formula (3) is Dye and Pigment 8
(1987) 381-388, the compound of formula (4) is synthesized by referring to JP-B-43-25335, and the compound of formula (5) is synthesized by referring to JP-A-50-100116 and JP-A-2-129268, respectively. it can.

Synthesis Example (Synthesis of Compound 1-28) 1,2,3,5-Tetramethyl-5-chloroindolenium p-toluenesulfonate 11.4 g, N- (2,5-dianilinomethylene cyclopentylidene ) -Diphenylaminium tetrafluoroborate 7.2 g, ethyl alcohol 100 ml,
Acetic anhydride 6ml, triethylamine 12ml external temperature 100 ℃
After stirring for 1 hour, the precipitated crystals were filtered off. Recrystallization was carried out with 100 ml of methyl alcohol and 7.3 g of compound 1-2.
8 was obtained. Melting point: 250 ° C or higher, λmax: 800.8n
m, ε: 2.14 × 10 ⁵ (chloroform)

The dye represented by (1a) or (2) can be added to the photosensitive layer, the dye layer near the support on the same side as the photosensitive layer, or the dye layer on the side opposite to the photosensitive layer. Dye varies depending desired purpose 0.1 to 1000 mg / m ^2, but it is preferable 1 to 200 mg / m ² is added. The dye is preferably added after being dissolved in an organic solvent. (3a),
The anti-fading agent represented by (4) or (5) is 0.1 to 1000 mg / m ² , preferably 1 to 1000 in the same layer as the above dye.
It is recommended to add 200 mg / m ² . The anti-fading agent is preferably added after being dissolved in an organic solvent. In the present invention, it is preferable that the dye and the anti-fading agent of the present invention are simultaneously added to the dye layer near the support on the same side as the photosensitive layer or to the dye layer on the side opposite to the photosensitive layer. Although the dye remains without being decolorized after being heat-developed, the light fastness is improved by the anti-fading agent.

From the viewpoint of being friendly to the earth, it is preferable that the photothermographic material is such that the dye substantially remains on the image sheet where it is observed. More preferably, it is a mono-sheet type (a type in which all materials provided for forming an image are completed as an image sheet to be observed) and a photothermographic material. Further, in order to achieve the object, a photothermographic material for infrared laser exposure is preferably used. Further, the wavelength of infrared laser exposure is preferably 750 nm or more, more preferably 800 nm or more.

The photothermographic material of the present invention forms a photographic image using a photothermographic method. Such a photothermographic material is disclosed in, for example, US Pat.
No. 152904, 3457075, and D.C. Morgan and B.A. "Thermally Processed SilverSy" by Shely
stems) "(Imaging Processors and
Materials (Imaging Processes and Materials) Neb
lette 8th edition, Sturge, V. Walworth, A. Edited by Shepp, page 2,
1969) and the like.

The heat-developable light-sensitive material of the present invention may be any one capable of forming a photographic image by using a heat-development treatment, but includes a reducible silver source (eg organic silver salt) and a catalytically active amount of photocatalyst (eg halogen). It is preferably a photothermographic material containing silver halide), a color tone controlling agent for controlling the color tone of silver, and a reducing agent in a state of being normally dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature,
After exposure, development is performed by heating to a high temperature (for example, 80 ° C. or higher). Heating produces silver through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. A filter layer may be formed on the same side or the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, and the photosensitive layer may be represented by the general formula (1a) or (2). Dye,
Other dyes or pigments may be included. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high sensitive layer / low sensitive layer or a low sensitive layer / high sensitive layer for adjusting gradation. Various additives may be added to any of the light-sensitive layer, the non-light-sensitive layer, and other forming layers.

The support applicable to the photothermographic material of the present invention includes, for example, paper, polyethylene-coated paper, polypropylene-coated paper, parchment, cloth and the like materials;
Sheets or films of metals such as aluminum, copper, magnesium, zinc; glass or chromium alloy, steel,
Glass coated with a metal such as silver, gold, platinum; poly (alkyl methacrylates) (eg, poly (methyl methacrylate)), poly (esters) (eg, poly (ethylene terephthalate)), poly (vinyl acetal) ), Poly (amides) (eg, nylon), and cellulose esters (eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate). The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

Each binder layer (eg, synthetic polymer) together with the chemical agent in the photothermographic material of the present invention may form a self-supporting film. The support is made of known auxiliary materials, for example, vinylidene chloride, acrylic acid monomers (for example, acrylonitrile and methyl acrylate)
And copolymers and terpolymers of unsaturated dicarboxylic acids (eg, itaconic acid, acrylic acid), carboxymethylcellulose, poly (acrylamide); and similar polymeric materials.

Suitable binders are transparent or translucent, generally colorless, and include natural polymeric synthetic resins, polymers and copolymers, and other film-forming media such as:
Gelatin, gum arabic, poly (vinyl alcohol),
Hydroxyethyl cellulose, cellulose acetate,
Cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
(Eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or an emulsion.

The addition of toning agents is highly desirable. Examples of suitable toning agents are disclosed in Research Report No. 17029,
There are the following: imides (eg, phthalimide);
Cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline, and 2,4-thiazolidinedione); naphthalimides (eg, , N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3-mercapto-1,2,4-triazole); N
-(Aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide);
Blocked pyrazoles, isothiuronium (isot
hiuronium) derivatives and certain photobleaching combinations (eg, N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-
A combination of dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl-2-benzothia) Zolinylidene (benzothiazolinylidene) -1
-Methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (e.g.,
4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione; a combination of phthalazinone and a sulfinic acid derivative (eg, ,
6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); combination of phthalazine + phthalic acid; phthalazine (including adduct of phthalazine), maleic anhydride, and phthalic acid , 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (for example,
Phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) in combination with at least one compound; quinazolinediones, benzoxazine, naltoxazine derivatives; benzoxazine-2,4-dione (Eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg
3,6-dimerocapto-1,4-diphenyl-1H, 4
H-2,3a, 5,6a-tetraazapentalene. A preferred toning agent is phthalazine:

[0082]

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Is as follows. The reducing agent may contain a so-called photographic developer, for example, phenidone, hydroquinones, catechol and the like, but hindered phenol is preferred. A color light-sensitive material as disclosed in U.S. Pat. No. 4,460,681 is also conceivable for realizing the present invention.

Examples of suitable reducing agents are described in US Pat. No. 3,770.
Nos. 448, 3773512, 3959633, and Research Disclosure Nos. 17029 and 29.
963, and include: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, Piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (for example, Np-
Methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfohydroxamic acids (eg, benzenesulfohydroxamic acid); sulfonamidoanilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Tetrahydroquinoxaline); amidooxins; azines (for example, aliphatic carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxanoic acids; azines and sulfones Combination of amidophenols; α-cyanophenylacetic acid derivative; bis-β-naphthol and 1,3-
5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (e.g., 2,6-dimethoxy-3) , 5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-
Hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4 -Ethylidene-bis (2
-T-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Preferred developers are hindered phenols of the general formula (A):

[0085]

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R ⁵⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, —C ₄ H ₉ , 2, 4,
4-trimethylpentyl), R ⁵¹ and R ⁵² are alkyl groups having 1 to 5 carbon atoms (for example, methyl, ethyl,
t-butyl).

Silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver silver, silver chlorobromide, silver iodobromide, chloroiodo). However, it is preferable that the iodide ion is contained. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. The latter is preferred.

The reducible silver source can be any material containing a source of reducible silver ions. Silver salts of organic and heteroorganic acids, especially long chains (10-30, preferably 15-25
) Aliphatic carboxylic acids are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are described in Research Disclosure No. 1702.
9 and 29996, and include the following:
Salts of organic acids (eg gallic acid, oxalic acid, behenic acid,
Stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); aldehyde Silver complexes (e.g., aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (e.g., salicylic acid, benzoic acid, 3,5-
Dihydroxybenzoic acid, 5,5-thiodisalicylic acid),
Silver salts or complexes of thioenes (eg, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole ,
Urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-
Complexes or salts of silver and nitrogen acids selected from triazoles and benzotriazoles; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. The preferred silver source is silver behenate. The reducible silver source preferably has a silver content of 3 g / m ² or less. More preferably, it is 2 g / m ² or less.

An antifoggant may be contained in such a light-sensitive material. The most effective antifoggant was mercury ion. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 03. However, mercury compounds are environmentally unfavorable. As the non-mercury antifoggant, for example, the antifoggants disclosed in U.S. Pat. Nos. 4,456,075 and 4,458,885 and JP-A-59-57234 are preferable.

Particularly preferred non-mercury antifoggants are compounds such as those disclosed in US Pat. Nos. 3,874,946 and 4,756,999, --C (X ¹ ) (X ² ) (X ³ ), where X ¹ and X ² Is a heterocyclic compound having one or more substituents represented by halogen (for example, F, Cl, Br and I) and X ³ is hydrogen or halogen). Examples of suitable antifoggants include:

[0091]

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[0092]

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Even more preferred antifoggants are US Pat. No. 5,028,523 and our British patent application No. 92221.
Nos. 383.4, 9300147.7, 931179
No. 0.1.

The photothermographic material of the present invention includes, for example, JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651 and 6-63.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used.

[0095]

【Example】

Example 1 Photosensitive mixture NaOH 89 g Distilled water 1500ml solution prepared solution stearate 131g behenic acid 635g of distilled water 13 liters 85 ° C. 15 minutes Emulsion A concentrated HNO ₃ 19 ml of distilled water 50ml solution AgNO ₃ 365 g Distilled water 2500ml solution of polyvinyl butyral 86 g ethyl acetate 4300 ml solution polyvinyl butyral 290 g isopropanol 3580 ml solution N-bromosuccinimide 9.7 g acetone 690 ml

The solution was added over 5 minutes with vigorous stirring while the temperature was kept at 85 ° C., and then the solution was added to 2
Add over 5 minutes. After stirring for 20 minutes as it is, 35
Cool down to ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes.
Thereafter, the solution was added, the stirring was stopped, and the mixture was left to stand. The aqueous phase was removed together with the contained salt to obtain an oil phase. The solvent was removed to remove traces of water. Then, the solution was added and the mixture was stirred vigorously at 50 ° C. Thereafter, the solution was added over 20 minutes and stirred for 105 minutes to obtain Emulsion A.

The following layers were successively formed on a polyethylene terephthalate support colored blue with Dye-A. Drying was performed at 75 ° C. for 5 minutes each.

Backside coating Antihalation layer (wet thickness 80 microns) 1: 1 mixture of polyvinyl butyral (10% isopropanol solution) and cellulose acetate butyrate (10% acetic acid ethyl ester solution) 150 ml Dye (solvent DMF, Acetone or methyl chloride is used) Listed in Table 1 62 ml Anti-fading agent (Acetic acid ethyl ester or methyl chloride is used as solvent) Listed in Table 1

Photosensitive layer side coating Photosensitive layer (wet thickness 140 microns) Photosensitive emulsion A 73g Sensitizing dye-1 (0.1% DMF solution) 2ml Antifoggant-1 (0.01% methanol solution) 3ml Fog Inhibitor-2 (0.85% methanol solution) 10 ml Antifoggant-3 (0.85% methanol solution) 10 ml Phthalazone (4.5% DMF solution) 8 ml Reducing agent-1 (10% acetone solution) 13 ml

Surface protective layer (wet thickness 100 micron) Acetone 175 ml 2-Propanol 40 ml Methanol 15 ml Cellulose acetate 8.0 g Phthalazine 1.0 g 4-Methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Tetrachlorophthalic anhydride 0.5 g

[0101]

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[0102]

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Sensitometry The photothermographic material prepared above is processed into a half-cut size,
An 830 nm laser diode was exposed with a beam tilted 13 ° from the vertical. Then use a heat drum for 1
Heat development was performed at 20 ° C for 5 seconds. Evaluation of sharpness Exposure was made to white light of 2856K with light dispersed by using an interference filter of 830 nm and processed under the above conditions, and sharpness was measured with an optical density of 1.0 and an MTF value of 15 lines / mm. evaluated.

Evaluation of Residual Color Samples subjected to heat development without exposure were visually evaluated. ：: good △: worried about residual color ×: problematic with residual color

Evaluation of light fastness A xenon irradiator (lamp: XENO manufactured by Atlas Electric Devices Co., Ltd.) was applied to the back coating surface side of the sample.
N BURNER WARRANTY LOG WATTAGE 3500/6500 type)
8500 lx 30 ° C. 30% RH 3.8 hours extinguished 20 ° C. 90% RH 1 hour cycle of 5 rounds of exposure for a total of 24 hours, and the residual rate of the dye was determined from the change in absorption spectrum.

[0106]

[Table 1]

From Table 1, the samples of the present invention have no problem in residual color, have good sharpness, and are light fast.

Example 2 Preparation of Photosensitive Emulsion B Solution Stearic acid 131 g Behenic acid 635 g Distilled water 13 liters 85 ° C. mixing for 15 minutes Solution A Preformed cubic AgBrI (I = 4 mol%) 0.06 μ (as Ag) 0.22 mole) distilled water 1250ml solution NaOH 89 g distilled water 1500ml solution of concentrated HNO ₃ 19 ml of distilled water 50ml solution AgNO ₃ 365 g distilled water 2500ml solution polyvinylbutyral 86g ethyl acetate 4300ml solution polyvinylbutyral 290g isopropanol 3580ml

Solution A was added over 10 minutes with vigorous stirring while maintaining the solution at 85 ° C., followed by addition of solution over 5 minutes, and then over 25 minutes. After stirring for 20 minutes as it is, the temperature is lowered to 35 ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes. Thereafter, the solution was added, the stirring was stopped and the mixture was left to stand, and the aqueous phase was extracted together with the salt contained therein to obtain an oil phase. After removing the traces of water by removing the solvent, the solution was added and the mixture was stirred vigorously at 50 ° C. Later, 10
Emulsion B was obtained by stirring for 5 minutes.

A test was conducted in the same manner as in Example 1 (however, the antihalation layer was provided below the photosensitive layer on the side of the photosensitive layer). It was found that the sample using the dye of the present invention had no residual color as in Example 1 and had high sharpness and light fastness.

Claims (5)

[Claims] 1. The following general formula (1a) or general formula (2):
A photothermographic material comprising a dye represented by the following formula and at least one compound represented by the following general formula (3a), (4) or (5). Embedded image In the formula, Z ¹ and Z ² each represent a non-metal atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle which may be condensed, and R ¹ and R ² are each an alkyl group or an alkenyl group. Or represents an aralkyl group, L represents a linking group formed by linking 5, 7 or 9 methine groups by a conjugated double bond, a, b and c each represent 0 or 1, and X represents an anion. . However, when X is an anion containing M of the general formula (3a), the general formula (3a), (4) or (5)
The compound represented by may not be contained. Embedded image In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ³ and R
⁴ and or R ⁵ and R ⁶ and or R ⁷ and R ⁸
And, or R ⁹ and R ¹⁰ or R ⁴ and R ^5, and or R ⁸ and R ⁹ may form a 5- or 6-membered ring. Embedded image In the formula, L represents a ligand, M represents Ni, Co, Cu, P
represents a metal atom of t, Pd, Fe, Mn or Zn, and n
¹ represents an integer of ¹ to 10, and m ¹ represents 1 or 2. Embedded image In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom or an alkyl group, and X represents an anion. Embedded image In the formula, R ¹⁵ is a hydrogen atom, a halogen atom, CONHR ²² ,
Represents _{^{SO 2 NHR 22, NHSO 2 R}} 22, NHCOR 22 or NHCONHR ^22, R ²² represents an alkyl group or an aryl group, each of R ¹⁶ and R ¹⁷ a hydrogen atom, an alkyl group, a halogen atom, NHCOR ^22, NHSO ₂ R
²² or a non-metal atom necessary to form an aromatic ring by being linked to each other, R ²² represents an alkyl group or an aryl group, R ¹⁸ and R ¹⁹ represent a hydrogen atom, an alkyl group,
Represents an alkoxy group, a hydroxyl group or a halogen atom, and R ²⁰ and R ²¹ each represent an alkyl group, an aralkyl group, or an atom necessary for forming a heterocycle by connecting to each other or a substituent R ¹⁹ adjacent to each other. , N ² is 0,
Represents 1 or 2. 2. The dye represented by the general formula (1a) is
The photothermographic material according to claim 1, which is a dye represented by the following general formula (1b). [Chemical 6] In the formula, Z ³ and Z ⁴ each represent an atom necessary for forming a benzo or naphtho condensed ring, R ²³ and R ²⁴ each represent an alkyl group, an aralkyl group or an alkenyl group, and R ²⁹
And R ³¹ is a hydrogen atom or 5 or 6 linked to each other.
Represents an atomic group necessary for forming a member ring, R ³⁰ is a hydrogen atom, an alkyl group, a halogen atom, an aryl group, NR ³² R
³³ , SR ³⁴ or OR ³⁴ , R ³² , R ³³ and R ³⁴ each represent an alkyl group or an aryl group, and R ³² and R ^34
33 may combine with each other to form a 5- or 6-membered ring.
R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ each represent an alkyl group, and R ²⁵ and R ²⁶ and R ²⁷ and R ²⁸ may be linked to form a ring. X represents an anion, and c represents 0 or 1. 3. The dye represented by the general formula (1a) is
A dye represented by the following general formula (1c),
The photothermographic material according to claim 1. Embedded imageWhere Z^ThreeAnd Z^FourAre each a benzo or naphtho fused ring
Represents an atom necessary to form^{twenty three}And R^{twenty four}Are each
R represents an alkyl group, an aralkyl group or an alkenyl group, and R
³²And R³³Each represents an alkyl group or an aryl group,
R^{twenty five}, R²⁶, R ²⁷And R²⁸Each represents an alkyl group
Then R^{twenty five}And R²⁶And R²⁷And R²⁸Connect to form a ring
You may. X represents an anion, c represents 0 or 1.
You. 4. The photothermographic material according to claim 1, wherein the compound represented by the general formula (3a) is a compound represented by the following general formula (3b). Embedded image In the formula, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each a hydrogen atom,
An alkyl group, an aryl group, a cyano group, or R ³⁵ and R ³⁶ or R ³⁷ and R ³⁸ each represent a non-metal atom necessary for forming an aromatic ring, and Y ¹ and Y ² are O and S, respectively. Or NH, M is Ni, Co, Cu, P
represents a metal atom of t, Pd, Fe, Mn or Zn, and A
Represents a quaternary ammonium salt or a quaternary phosphonium salt, m ² represents 0, -1 or -2, and m ³ represents 0, 1 or 2. 5. The photothermographic material according to claim 1, which is for infrared laser exposure.