JPH095926A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material less liable to fog and having improved preservability of the material and an image without lowering sensitivity or deteriorating color tone by incorporating at least one kind of specified compd. SOLUTION: This heat developable photosensitive material contains at least one kind of compd. represented by the formula R1 -S-S-R2 , wherein R1 is aryl, pyridyl or quinolyl and R2 is aryl, pyridyl or quinolyl having at least one substituent selected from among aliphatic hydrocarbon, aryl, amino, alkoxy, aryloxy, alkoxycarbonylamino, aryloxycarbonylamino, acyloxy, acylamino, carbamoyl, sulfonyl amino, phosphoric acid amido, sulfamoyl, alkylthio, arylthio, thio- carbonyl, sulfonyl, sulfinyl, ureido, thioureido, thioamido, etc.

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 technology for preventing fog, improving the storability of a light-sensitive material and the storability of an image without deteriorating the sensitivity and the color tone.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat. No. 3,152,904.
No. 3457075 and D.C. Morgan and B.A. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials) Neblette 8th
Edition, Sturge, V. Walworth
th), A. Edited by Shepp, page 2, 1969
Year). Such a photothermographic material is
It contains a reducible silver source (eg organic silver salt), a catalytically active amount of photocatalyst (eg silver halide), a toning agent controlling the color tone of silver and a reducing agent, usually dispersed in an (organic) binder matrix. ing. The photothermographic material is stable at room temperature, but it is a reducible silver source (functions as an oxidizing agent) when heated to a high temperature (for example, 80 ° C or higher) after exposure.
Silver is produced through a redox reaction between a reducing 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 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 most effective antifoggant as a conventional fog preventing technique has been mercury ion. The use of mercury compounds as antifoggants in light-sensitive materials is disclosed, for example, in US Pat. No. 3,589,903. However, mercury compounds are environmentally unfavorable. Non-mercury antifoggants are also disclosed in U.S. Pat. Nos. 3,874,946 and 47.
Compounds as disclosed in 56999, -C (X
¹ ) (X ² ) (X ³ ), wherein X ¹ and X ² are halogen (eg F, Cl, Br and I) and X ³ is hydrogen or halogen) Although they are heterocyclic compounds, if they are used as they are, there are problems such that the color tone of silver is remarkably deteriorated and the sensitivity is lowered, so that there is a need for improvement. Further, after aging under a forced humidification / warming condition in a laminated form of the photosensitive material, exposure /
There is a problem that fogging in the unexposed area increases when developed, and development of an antifoggant without these problems has been desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material which has low fog and improved storability of light-sensitive material and image storability without deterioration of sensitivity and deterioration of color tone.

[0005]

The above object has been achieved by the following means. (1) A photothermographic material containing at least one compound represented by the following general formula (I). General formula (I)

[0006]

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(In the formula, R ₁ represents an aryl group, a pyridyl group or a quinolyl group. R ₂ represents an aliphatic hydrocarbon group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkoxycarbonylamino group or an aryl group. Oxycarbonylamino group, acyloxy group, acylamino group,
Carbamoyl group, sulfonylamino group, phosphoramide group, sulfamoyl group, alkylthio group, arylthio group, thiocarbonyl group, sulfonyl group, sulfinyl group, ureido group, thioureido group, thioamide group, hydroxy group, mercapto group, sulfo group, phosphono group Represents an aryl group, a pyridyl group or a quinolyl group having at least one substituent selected from a group, a hydroxamic acid group and a heterocyclic group. )

(2) A photothermographic material containing at least one compound represented by the general formula (I) and at least one compound represented by the following general formula (II). General formula (II)

[0009]

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(In the formula, Q represents an aryl group or a heterocyclic group. X ₁ and X ₂ each represent a halogen atom. Y represents —C (═O) —, —SO— or —SO ₂ —. . A represents a hydrogen atom, a halogen atom or an electron-withdrawing group, and n represents 0 or 1.)

(3) The photothermographic material according to the above (1) or (2), which is for infrared laser exposure.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, general formula (I) will be described in detail. The aryl group represented by R ₁ and R ₂ is preferably an aryl group having 6 to 30 carbon atoms, more preferably a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms, such as phenyl and naphthyl. And the like, and particularly preferably phenyl.

An aryl group represented by R ₁ , a pyridyl group,
The quinolyl group may have a substituent, and as the substituent,
For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms).
An alkyl group of, for example, methyl, ethyl, iso-
Propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, and particularly preferably a carbon number of 2 to 8), such as vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms,
An alkynyl group having 2 to 8 carbon atoms is particularly preferable, and examples thereof include propargyl and 3-pentynyl. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 1 carbon atoms).
2 is an aryl group, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An amino group (preferably having a carbon number of 0 to 20, and more preferably having a carbon number of 0 to 1).
0, particularly preferably an amino group having 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. ), An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, and butoxy). An oxy group (preferably an aryloxy group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy). Acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 1 carbon atoms)
12 acyl groups, such as acetyl, benzoyl,
Formyl, pivaloyl and the like can be mentioned. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms).
Is an alkoxycarbonyl group, and examples thereof include methoxycarbonyl and ethoxycarbonyl. ), An aryloxycarbonyl group (preferably having 7 to 2 carbon atoms)
It is 0, more preferably an aryloxycarbonyl group having 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl. ),
Acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms).
Is an acyloxy group, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms,
Particularly preferably, it is an acylamino group having 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms,
An alkoxycarbonylamino group having 2 to 12 carbon atoms is particularly preferable, and examples thereof include methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino. ), A sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino. ), A sulfamoyl group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 16, and particularly preferably a carbon number of 0 to 12), such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfyl. Famoyl, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms,
Particularly preferred is a carbamoyl group having 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 20 carbon atoms,
More preferably, it is an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio,
Examples include ethylthio. ), An arylthio group (preferably having 6 to 20 carbon atoms, and more preferably having 6 to 1 carbon atoms).
6, particularly preferably an arylthio group having 6 to 12 carbon atoms, and examples thereof include phenylthio. ), A sulfonyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, and particularly preferably a carbon number of 1 to 12 and examples thereof include mesyl and tosyl) and a sulfinyl group ( Preferably 1 to 20 carbon atoms,
It is more preferably a sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ),
Ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, and phenylureido). Acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
To 16, particularly preferably a phosphoric acid amide group having 1 to 12 carbon atoms, and examples thereof include diethylphosphoric acid amide and phenylphosphoric acid amide. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (eg imidazolyl,
Pyridyl, furyl, piperidyl, morpholino and the like can be mentioned. ). These substituents may be further substituted. When there are two or more substituents,
They may be the same or different.

The substituent is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino. Group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, ureido group, phosphoramide group, hydroxy group, mercapto group, sulfo group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group And more preferably an alkoxy group,
Aryloxy group, acyloxy group, acylamino group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, and heterocyclic group, and more preferably Alkoxy group, aryloxy group, acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid amide group, particularly preferably acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group. .

R ₁ is preferably a phenyl group, a naphthyl group, a pyridyl group or a quinolyl group, more preferably a phenyl group or a naphthyl group, further preferably a phenyl group, particularly preferably an acylamino group or a sulfonylamino group. , A phenyl group substituted with a substituent selected from a sulfamoyl group, a carbamoyl group and an ureido group.

An aryl group represented by R ₂ , a pyridyl group,
The substituent of the quinolyl group will be described. The aliphatic hydrocarbon group is an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms).
An alkyl group of, for example, methyl, ethyl, iso-
Propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, and particularly preferably a carbon number of 2 to 8), such as vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms,
An alkynyl group having 2 to 8 carbon atoms is particularly preferable, and examples thereof include propargyl and 3-pentynyl. ), An aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, still more preferably 7 carbon atoms).
To 12 aralkyl groups, and examples thereof include benzyl and phenethyl. ), Preferably an alkenyl group or an alkynyl group. Aryl group, amino group, alkoxy group, aryloxy group, alkoxycarbonylamino group, aryloxycarbonylamino group, acyloxy group, acylamino group, carbamoyl group, sulfonylamino group, phosphoramide group, sulfamoyl group, alkylthio group, arylthio group , Thiocarbonyl group, sulfonyl group, sulfinyl group, ureido group, thioureido group, thioamide group, hydroxy group, mercapto group, sulfo group, phosphono group, hydroxamic acid group and heterocyclic group are the groups described for the substituent of R _1. It is synonymous with and the preferable range is also the same.

In addition to the above-mentioned substituents, R ₂ may be substituted with the above-mentioned substituents for R ₁ .

R ₂ is preferably a phenyl group, a naphthyl group, a pyridyl group or a quinolyl group substituted with the above substituents, more preferably a phenyl group or a naphthyl group substituted with the above substituents, further preferably Is a phenyl group substituted with the above-mentioned substituent, particularly preferably a phenyl group substituted with a substituent selected from an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group and a ureido group. Among the compounds represented by the general formula (I), the compound represented by the general formula (Ia) is preferable. General formula (Ia)

[0019]

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(In the formula, R ₂ has the same meaning as that in the general formula (I), and the preferable range is also the same.) Of the compounds represented by the general formula (I), the more preferable one is the general formula (I). -A compound represented by b). General formula (Ib)

[0021]

[Chemical 6]

(Wherein X represents an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group or a ureido group, m represents 1, 2 or 3, and a phenyl group is a substituent of R ₁ in addition to X. The acylamino group, the sulfonylamino group, the sulfamoyl group, the carbamoyl group, and the ureido group represented by X are as described for the substituent of R ₁ in the general formula (I). It has the same meaning as those groups and the preferred range is also the same. X is preferably an acylamino group, a sulfonylamino group or a ureido group, more preferably a sulfonylamino group. When m is 2 or 3, X may be the same or different from each other. m is preferably 1 or 2,
It is more preferably 1.

Of the compounds represented by the general formula (Ib), more preferred are compounds in which X is substituted at the ortho position or para position with respect to the disulfide group. General formula (I)
More preferably, among the compounds represented by the general formula (I-
The compound represented by c) or (Id). General formula (I-c)

[0024]

[Chemical 7]

General formula (Id)

[0026]

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(In the formula, R _c1 and R _d1 each represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R _c2 and R _d2 respectively represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or Represents a heterocyclic group, and has the general formula (Ic),
(I-d) phenyl group in the, -N (R _C2) SO ₂
In addition to the group represented by R _C1 and —N (R _d2 ) SO ₂ R _d1, it may be substituted. ) R _C1 and R _d1 are preferably an aliphatic hydrocarbon group or an aryl group, more preferably an alkyl group having 1 to 20 carbon atoms or a phenyl group having 6 to 20 carbon atoms, and further preferably 4 to 4 carbon atoms. It is an alkyl group having 16 carbon atoms and a phenyl group having 6 to 16 carbon atoms, and particularly preferably an alkyl group having 6 to 14 carbon atoms and a phenyl group having 6 to 14 carbon atoms. R _C2 and R _d2 are preferably a hydrogen atom or an aliphatic hydrocarbon group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably Is a hydrogen atom or a methyl group.

--N (R _d2 ) SO ₂ R _d1 and --N (R _e2 ) SO of the phenyl group in the general formulas (I-c) and (I-d).
The preferred substituent other than ₂ R _e1, an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group. Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

[Chemical 12]

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

[Chemical 21]

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

[Chemical formula 26]

If possible, the above compounds may be used in the form of salts. The compound represented by the general formula (I) of the present invention is, for example, 1
4-III, Chapter 8 8.4 or ORANIC FUNCTIONAL GR
OUP PREPARATIONS (Sandler, Karo, ACADEMIC PRESS Ne
w York and London) It can be synthesized by various methods such as those described in I-Chapt.18. The synthesis methods are roughly classified as follows. (1) Method by oxidation of corresponding mercaptan (2) Method by nucleophilic substitution of corresponding alkyl (aryl) halide with alkali metal polysulfide salt (3) Conversion of corresponding aniline derivative into diazinium salt and then alkali polysulfide Method for nucleophilic substitution reaction with metal salt

With respect to the mercaptans used in the method (1), there is no particular limitation on both alkyl and aryl mercaptans. As oxidation means, there are air oxidation (oxygen oxidation), dimethylsulfoxide oxidation, hydrogen peroxide oxidation. , Hypochlorous acid oxidation and the like. When performing these methods, the reaction can be accelerated by making the reaction system alkaline. It is also known that the reaction can be accelerated by adding a metal catalyst such as copper or iron.

The alkyl halide which can be used in the method (2) is preferably one having no functional group (eg, ketone, aldehyde, enone, etc.) which is susceptible to nucleophilic attack in its molecule. As for the series, the first class has the highest reactivity, and the reactivity decreases in the order of the second class and the third class. The aryl halide that can be used in the method (2) is generally preferably one having an electron-withdrawing character, and a benzene ring-type halide having a substituent such as halogen or nitro is highly reactive. It is preferable in that the target product can be obtained efficiently. In the case of a heteroaromatic halide having a hetero atom in the aromatic ring, it is more electron-withdrawing than a benzene ring, so that the target product can be obtained without particularly having an electron-withdrawing group in the heteroaromatic ring. Many. Further, as in the case of the alkyl halide, it is preferable that these aryl halides do not have a functional group (for example, ketone, aldehyde, enone, etc.) which is susceptible to nucleophilic attack in the molecule.

The aniline derivative which can be used in the method (3) is not particularly limited, but for the convenience of forming a diazonium salt and reacting it with an alkali metal polysulfide salt under an aqueous condition, it is an aniline derivative. And the diazonium salt formed is water-soluble.
When using an aniline derivative which has relatively low water solubility and does not efficiently form a diazonium salt, it is also possible to use a mixture of alcohols with water as a solvent. Also,
Hydrochloric acid and sulfuric acid are generally used as the acid for forming the diazonium salt, but borofluoric acid may be used for the purpose of improving the stability of the salt formed.

As a method for synthesizing the mercaptans used in the method (1), a new experimental chemistry course (edited by the Chemical Society of Japan, Maruzen)
14-III, Chapter 8, 8.1, ORANIC FUNCTIONAL GROUP PR
EPARATIONS (Sandler, Karo, ACADEMIC PRESS New York
and London) I-Chapt.18 or THE CHEMISTRY OF F
UNCTINONAL GROUPS (Patai, JONE WILLY & SONS) "
It can be synthesized by various methods such as those described in The Chemistry of the thiol group "-Chapt.

Next, typical examples of the synthesis of the compound represented by formula (I) of the present invention are shown below. Synthesis Example Synthesis of Compound I-3 4,4′-dithiodianiline 5.00 g (0.020 mol) was dissolved in acetonitrile 40 ml, cooled to 0 ° C. or lower under nitrogen atmosphere, and stirred with triethylamine 4.45 g. (0.044 mol) was added, and 6.19 g (0.044 mol) of benzoyl chloride was added to the reaction solution at 5 ° C.
It was dropped so that it would not exceed. After stirring at 5 ° C or lower for 20 minutes, the mixture was further stirred at room temperature for 1 hour. Pour the reaction solution into water,
The precipitated solid was collected by filtration and recrystallized from dimethylformamide / methanol to obtain 6.80 g (0.0149 mol) of the target compound I-3. Yield 74.5
% Melting point 260 ° C or higher

Synthesis Example 2 Synthesis of Compound I-4 25.0 g (0.1 mol) of 2,2'-dithioaniline was dissolved in 250 ml of acetonitrile, and 15.6 ml (0.2 20.4 g (0.2 mol) of acetyl chloride
Was slowly added dropwise. After stirring for 2 hours at room temperature,
Since the target substance was precipitated, 150 ml of acetonitrile was added, heated and dissolved, and then ice-cooled and recrystallized. The precipitate was collected by filtration, and 28.0 g (0.0
84 mol) was obtained. Yield 84.2% Melting point 167-168
° C

Synthesis Example 3 Synthesis of Compound I-16 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.2 g (0.040 mol) of pentafluorobenzoyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 10.5 g (0.016 mol) of the target compound I-16. Yield 8
2.7% melting point 218-219 ° C

Synthesis Example 4 Synthesis of Compound I-45 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring, pyridine 3.4 ml
(0.044 mol) was added, and 7.4 g (0.042 mol) of benzenesulfonyl chloride was added to the reaction solution at 10 ° C.
It was dropped so that it would not exceed. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours.
The reaction solution was poured into water and 250 ml of ethyl acetate was added for extraction. After the extract was dried and concentrated, the origin compound was removed and purified by silica gel chromatography (ethyl acetate / hexane = 1/1) to give the desired compound I-45.
3 g (0.017 mol) was obtained. Yield 87.7% Melting point 166-167 ° C

Synthesis Example 5 Synthesis of Compound I-46 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring, pyridine 3.4 ml
(0.044 mol) was added, and 7.4 g (0.042 mol) of benzenesulfonyl chloride was added to the reaction solution at 15 ° C.
It was dropped so that it would not exceed. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours.
The reaction solution was poured into water, the precipitated solid was collected by filtration, and recrystallized from ethyl acetate / isopropyl alcohol to obtain 8.4 g (0.016 mol) of the target compound I-46. Yield 79.0% Melting point 148-149 ° C

Synthesis Example 6 Synthesis of Compound I-48 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 10.7 g (0.040 mol) of diphenylphosphoric acid chloride was added to the reaction liquid at 15 ° C.
It was dropped so that it would not exceed. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours.
The reaction solution was poured into water, and the precipitated solid was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to give 8.9 g (0.012) of the target compound I-48.
Mol) obtained. Yield 62.2% Melting point 183-185
° C

Synthesis Example 7 Synthesis of Compound I-56 7.45 g (0.030 mol) of 2,2′-dithioaniline was dissolved in 50 ml of acetonitrile, cooled to 5 ° C. or lower under a nitrogen atmosphere, and stirred with phenyl. 7.14 g (0.060 mol) of isocyanate was added to the reaction solution at 15 ° C.
It was dropped so that it would not exceed. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited.
The precipitate is collected by filtration and washed with acetonitrile, the target compound I
13.6 g (0.028 mol) of -56 was obtained. Yield 93.
0% melting point 209-211 ° C

Synthesis Example 8 Synthesis of Compound I-105 7.45 g (0.030 mol) of 4,4′-dithioaniline was dissolved in 50 ml of acetonitrile, cooled to 5 ° C. or lower under a nitrogen atmosphere, and stirred with phenyl. 7.14 g (0.060 mol) of isocyanate was added to the reaction solution at 15 ° C.
It was dropped so that it would not exceed. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited.
The precipitate was collected by filtration and washed with acetonitrile to obtain 14.0 g (0.029 mol) of the target compound I-105. Yield 95.9% Melting point 250 ° C or higher

Synthesis Example 9 Synthesis of Compound I-81 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 12.4 g (0.040 mol) of pentafluoropropionic anhydride was added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from ethyl acetate / ethyl alcohol to give the desired compound I-81 as 4.6.
g (0.0085 mol) was obtained. Yield 42.6% Melting point
210-211 ° C

Synthesis Example 10 Synthesis of Compound I-83 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 12.4 g (0.040 mol) of pentafluoropropionic anhydride was added dropwise so that the reaction liquid did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water, and the precipitated solid was collected by filtration and recrystallized from ethyl alcohol / water to obtain 6.0 g (0.011 mol) of the target compound I-83. Yield 5
6.0% melting point 97-97.5 ° C

Synthesis Example 11 Synthesis of Compound I-84 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.2 g (0.040 mol) of pentafluorobenzoyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 8.2 g (0.013 mol) of the target compound I-84. Yield 6
4.6% melting point 236-238 ° C

Synthesis Example 12 Synthesis of Compound I-85 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.1 g (0.040 mol) of 1-naphthalenesulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 5.4 g (0.0086 mol) of the target compound I-85. Yield 4
2.8% melting point 220-222 ° C

Synthesis Example 13 Synthesis of Compound I-86 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.1 g (0.040 mol) of 2-naphthalenesulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water and the precipitated solid was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 8.3 g (0.01%) of the target compound I-86.
3 mol) was obtained. Yield 65.9% Melting point 171-17
2 ℃

Synthesis Example 14 Synthesis of Compound I-87 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 7.6 g (0.040 mol) of p-toluenesulfonyl chloride was added to the reaction solution to give 1
It was added dropwise so as not to exceed 5 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water and 250 ml of ethyl acetate was added for extraction. When the extract was dried and concentrated, the target product was precipitated. The precipitate was collected by filtration and recrystallized from ethyl acetate / hexane to give 9.0 g (0.0
16 mol) was obtained. Yield 80.8% Melting point 164-166
° C

Synthesis Example 15 Synthesis of Compound I-88 5.0 g (0.020 mol) of 2,2'-dithioaniline
Is dissolved in 100 ml of acetonitrile, and under a nitrogen atmosphere,
Cool to below 5 ° C and agitate 3.1 ml of pyridine
(0.040 mol) was added, and 8.3 g (0.040 mol) of p-methoxybenzenesulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After dropping,
The temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. Pour the reaction mixture into water and add 250 ml of ethyl acetate.
And extracted. The extract was dried and concentrated, the obtained oily product was dissolved in ethyl acetate, and hexane was added to cause crystallization to give 6.8 of the target compound I-88.
g (0.012 mol) was obtained. Yield 58.0% Melting point 1
31-132 ° C

Synthesis Example 16 Synthesis of Compound I-89 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 11.2 g (0.04 mol) of 2,4,5-trichlorobenzenesulfonyl chloride was further added.
0 mol) was added dropwise so that the reaction liquid did not exceed 15 ° C.
After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water and the precipitated solid was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 9.9 g (0.013 mol) of the target compound I-89. Yield 67.3% Melting point 228-229 ° C

Synthesis Example 17 Synthesis of Compound I-90 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 8.7 g (0.040 mol) of 2-mesitylene sulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring and left overnight,
The target substance was deposited. The precipitate was collected by filtration and recrystallized from ethyl acetate / isopropyl alcohol to obtain 8.2 g (0.013 mol) of the target compound I-90. Yield 6
6.7% melting point 140-141 ° C

Synthesis Example 18 Synthesis of Compound I-91 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and further 7.6 g (0.040 mol) of 2-naphthalenecarboxylic acid chloride was added dropwise so that the reaction liquid did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring and the reaction was carried out for 2 hours, whereupon the target product was precipitated. 50m acetonitrile in the precipitate
1 was added, heated and dissolved, and then ice-cooled and recrystallized. The precipitate was collected by filtration, and 10.6 g of the target compound I-91 was obtained.
(0.019 mol) was obtained. Yield 95.5% Melting point 1
78-179 ° C

Synthesis Example 19 Synthesis of Compound I-92 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 10.7 g (0.040 mol) of diphenylphosphoric acid chloride was added to the reaction liquid at 15 ° C.
It was dropped so that it would not exceed. After the completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was allowed to proceed for 2 hours. Acetonitrile 50 for precipitate
After adding ml, heating and dissolving, ice-cooling and recrystallization were performed. The precipitate was collected by filtration and 4.6 g of the target compound I-92 was obtained.
(0.0065 mol) was obtained. Yield 32.2% Melting point
121-123 ° C

Synthesis Example 20 Synthesis of Compound I-93 1) Synthesis of (2,2'-diamino-5,5'-dichlorodiphenyl) disulfide To 50 g of potassium hydroxide, 100 ml of ethylene glycol was added and dissolved by heating at 90 ° C. After 2-amino-6-chlorobenzothiazole 1
0.3 g (0.056 mol) was added to the alkaline solution. The reaction solution was heated to 165 ° C. and reacted for 24 hours.
The reaction solution was allowed to cool to room temperature, 1.5 l of water was added for dilution, and then air was passed through for 24 hours for oxidation. After the precipitate was filtered off, hydrochloric acid was added to adjust the pH to 6-7, and the precipitated solid was collected by filtration and recrystallized with ethyl alcohol / water to give 5.6 g (0.018 mol) of the desired product. Obtained. 63% yield

2) Synthesis of I-93 2 g (0.0063 mol) of (2,2'-diamino-5,5'-dichlorodiphenyl) disulfide was dissolved in 25 ml of acetonitrile and cooled to 5 ° C or lower under a nitrogen atmosphere. And, with stirring, 1 ml of pyridine (0.013 mol)
Was added, and benzoyl chloride 1.8 g (0.01
28 mol) was added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / ethyl alcohol to obtain 3.3 g (0.0063 mol) of the target compound I-93. Yield 99.7% Melting point 192-193 ° C

Synthesis Example 21 Synthesis of Compound I-94 (2,2'-diamino-5,5 'synthesized in the section of I-93)
-Dichlorodiphenyl) disulfide 2 g (0.006
3 mol) in 25 ml of acetonitrile, cooled to 5 ° C. or lower under a nitrogen atmosphere, and stirred with 1 ml of pyridine.
(0.013 mol) was added, and 2.2 g (0.0125 mol) of benzenesulfonyl chloride was added to the reaction solution to give 15
It was added dropwise so as not to exceed ℃. After the dropwise addition was completed, the temperature was gradually raised to room temperature with stirring, and the mixture was allowed to stand overnight, whereupon the target substance was precipitated. The precipitate was collected by filtration, and ethyl acetate /
By recrystallization from methyl alcohol, 1.2 g (0.0020 mol) of the target compound I-94 was obtained. Yield 3
1.8% melting point 175-178 ° C

Synthesis Example 22 Synthesis of Compound I-95 1) Synthesis of (2,2'-diamino-5,5'-dimethyldiphenyl) disulfide 50 g of potassium hydroxide and 100 ml of ethylene glycol
Was added and dissolved by heating at 90 ° C., and then 2-amino-6-
Methylbenzothiazole 10.0 g (0.061 mol)
Was added to the alkaline solution. The reaction solution was heated to 165 ° C. and reacted for 24 hours. The reaction solution was allowed to cool to room temperature, 1.5 l of water was added for dilution, and then air was passed through for 24 hours for oxidation. The precipitate was filtered off and 4.1 g (0.01
5 mol). Yield 49%

2) Synthesis of I-95 2 g (0.0072 mol) of (2,2′-diamino-5,5′-dimethyldiphenyl) disulfide was dissolved in 25 ml of acetonitrile and cooled to 5 ° C. or lower under a nitrogen atmosphere. Then, 1.1 ml of pyridine (0.0144) with stirring.
Mol), and further 2.0 g of benzoyl chloride
(0.0144 mol) was added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / ethyl alcohol to give 3.0 g (0.
(0062 mol) was obtained. Yield 86.0% Melting point 158
-159 ° C

Synthesis Example 23 Synthesis of Compound I-96 (2,2'-diamino-5,5 'synthesized in the section of I-95).
-Dimethyldiphenyl) disulfide 2 g (0.007
2 mol) in 25 ml of acetonitrile, cooled to 5 ° C. or lower under a nitrogen atmosphere, and stirred with pyridine 1.1.
ml (0.0144 mol) was added, and 2.5 g (0.0144 mol) of benzenesulfonyl chloride was further added dropwise so that the temperature of the reaction solution did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water, and the precipitated solid was collected by filtration and recrystallized from dimethylformamide / ethyl alcohol to give 3.6 g (0.006) of the desired compound I-96.
5 mol). Yield 89.8% Melting point 164-16
5 ℃

Synthesis Example 24 Synthesis of Compound I-97 9.2 g (0.030 mol) of 2,2'-dithiobenzoic acid
Is suspended in 100 ml of toluene, and 1 m of pyridine is added with stirring.
1, thionyl chloride 4.8 ml (0.066 mol) were added. The reaction solution was heated to 80 ° C. and reacted for 3 hours, and then the pressure in the reaction system was reduced to distill off toluene to dryness. After cooling the obtained solid, 50 ml of acetonitrile and 50 ml of tetrahydrofuran were added and dissolved, and 6.6 g (0.060 mol) of aniline and 4.7 ml of pyridine were added thereto.
(0.060 mol) in acetonitrile (50 ml)
Was dripped. After reacting for 3 hours at room temperature, the reaction mixture was poured into water, and the precipitated solid was recrystallized from dimethylformamide / ethyl alcohol to give the target product I-97 as 1
0.8 g was obtained. Yield 78.8% Melting point 239-242
° C.

Synthesis Example 25 Synthesis of Compound I-98 8.7 g (0.035 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
The reaction liquid was cooled to below 1 ° C and stirred with 12.4 g (0.0735 mol) of 1-naphthalene isocyanate.
It was added dropwise so as not to exceed ℃. After the dropwise addition was completed, the temperature was gradually raised to room temperature with stirring, and the mixture was allowed to stand overnight, whereupon the target substance was precipitated. The precipitate was collected by filtration and washed with acetonitrile to obtain 18.2 g (0.031) of the target compound I-98.
Mol) obtained. Yield 88.8% Melting point 220-224 ° C

Synthesis Example 26 Synthesis of Compound I-99 8.7 g (0.035 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
The reaction liquid was cooled to below 1 ° C and stirred with 12.4 g (0.0735 mol) of 1-naphthalene isocyanate.
It was added dropwise so as not to exceed ℃. After the completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was allowed to proceed for 2 hours. The precipitate was collected by filtration and washed with acetonitrile to give 18.8 g (0.0
32 mol) was obtained. Yield 91.7% melting point 256-259
° C

Next, the compound represented by formula (II) will be described in detail. As the aryl group represented by Q,
It is preferably an aryl group having 6 to 30 carbon atoms, more preferably a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl, with phenyl being particularly preferred. The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic group having 1 to 30 carbon atoms and containing at least one N, O or S atom, and these are monocyclic rings. It may be present or may form a condensed ring with another ring.

The heterocyclic group is preferably 5 to 6
Membered aromatic heterocyclic group, more preferably a 5- or 6-membered aromatic heterocyclic group containing a nitrogen atom, and still more preferably a 5- or 6-membered aromatic heterocyclic group containing 1 to 3 nitrogen atoms. It is a base. Specific examples of the heterocycle include
For example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole,
Pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,
Examples thereof include cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole and benzthiazole. The heterocycle is preferably thiophene, furan, pyrrole, imidazole,
Pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole. , Indolenine, more preferably pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, tetrazole, thiazole, oxazole, benz. Imidazole, benzoxazole, benzthiazole, indolenine , Particularly preferably, pyridine,
Triazole, triazine, thiadiazole, oxadiazole, quinoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole,
Benzthiazole and indolenine.

Q is preferably an aromatic nitrogen-containing heterocyclic group.

The halogen atoms represented by X ₁ and X ₂ may be the same or different from each other, and may be a fluorine atom, a chlorine atom,
A bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom,
A bromine atom, particularly preferably a bromine atom.

Y is -C (= O)-, -SO- or -S
It represents O ₂ —, preferably —SO ₂ —.

The halogen atom represented by A is a fluorine atom,
Chlorine atom, bromine atom and iodine atom are preferable, chlorine atom, bromine atom and iodine atom are more preferable, chlorine atom and bromine atom are more preferable, and bromine atom is particularly preferable.

The electron withdrawing group represented by A is preferably a substituent having a σ _p value of 0.01 or more and 1.0 or less,
The substituent is more preferably 0.1 or more and 1.0 or less.
Examples of the electron-withdrawing group include a trihalomethyl group (CB
r ₃ (0.29), CCl ₃ (0.33), CF
₃ (0.54)), cyano group (0.66), nitro group (0.78), sulfonyl group having 1 to 10 carbon atoms (methanesulfonyl (0.72)), acyl group having 2 to 10 carbon atoms (Acetyl (0.50)), an alkynyl group having 2 to 10 carbon atoms (C≡CH (0.23)), an alkoxycarbonyl group having 2 to 10 carbon atoms (methoxycarbonyl (0.4
5)), an aryloxycarbonyl group having 7 to 12 carbon atoms (phenoxycarbonyl (0.44)), and 1 to 1 carbon atoms.
Examples thereof include a carbamoyl group having 0 (carbamoyl (0.36)) and a sulfamoyl group having 0 to 10 carbon atoms (sulfamoyl (0.57)), and the like, preferably a sulfonyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Is.

A is preferably a halogen atom,
Chlorine atom, bromine atom and iodine atom are more preferable, chlorine atom and bromine atom are still more preferable, and bromine atom is particularly preferable. n represents 0 or 1, and is preferably 1 when Y is —SO ₂ —.

Among the compounds represented by the general formula (II), the compounds represented by the following general formula (II-a) are preferable. General formula (II-a)

[0089]

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(In the formula, X ₁ , X ₂ , A and n have the same meanings as those in formula (II), respectively, and the preferred ranges are also the same. Q ′ represents an aromatic nitrogen-containing heterocyclic group. Represents.)

The aromatic nitrogen-containing heterocyclic group represented by Q ′ is preferably a 5- to 6-membered aromatic heterocycle containing 1 to 3 nitrogen atoms, such as pyrrole, imidazole, pyrazole, pyridine and pyrazine. , Pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole. , Benzthiazole, indolenine and the like, more preferably pyridine, triazole, triazine, thiadiazole, oxadiazole, quinoline, tetrazole, thiazo. And oxazole, benzimidazole, benzoxazole, benzthiazole and indolenine.

Among the compounds represented by the general formula (II), the compounds represented by the following general formula (II-b) are preferable. General formula (II-b)

[0093]

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(In the formula, X ₁ and X ₂ have the same meanings as those in formula (II), and the preferred ranges are also the same. Q ′ has the same meaning as that in formula (II-a). Also, the preferable range is the same. X ₃ represents a halogen atom.)

The halogen atom represented by X ₃ is preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a bromine atom. Specific examples of the compound represented by formula (II) are shown below, but the invention is not limited thereto.

[0096]

[Chemical 29]

[0097]

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[0098]

[Chemical 31]

[0099]

Embedded image

[0100]

[Chemical 33]

[0101]

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If possible, the above compounds may be used in the form of salts. The compound represented by the general formula (II) of the present invention can be synthesized according to the method described in, for example, US Pat. No. 3,874,946, European Patent Publication No. 605981, and the like.
The compound represented by the general formula (I) or (II) can be added in either the light-sensitive layer or the non-light-sensitive layer. It is preferably a photosensitive layer. The compounds represented by the general formulas (I) and (II) also differ depending on the desired purpose, but they are 10 ^-4 mol to 1 mol / A.
It is advisable to add g mol, preferably 10 ⁻³ mol to 0.3 mol / Ag mol. It is preferable that any compound be dissolved in an organic solvent and added.

The photothermographic material of the present invention is preferably a monosheet type (a type in which all the materials donated to form an image are completed as an image sheet to be observed) because of its gentleness to the earth. is there. Further, it is preferably a photothermographic material for infrared laser exposure. Further, the wavelength of infrared laser exposure is 750 nm or more, more preferably 800 nm or more. In order to support a laser in such a wavelength range, it is necessary to perform spectral sensitization so as to have sensitivity in these wavelength ranges, that is, the infrared range. Known infrared spectral sensitizing dyes may be used.

The photothermographic material of the present invention forms a photographic image by using a heat development processing 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, including 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) and a reducing agent usually dispersed in a (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but at a high temperature (for example, 80 ° C.) after exposure.
Above) to develop. 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 on the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. The photosensitive layer may be composed of multiple layers, and the sensitivity is high for adjusting the gradation.
It may be a low sensitive layer or a low sensitive layer / high sensitive layer. 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, etc .;
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 (for example, synthetic polymer) together with chemicals in the photothermographic material of the 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); phthalazine; combination of phthalazinone and sulfinic acid derivative (For example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-toluenesulfinate); a combination of phthalazine + phthalic acid; phthalazine (including an adduct of phthalazine) and maleic anhydride, And phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (eg phthalic acid, 4-methylphthalic acid, 4
-A combination with at least one compound selected from nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, nartoxazine derivatives; benzoxazine-2,4-diones (eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg 2,4 −
Dihydroxypyrimidine), and tetraazapentalene derivatives (for example, 3,6-dimerocapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene. Preferred toning agents are phthalazone or phthalazine. Is:

[0111]

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The reducing agent may contain so-called photographic developers such as phenidone, hydroquinones, catechol and the like, but hindered phenol is preferable. 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); aldehyde or ketone hydrazones (eg, anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methyl sulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamide anilines (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. A preferred reducing agent is a hindered phenol of general formula (A):

[0114]

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Here; R is a hydrogen atom or a carbon atom of 1
10 alkyl group (e.g., -C ₄ H _9, 2,4,4
-Trimethylpentyl), R ⁵ and R ⁶ are alkyl groups having 1 to 5 carbon atoms (eg, 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. Preferred silver sources are stearic acid and silver behenate, with behenic acid being especially preferred. 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.

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.

[0119]

【Example】

Example 1 Photosensitive mixture NaOH 89 g Distilled water 1500ml solution prepared solution stearate 135g 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 700 ml

The solution was added over 5 minutes with vigorous stirring while keeping the solution at 85 ° C.
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.
Then, the solution was added, and the mixture was left without stirring, and the aqueous phase was removed together with the salt contained therein to obtain an oil phase, which was desolvated to remove traces of water, and then the solution was added and vigorously stirred at 50 ° C. Then, the solution was added over 20 minutes and stirred for 105 minutes to obtain a photosensitive emulsion A.

The following layers were successively formed on a biaxially stretched 175 μm thick polyethylene terephthalate support (without an undercoat layer) which was colored blue with Dye-A. Drying was performed at 75 ° C. for 5 minutes each.

<Back side coating> o Antihalation layer (wet thickness 80 micron) Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-C (solvent DMF) 70 mg

<Photosensitive layer side coating> o Photosensitive layer (wet thickness 140 μm) Photosensitive emulsion A 73 g Sensitizing dye-1 (0.1% DMF solution) 2 ml Antifoggant-1 (0.01% methanol solution) ) 3 ml Phthalazone (4.5% DMF solution) 8 ml Reducing agent-1 (10% acetone solution) 13 ml Compounds described in Tables 1 and 2.

O Surface protection 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 Thing 0.5g

[0125]

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[0126]

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Sensitometry The photothermographic material prepared above was 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
A heat development treatment was performed at 20 ° C. for 5 seconds and 125 ° C. for 10 seconds. Then, the fog value at that time was measured and the color tone was visually evaluated.

[0128]

[Table 1]

[0129]

[Table 2]

From Tables 1 and 2, it can be seen that the samples of the present invention have a low fog and a good color tone.

Example 2 Preparation of Photosensitive Emulsion B Solution Stearic acid 135 g Behenic acid 635 g Distilled water 13 liters 85 ° C. and mixed 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 keeping 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, except that the antihalation layer was provided below the photosensitive layer on the side of the photosensitive layer. As in the case of Example 1, the sample using the compound of the present invention had good fog and black color tone. Example 3 << Preparation of Silver Halide Grain A >> 16 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water and the temperature was adjusted to 3
After adjusting the pH to 5.0 at 5 ° C, 18.6 g of silver nitrate
159 ml of an aqueous solution containing potassium bromide and an aqueous solution containing potassium bromide and potassium iodide (92/8) were added over 10 minutes by the control double jet method while keeping the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and an aqueous solution containing potassium bromide were added over 30 minutes while keeping the pAg at 7.7, and the pH was lowered to cause aggregation and sedimentation for desalting, followed by addition of 0.1 g of phenoxyethanol. , P
Preparation of silver iodobromide grains A (core 8 mol%, average 2 mol%, 0.05 μ cube, projected diameter area variation coefficient 8%, (100) plane ratio 88%) adjusted to H7.9 and pAg8.2. Finished.

The temperature of the silver halide grains A was raised to 60 ° C., sodium thiosulfate, selenium compound II-1, tellurium compound a-1, chloroauric acid and potassium thiocyanate were added.
After ripening for 0 minute, it was rapidly cooled to 35 ° C. to terminate the chemical sensitization to prepare silver halide grains. The added amount was as follows. Sodium thiosulfate 8.5 × 10 ^-5 mol / silver mol Selenium compound S-1 1.1 × 10 ^-5 mol / silver mol Tellurium compound T-1 1.5 × 10 ^-5 mol / silver mol Chloroauric acid 3 0.5 × 10 ^-6 mol / silver mol Potassium thiocyanate 2.7 × 10 ^-4 mol / silver mol

[0135]

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<< Preparation of Organic Fatty Acid Silver Emulsion B >> 300 ml of water
10.6 g of behenic acid was put thereinto, dissolved by heating at 90 ° C., 31.1 ml of 1N sodium hydroxide was added with sufficient stirring, and the mixture was left as it was for 1 hour. Then 30
The mixture was cooled to 0 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, silver halide grains A prepared in advance
Was added to the behenic acid while stirring at a temperature of 40 ° C. so that the amount of silver was 10 mol%. Further, 25 ml of a 1N silver nitrate aqueous solution was continuously added over 2 minutes, and the mixture was left stirring for 1 hour.

To this water-based mixture, 37 g of a 1.2 wt% butyl acetate solution of polyvinyl acetate was gradually added with stirring to form flocs of the dispersion. After that, the water was removed, and the water was washed twice more. (Wash water conductivity 30 μS
(Cm) Then, 2.5 wt% of 20 cc of 2-butanone solution of polyvinyl butyral (molecular weight 3000) was added and stirred for 10 minutes at a sufficient speed. Next, the following compound, 2-butanone 40 g, and polyvinyl butyral (molecular weight 400
0) 6.0 g was added and stirred at a sufficient speed for 1 hour to complete the preparation of the organic fatty acid silver emulsion B.

[0138]

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<< Preparation of Emulsion Coating Solution >> The following chemicals were added to the organic fatty acid silver prepared as described above to prepare an emulsion coating solution. (Hereinafter, added amount per mol of silver) Isocyanate (N3300 manufactured by Desmodur) 2.6 g Sensitizing dye-2 0.01 mmol Sensitizing dye-3 0.01 mmol 2-Mercapto-5-methylbenzimidazole 7.65 mmol p-Chlorobenzoylbenzoic acid 53 mmol Reducing agent-1 0.27 mmol Tetrachlorophthalic acid 10.8 mmol Coating aid-1 0.001 mmol Compound Table 3

[0140]

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<< Preparation of Surface Protective Layer Coating Solution >> A surface protective layer coating solution was prepared as follows. Cellulose acetate butyrate 7.5 g 2-butanone 80 g Methanol 10 g Phthalazine 71.5 mmol 4-Methylphthalic acid 0.3 g Tetrachlorophthalic anhydride 0.07 g Coating aid-1 0.01 g

[0142]

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<< Preparation of Backing Layer Coating Liquid >> A backing layer coating liquid was prepared as follows. Polyvinyl butyral (10% 2-butanone solution) 30 ml Cellulose acetate butyrate 30 ml (10% ethyl acetate solution) Antihalation dye (b) 0.05 g Antihalation dye (b) 0.06 g Color control dye (c) 0. 1 g Color tone adjusting dye (d) 0.002 g Silica matting agent (Cyroid 162) 0.1 g Isocyanate (N3300 manufactured by Desmodur) 0.8 g Acetic acid ethyl ester 140 ml Coating aid-1 0.1 g

[0144]

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The coating solution for the backing layer prepared as described above was applied to a biaxially stretched blue-colored polyethylene terephthalate film having a thickness of 175 μm so that the absorbance at 810 nm was higher than that of the 1.2 polyethylene terephthalate film.

(Preparation of Coating Sample) The prepared coating solution was coated on the opposite surface coated with the backing layer of polyethylene terephthalate so that the coated silver amount was 2.0 g / m ² and dried. After that, the surface protective layer coating solution was applied so that the cellulose acetate butyrate was 2.5 g / m ² . Thus, a coated sample was prepared.

<< Evaluation of Photographic Performance >> Sensitometry After processing the photothermographic material prepared above into a half-cut size, it was manufactured by Fuji Photo Film Co., Ltd. F
CR7000 was modified and imagewise exposed using a semiconductor laser of 810 nm. The angle between the exposed surface of the coated sample and the exposure laser beam was 80 deg. The output of the laser was 150 mW, provided that the output was superimposed at a high frequency and output in a vertical multi-mode. The heat development treatment was carried out by uniformly heating using a heat drum, and two kinds of heat treatment were carried out: 120 ° C. × 15 seconds and 125 ° C. × 15 seconds. Then, the fog value at that time was measured. Further, when the maximum concentration of Sample No. 1 in Table 3 was set to 100, the maximum concentration of each sample was evaluated by a relative value. The results are shown in Table 3.

Evaluation of storability Three coated samples were placed in a closed container whose inside was kept at 55% at 25 ° C., and then stored at 50 ° C. for 7 days (forced storage). The second sample of these and the sample for comparison aged (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for evaluation of photographic properties, and the density of the fog portion was measured. (Increase in fog) = (fog during forced aging) − (fog during comparative aging)

The results are shown in Table 3.

[0150]

[Table 3]

[0151]

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From Table 3, it can be seen that the samples of the present invention have sufficient sensitivity and low fog. Further, it can be seen that the storage stability of the light-sensitive material is also good.

[0153]

The photothermographic material of the present invention has low fog and good color tone. Further, the storage stability of the light-sensitive material is good.

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[Procedure amendment]

[Submission date] May 22, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

An aryl group represented by R ₁ , a pyridyl group,
The quinolyl group may have a substituent, and as the substituent,
For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms).
An alkyl group of, for example, methyl, ethyl, iso-
Propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, and particularly preferably a carbon number of 2 to 8), such as vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms,
An alkynyl group having 2 to 8 carbon atoms is particularly preferable, and examples thereof include propargyl and 3-pentynyl. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 6 carbon atoms).
12 aryl groups such as phenyl, p-methylphenyl, and naphthyl. ), An amino group (preferably having 0 to 20 carbon atoms, and more preferably having 0 carbon atoms).
-10, particularly preferably an amino group having 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino and dibenzylamino. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 carbon atoms.
~ 8 alkoxy groups, such as methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, and more preferably having 6 carbon atoms).
To 16, particularly preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably an acyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl and pivaloyl). , An alkoxycarbonyl group (preferably having 2 carbon atoms
To 20, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl and ethoxycarbonyl. ), An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl). , An acyloxy group (preferably having 2 to 2 carbon atoms)
It is an acyloxy group having 20, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). Amino group (preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino) and aryloxycarbonyl. Amino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino). Amino group (preferably having a carbon number of 1 to 20, more preferably C1-16, especially preferably having a carbon number of 1 to 1
2 is a sulfonylamino group, and examples thereof include methanesulfonylamino and benzenesulfonylamino. ), A sulfamoyl group (preferably having a carbon number of 0 to 2)
It is a sulfamoyl group having 0, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ),
Carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms).
Carbamoyl group, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms,
Particularly preferably, it is an alkylthio group having 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio. ), An arylthio group (preferably having 6 to 20 carbon atoms,
It is more preferably an arylthio group having 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio. ), A sulfonyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16, and particularly preferably a carbon number of 1 to 12 and examples thereof include mesyl and tosyl) and a sulfinyl group ( Preferably 1 to 20 carbon atoms, more preferably 1 carbon atoms
To 16 and particularly preferably a sulfinyl group having 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), An ureido group (preferably an ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, phenylureido and the like). , A phosphoric acid amide group (preferably having a carbon number of 1 to
A phosphoric acid amide group having 20, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoric acid amide and phenylphosphoric acid amide. ), Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group,
Heterocyclic groups (eg imidazolyl, pyridyl, furyl,
Piperidyl, morpholino and the like. ). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

--N (R _c2 ) SO ₂ R _c1 and --N (R _d2 ) SO of the phenyl group in the general formulas (I-c) and (I-d).
The substituent other than ₂ R _d1 is preferably an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group. Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

[0030]

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[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction contents]

[0032]

[Chemical 12]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

[0034]

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[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction contents]

[0044]

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[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

If possible, the above compounds may be used in the form of salts. The compound represented by the general formula (I) of the present invention is, for example, 1
4-III, Chapter 8 8.4 or ORGANIC FUNCTIONAL G
ROUP PREPARATIONS (Sandler, Karo, ACADEMIC PRESS
New York and London) I-Chapt.18. The synthesis methods are roughly classified as follows. (1) Method by oxidation of corresponding mercaptan (2) Method by nucleophilic substitution of corresponding alkyl (aryl) halide with alkali metal polysulfide salt (3) Conversion of corresponding aniline derivative into diazinium salt and then alkali polysulfide Method for nucleophilic substitution reaction with metal salt

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction contents]

As a method for synthesizing the mercaptans used in the method (1), a new experimental chemistry course (edited by the Chemical Society of Japan, Maruzen)
14-III, Chapter 8, 8.1, ORGANIC FUNCTIONAL GROUP P
REPARATIONS (Sandler, Karo, ACADEMIC PRESS New Yo
rk and London) I-Chapt.18 or THE CHEMISTRY OF
FUNCTINONAL GROUPS (Patai, JONE WILLY & SONS
) It can be synthesized by various methods such as those described in "The Chemistry of the thiol group" -Chapt.

Claims (3)

[Claims] 1. A photothermographic material comprising at least one compound represented by the following general formula (I). General formula (I) (In the formula, R ₁ represents an aryl group, a pyridyl group or a quinolyl group. R ₂ represents an aliphatic hydrocarbon group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkoxycarbonylamino group, an aryloxycarbonylamino group. Group, acyloxy group, acylamino group, carbamoyl group, sulfonylamino group, phosphoramide group, sulfamoyl group, alkylthio group, arylthio group, thiocarbonyl group, sulfonyl group, sulfinyl group, ureido group,
It represents an aryl group, a pyridyl group or a quinolyl group having at least one substituent selected from a thioureido group, a thioamide group, a hydroxy group, a mercapto group, a sulfo group, a phosphono group, a hydroxamic acid group and a heterocyclic group. ) 2. A photothermographic material comprising at least one compound represented by general formula (I) and at least one compound represented by general formula (II). General formula (II) (In the formula, Q represents an aryl group or a heterocyclic group. X ₁
And X ₂ each represent a halogen atom. Y is -C
(= O) -, - SO- or -SO ₂ - represents a. A is
It represents a hydrogen atom, a halogen atom or an electron-withdrawing group. n
Represents 0 or 1. ) 3. The photothermographic material according to claim 1, which is for infrared laser exposure.