JPH09265150A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material reducing fog and having satisfactory preservability and image preservability without reducing sensitivity or deteriorating a color tone by incorporating a polyhalomethane compd. having a diffusion resistant group in each molecule. SOLUTION: A polyhalomethane compd. having a diffusion resistant group in each molecule is incorporated. The diffusion resistant group is a diffusion resistant group called a ballast group in a photographic coupler, etc. The ballast group is a group capable of preventing the polyhalomethane compd. incorporated into a specified layer from diffusing easily in other layer and has >=8, preferably 8-100, especially preferably 8-60, more especially preferably 10-40 total carbon atoms. The ballast group is preferably an aliphatic hydrocarbon group (e.g. alkyl, alkenyl or alkynyl), an aryl group, a heterocyclic group or a combination of the group with an ether group, a thio-ether group or a carbonyl group.

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 improving fog reduction, photosensitive material storability, and image storability without deteriorating sensitivity or 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 8
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 produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and forms the image.

The most effective conventional fog prevention technique has been a method using a mercury compound as an antifoggant. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat. No. 3,589,990.
No. 3. However, mercury compounds are not environmentally preferable, and development of a non-mercury antifoggant has been desired. As non-mercury antifoggants, various polyhalogen compounds have hitherto been disclosed (for example, US Pat. No. 3,874,946).
No. 4,452,885, No. 4546075, No. 47
56999, 5340712, and European Patent No. 605.
981A1, 622666A1, 631176
A1, Japanese Patent Publication No. 54-165, Japanese Patent Laid-Open No. 50-371
No. 26, JP-A-7-2781). However, these compounds have a low effect of preventing fogging, deteriorate the color tone of silver, and after aging under the forced conditions of being moist and warm in a laminated form of the photosensitive material,
When exposed and developed, there was a problem that the fog increased in the unexposed area. Further, among the polyhalogen compounds described in the above-mentioned patents, those having a high fogging prevention effect are
It was found that the spectral sensitizing dye (particularly the infrared sensitizing dye) is easily decomposed. When such a polyhalogen compound is used,
There is a problem that the photographic performance tends to fluctuate due to slight differences in the manufacturing conditions of the light-sensitive material, and the 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 good fog reduction, sensible material storage stability, and image storability without deterioration of sensitivity or deterioration of color tone.

[0005]

The above-mentioned objects can be achieved by the following means. (1) A photothermographic material comprising a polyhalomethane compound having a diffusion resistant group in its molecule.

(2) It contains a reducible silver source, (b) a photocatalyst, (c) a reducing agent, (d) a binder, and (e) a polyhalomethane compound having a diffusion resistant group in the molecule. Characterized photothermographic material.

(3) (a) organic silver salt, (b) reducing agent,
A photothermographic material comprising (c) a photosensitive silver halide and / or a photosensitive silver halide-forming component, (d) a binder and (e) a polyhalomethane compound having a diffusion resistant group in the molecule. .

(4) The polyhalomethane compound having a diffusion resistant group in the molecule is a compound represented by the following general formula (I), (1), (2) or (3) Photothermographic material. General formula (I)

[0009]

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(In the formula, Q represents an atomic group necessary for forming an aryl group or a heterocyclic group. Y represents -CO- or -SO.
- or -SO ₂ - represents a. n represents 0 or 1. X ₁ and X ₂ each represent a halogen atom. A represents a hydrogen atom or an electron-withdrawing group. However, the electron withdrawing group of Q or A has at least one diffusion resistant group. )

(5) The photothermographic material according to any one of (1) to (4), wherein the polyhalomethane compound having a diffusion resistant group in the molecule has a molecular weight of 600 or more and less than 3000. material.

(6) The photothermographic material according to any one of (1) to (4), wherein the polyhalomethane compound having a diffusion resistant group in the molecule has a molecular weight of 700 or more and less than 2000. material.

(7) The photothermographic material according to any one of (1) to (6), which is infrared-sensitized for infrared laser exposure.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION First, the polyhalomethane compound having a diffusion resistant group in the molecule used in the present invention will be explained. The diffusion resistant group is a so-called ballast group, which is a diffusion resistant group in a photographic coupler or the like. The ballast group is a group capable of preventing the polyhalomethane compound of the present invention from easily diffusing into another layer when it is added to a specific layer, and has a total carbon number of 8 or more, preferably 8 to It is 100, more preferably 8 to 60, and even more preferably 10 to 40 groups. The ballast group is preferably an aliphatic hydrocarbon group (for example, an alkyl group,
Alkenyl groups, alkynyl groups, etc.), aryl groups, heterocyclic groups and these groups and ether groups, thioether groups,
A group consisting of a combination with a group such as a carbonyl group, an amino group, a sulfonyl group and a phosphonyl group. Also, the ballast group may be a polymer. Specific examples of the ballast group include, for example, Research Disclosure Magazine (Rese
arch Disclosure) 1995/2, 37938, p. 82-
89, JP-A-1-280747, 1-28354.
No. 8 and the like. The ballast group preferably has a total carbon number of 7 to 50, more preferably 10 to 3
0. Typical examples of the diffusion resistant group are shown below,
The present invention is not limited to these.

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[0018]

[Chemical 6]

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[0020]

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The polyhalomethane compound used in the present invention may have a substituent in addition to the diffusion resistant group, and as the substituent, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms). , Particularly preferably 1 to 8 carbon atoms
And, for example, methyl, ethyl, iso-propyl, t
Examples include ert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 carbon atoms).
To 8, and examples thereof include propargyl and 3-pentynyl. ), An aryl group (preferably having 6 to 6 carbon atoms).
30 and more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, 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 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino,
Examples thereof include dibenzylamino. ), An alkoxy group (preferably having a carbon number of 1 to 20, and more preferably having a carbon number of 1).
To 12, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably 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. ), An acyl group (preferably having a carbon number of 1 to
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, 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).
And examples thereof include methoxycarbonyl and ethoxycarbonyl. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, and more preferably having 7 carbon atoms).
To 16, particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably 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 acetoxy and benzoyloxy). Acylamino group (preferably). 2 to 2 carbon atoms
It has 0, more preferably 2 to 16 carbon atoms, and particularly preferably 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, and particularly preferably 2 to 12 carbon atoms,
For example, methoxycarbonylamino and the like can be mentioned. ), An aryloxycarbonylamino group (preferably 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). Group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably carbon) Number 0 to 20, more preferably carbon 0 to 1
6, particularly preferably having 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 1 to 20 carbon atoms,
More preferably 1 to 16 carbon atoms, and particularly preferably 1 carbon atom.
To 12 and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio 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 methylthio and ethylthio), and an arylthio group (preferably carbon). C6-20, more preferably C6-16, particularly preferably C6-12, such as phenylthio, etc.), sulfonyl group (preferably C1-20, more preferably C12). 1 to 16, particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl.), A sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon). The number is 1 to 12, and examples thereof include methanesulfinyl and benzenesulfinyl.), An ureido group (preferably having a carbon number of 1 to 1). 0, 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, phosphoric acid amide group (preferably 1 to 20 carbon atoms, More preferably, it has 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.

The substituent is preferably an alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoramide group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group , A sulfino group, a hydrazino group, a heterocyclic group, more preferably an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group,
A hydroxy group, a halogen atom, a cyano group, a heterocyclic group, more preferably an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group,
A halogen atom, a cyano group and a heterocyclic group are preferable, and an alkyl group, an aryl group, an aralkyl group and a heterocyclic group are particularly preferable.

The polyhalomethane compound used in the present invention is preferably a compound represented by the following general formula (I). General formula (I)

[0024]

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(In the formula, Q represents an atomic group necessary for forming an aryl group or a heterocyclic group. Y represents —CO— or —SO.
- or -SO ₂ - represents a. n represents 0 or 1. X ₁ and X ₂ each represent a halogen atom. A represents a hydrogen atom or an electron-withdrawing group. However, the electron withdrawing group of Q or A has at least one diffusion resistant group. )

The aryl group formed by Q may be monocyclic or condensed and is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg phenyl, naphthyl, etc.), and Preferred is a phenyl group or a naphthyl group,
More preferably, it is a phenyl group.

The heterocyclic group formed by Q is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one N, O or S atom, which may be a monocyclic ring. , And may form a condensed ring with another ring. The heterocyclic group is preferably a 5- or 6-membered unsaturated heterocyclic group, and more preferably a 5- or 6-membered aromatic heterocyclic group. More preferred is a 5- to 6-membered aromatic heterocyclic group containing a nitrogen atom, and particularly preferred is a 5- or 6-membered aromatic heterocyclic group containing 1 to 4 nitrogen atoms.

Specific examples of the heterocycle include pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrimidine, 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, benzthiazole, indolenine and tetraazaindene. Preferably as a heterocycle, imidazole, pyrazole, pyridine, pyrimidine, 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, tetraazaindene, more preferably imidazole,
Pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, tetraazaindene. More preferably, they are imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, benzimidazole and benzthiazole.

The aryl group and heterocyclic group formed by Q may have a substituent, and as the substituent, those mentioned above as the substituent of the polyhalomethane compound can be applied.

Y represents --CO--, --SO-- or --SO _2- , preferably --CO--, --SO _2- , and more preferably --SO _2- . n represents 0 or 1, and is preferably 1.

The halogen atoms represented by X ₁ and X ₂ may be the same or different and are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, 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 Hammett's substituent constant σ _p value of 0.01 or more, more preferably 0.1 or more.
For Hammett's substituent constants, see the Journal of Medical
Chemistry, 1973, vol.16, No.11, 1207-1216, etc. can be referred to. Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σ _p value: 0.06), chlorine atom (σ _p value: 0.23), bromine atom (σ _p value: 0.2)
3), iodine atom (σ _p value: 0.18), trihalomethyl group (tribromomethyl (σ _p value: 0.29), (trichloromethyl (σ _p value: 0.33), trifluoromethyl (σ _p value: 0.54)), cyano group (σ _p value: 0.6
6), nitro group (σ _p value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ _p value: 0.72)), aliphatic / aryl or heterocyclic acyl group ( For example, acetyl (σ _p value: 0.5
0), benzoyl (σ _p value: 0.43)), an alkenyl group (for example, 3,4- (CH = CHCH = CH) (σ _p value: 0.0
4)), an alkynyl group (for example, C ₃ H ₃ (σ _p value: 0.0
9)), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σ _p value: 0.4
5), phenoxycarbonyl (σ _p value: 0.45)) carbamoyl group (σ _p value: 0.36), sulfamoyl group (σ _p value: 0.57) and the like.

A is preferably an electron-withdrawing group, more preferably a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group. A group, particularly preferably a halogen atom.
Among the halogen atoms, chlorine atom, bromine atom and iodine atom are preferable, chlorine atom and bromine atom are more preferable, and bromine atom is particularly preferable.

In the general formula (I), the electron withdrawing group of Q or A has at least one diffusion resistant group. Here, having at least one nondiffusion group in Q means that the aryl group or heterocyclic group represented by Q has at least one nondiffusion group as a substituent. Further, at least 1 is contained in the electron-withdrawing group of A.
Having one diffusion resistant group means having at least one diffusion resistant group in the electron-withdrawing group. The definition and preferred range of the diffusion resistant group are as described above.

Among the compounds represented by the general formula (I), those having a molecular weight of 600 or more and less than 3000 are preferable, those having a molecular weight of 700 or more are more preferable, and those having a molecular weight of 700 or more and less than 2000 are more preferable. .

Among the compounds represented by the general formula (I), the compounds represented by the general formula (Ia) are preferable. General formula (Ia)

[0037]

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Q, X ₁ , X ₂ and A have the same meanings as those in formula (I), and the preferred ranges are also the same. T represents a diffusion resistant group, and the definition and the preferred range of the diffusion resistant group are as described above.

Among the compounds represented by the general formula (I), the compound represented by the general formula (Ib) is more preferable. General formula (Ib)

[0040]

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Q has the same meaning as in formula (I), and the preferred range is also the same. T is a general formula (I
-Synonymous with that in a).

Of the compounds represented by the general formula (I), most preferred are the compounds represented by the general formula (Ic). General formula (I-c)

[0043]

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In the formula, Q'represents an atomic group necessary for forming an aromatic heterocycle containing at least one nitrogen atom.
T has the same meaning as in formula (Ia). Q '
As the aromatic heterocycle formed by, preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, benzimidazole, benzthiazole. is there. )

Specific examples of the compounds represented by formula (I) are shown below, but the invention is not limited thereto.

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[0052]

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[0053]

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The polyhalomethane compound having a diffusion resistant group in the molecule used in the present invention is described in, for example, JP-A-54-165.
JP-A-6-340611, JP-A-7-2781, JP-A-7-5621, JP-B-7-119953, U.S. Pat. No. 5,369,9000, 5374514, and 5460.
No. 938, 5464737, European Patent No. 605981.
No. 631176 and the like.

Specific examples of the synthesis of the polyhalomethane compound used in the present invention are shown below. Synthesis Example (Synthesis of Exemplified Compound 4) 4-Phenyl-3-mercapto-5-heptadecyl-
Synthesis of 1,2,4-triazole 4-phenyl-3-thiosemicarbazide 51.0 g
600 ml of tetrahydrofuran (0.305 mol)
Suspended in 46 ml of triethylamine (0.3 ml).
(3 mol), the mixture was cooled with ice and kept at 10 ° C or lower. Add stearoyl chloride 10 to the mixture under ice cooling.
0.0 g (0.33 mol) was added dropwise while keeping the temperature in the system at 10 ° C or lower. After completion of dropping, stirring was continued for 3 hours, then the reaction temperature was returned to room temperature, 2 liters of water was added to the reaction solution, and the precipitate was collected by filtration. Yield 126g (Yield 95
%) Next, sodium hydroxide (content 93%) 31.0 g
To a solution of (0.72 mol) in 270 ml of water,
104.1 g (0.24 mol) of the precipitate obtained above was added, the reaction solution was heated at 100 ° C. for 1 hour, cooled with ice water for 30 minutes, 62 ml of concentrated hydrochloric acid was added, and the precipitate was collected by filtration. did. The crystal obtained was recrystallized from water / methanol to obtain the target triazole. Yield 70.7
g (71% yield)

Synthesis of 3-carboxymethylthio-4-phenyl-5-heptadecyl-1,2,4-triazole 4-phenyl-3-mercapto-5-heptadecyl-
7.0.7 g (0.17 mol) of 1,2,4-triazole and 27.0 g (0.23 mol) of sodium chloroacetate were suspended in 400 ml of ethanol, and sodium hydroxide (content 93%) was suspended therein. After adding an aqueous solution of 89 g (0.23 mol) dissolved in 70 ml of water, 5
The reaction was performed at 0 ° C. for 3 hours. The reaction solution was cooled to room temperature, and 19.7 ml (0.23 mol) of concentrated hydrochloric acid was added dropwise. 10
After cooling to below ℃, the precipitated solid was collected by filtration and washed with water to obtain the target mercaptoacetic acid derivative. Yield 71.7 g (88% yield)

Synthesis of Compound 4 70 g (1.6 mol) of sodium hydroxide (content 93%) was dissolved in 1.8 liters of water, cooled to 10 ° C. or lower, and 44 ml (0.854 mol) of bromine was added. Dropped. A solution prepared by dissolving 37.9 g (0.08 mol) of a separately obtained mercaptoacetic acid derivative and 9.2 g (0.11 mol) of sodium hydrogen carbonate in 700 ml of water was added to the prepared reaction solution at the temperature of the reaction system. Was maintained at 5 ° C. or lower and slowly added dropwise over 3 hours with stirring. After completion of dropping, the reaction solution was gradually returned to room temperature with stirring and left overnight. The precipitated solid was collected by filtration, washed thoroughly with water and dried,
The target compound 4 was obtained by recrystallizing with ethanol. Yield 26.8 g (48% yield)

The polyhalomethane compound having a diffusion resistant group in the molecule used in the present invention can be added to either the photosensitive layer or the non-photosensitive layer. It is preferably a photosensitive layer. The polyhalomethane compound having a diffusion resistant group in the molecule used in the present invention varies depending on the desired purpose, but it is 10 ^-4 mol to 1 mol / A.
It is advisable to add g mol, preferably 10 ⁻³ mol to 0.3 mol / Ag mol. The polyhalomethane compound having a diffusion resistant group in the molecule used in the present invention is preferably added after being dissolved in an organic solvent.

The photothermographic material of the present invention forms a photographic image using a photothermographic process. 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. Further, it is preferable to contain a toning agent that controls the color tone of silver. The photothermographic material of the present invention is stable at room temperature, but at a high temperature after exposure (for example, 8
It is developed by heating to 0 ° 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 produced by the reaction of the organic silver salt in the exposed areas provided a black image, which contrasts with the unexposed areas,
An image is formed.

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, 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 (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 polymer 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 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); phthalazone; a combination of phthalazinone and a 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 a tetraazapentalene derivative (for example, 3,6-dimerocapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene. Preferred toning agents are:

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[Chemical 21]

And more preferably phthalazine. The reducing agent may contain a so-called photographic developer, for example, phenidone, hydroquinones, catechol and the like, but hindered phenol is preferred. US Patent No. 4
A color light-sensitive material as disclosed in 460681 is also conceivable in the realization of 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):

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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).

A silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, chloroiodobromide). It may be silver or the like) but preferably contains iodide ions. 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.

The heat-developable light-sensitive material of the present invention is preferably a mono-sheet 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 be compatible with a laser in such a wavelength range, it is necessary to be spectrally sensitized so as to have sensitivity in these wavelength ranges, that is, in the infrared range. As the infrared sensitizing dye, known ones may be used, and those disclosed in JP-A-4-182639 and JP-A-5-341432,
Japanese Patent Publication No. 6-52387, No. 3-10931, US 5,4
41,866, JP-A-7-13295, and the like. Specific examples of the infrared sensitizing dye are shown below, but the present invention is not limited thereto.

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In the present invention, the content of the sensitizing dye is about 1 × 10 ^-5 mol to about 1 mol, and preferably 1 × 10 ^-3 mol to 10 ^-1 mol per mol of silver halide. The polyhalomethane compound having a diffusion resistant group of the present invention can be used for a silver halide light-sensitive material having a hard gradation. Any silver halide light-sensitive material may be used as long as it has a light-sensitive silver halide emulsion layer on a support.

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【Example】

Example 1 Preparation of Photosensitive Emulsion A Solution Stearic acid 135 g Behenic acid 635 g Distilled water 13 liter Mixed at 15 minutes at 85 ° C. Solution NaOH 89 g Distilled water 1500 ml Solution concentrated HNO ₃ 21 ml Distilled water 50 ml Solution AgNO ₃ 365 g Distilled water 2500 ml Solution 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 the temperature was kept 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 sequentially 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.

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<Back side coating> ○ Antihalation layer (wet thickness 80 micron) Polyvinyl butyral (10% isopropanol solution) 150 ml Dye C (0.2% DMF solution) 70 mg

<Photosensitive layer side coating> ○ 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 Phtharazone (4.5% DMF solution) 8 ml Reducing agent-1 (10% acetone solution) 13 ml Compounds described in Table 1.

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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

Cesitometry 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
Heat development treatment was carried out at 20 ° C. for 15 seconds and 125 ° C. for 15 seconds. Then, the fog value at that time was measured. Further, when the maximum concentration of Sample No. 1 in Table 1 was set to 100, the maximum concentration of each sample was evaluated as a relative value. The results are shown in Table 1.

Evaluation of storability Three coated samples were put in a closed container whose inside was kept at a humidity of 55% at 25 ° C., and then stored at 50 ° C. for 7 days (forced storage). The second sample of these and the sample for comparative aging (stored in a light-shielding container at room temperature) were subjected to the same treatment as used for the evaluation of photographic properties, and the density of the fog portion was measured. The results are shown in Table 1. (Increase in fog) = Fog after forced aging-Fog after aging for comparison

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[Table 1]

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From Table 1, it can be seen that the samples of the present invention have sufficient sensitivity, low fog, and good storage stability of the light-sensitive material.

Example 2 Preparation of Photosensitive Emulsion B Solution Stearic acid 135 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 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. The sample using the compound of the present invention had low fog as in Example 1.

Example 3 <Preparation of silver halide grains 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 silver halide grain A was heated to 60 ° C. and sodium thiosulfate, selenium compound S-1, tellurium compound T-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

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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 aqueous 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. (Washing water conductivity 60)
Next, 2.5 wt% of 20 cc of a 2-butanone solution of polyvinyl butyral (molecular weight 3000) was added and stirred at a sufficient speed for 10 minutes. Next, the following compound and 2-butanone 4
0 g and polyvinyl butyral (molecular weight 4000) 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.

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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 2

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<< Preparation of Surface Protective Layer Coating Liquid >> A surface protective layer coating liquid 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

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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

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The backing layer coating solution 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, an FCR 7000 manufactured by Fuji Photo Film Co., Ltd. was modified and imaged using a semiconductor laser of 810 nm. Like exposure. The angle between the exposed surface of the coated sample and the exposure laser beam is 80d.
eg. 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. In the heat development treatment, uniform heating is performed using a heat drum.
Two kinds, 0 ° C. × 15 seconds and 125 ° C. × 15 seconds, were performed. Then, the fog value at that time was measured. Further, when the maximum concentration of Sample No. 1 in Table 2 was set to 100, the maximum concentration of each sample was evaluated by a relative value. Table 2 shows the results.

Evaluation of storability As in Example 1, three coated samples were placed in a closed container whose inside was kept at 25 ° C. and a humidity of 55%, 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 after forced aging) − (Fog after comparative aging) The results are shown in Table 2.

Effect of Elapsed Time of Emulsion Coating Solution on Photographic Property Comparison of photographic performance between a photosensitive material coated 1 hour after preparation of the emulsion coating solution and a photosensitive material coated 24 hours after preparation. did. The result of the measurement was evaluated by the sensitivity (the reciprocal of the ratio of the exposure dose giving a density 1.0 higher than Dmin). ΔSensitivity = (sensitivity of coating light-sensitive material after 1 hour from preparation of emulsion coating solution) − (sensitivity of coating light-sensitive material after 24 hours from preparation of emulsion coating solution) Δ A smaller sensitivity value is preferable because of less fluctuation in photographic performance. Indicates. (Comparative values were compared with the Δ sensitivity of Sample No. 2 being 100.) The results are shown in Table 2.

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[Table 2]

It can be seen from Table 2 that the sample of the present invention has sufficient sensitivity and low fog as in Example 1.
Further, it can be seen that the storage stability of the light-sensitive material is also good. Further, it can be seen that the sensitivity fluctuation due to the difference in elapsed time of the emulsion coating solution is small.

[0118]

The light-sensitive material of the present invention has high sensitivity and low fog. Further, the storage stability of the photographic material is good.

Claims (7)

[Claims] 1. A photothermographic material comprising a polyhalomethane compound having a diffusion resistant group in its molecule. 2. (a) a reducible silver source, (b) a photocatalyst,
A photothermographic material comprising (c) a reducing agent, (d) a binder, and (e) a polyhalomethane compound having a diffusion resistant group in the molecule. 3. (a) Organic silver salt, (b) reducing agent, (c)
A photothermographic material comprising a photosensitive silver halide and / or a photosensitive silver halide-forming component, (d) a binder and (e) a polyhalomethane compound having a diffusion resistant group in the molecule. 4. The photothermographic material according to claim 1, wherein the polyhalomethane compound having a diffusion resistant group in the molecule is a compound represented by the following general formula (I). . General formula (I) (In the formula, Q represents an atomic group necessary for forming an aryl group or a heterocyclic group. Y represents —CO—, —SO— or —SO.
Represents _2- . n represents 0 or 1. X ₁ and X ₂ each represent a halogen atom. A represents a hydrogen atom or an electron-withdrawing group. However, the electron withdrawing group of Q or A has at least one diffusion resistant group. ) 5. The photothermographic material according to claim 1, wherein the polyhalomethane compound having a diffusion resistant group in the molecule has a molecular weight of 600 or more and less than 3000. 6. The photothermographic material according to claim 1, wherein the polyhalomethane compound having a diffusion resistant group in the molecule has a molecular weight of 700 or more and less than 2000. 7. The photothermographic material according to claim 1, which is infrared-sensitized for infrared laser exposure.