JP2001166420A - Heat developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material excellent in dimensional stability and silver tone and free from the increase of fog with the lapse of time. SOLUTION: The heat developable photographic sensitive material has a photosensitive layer containing an organic silver salt, photosensitive silver halide grains and a reducing agent on a polyester substrate derived from a cycloaliphatic diol and an aromatic dicarboxylic acid and has a non- photosensitive layer next to the photosensitive layer on the substrate side and the amount of silver of the photosensitive silver halide grains is 0.03-0.3 g/m2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material (hereinafter simply referred to as a photothermographic material), and more particularly to a photothermographic material having excellent stability.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical care,
Waste liquids associated with wet processing of image forming materials have become a problem in terms of workability, and in recent years, reduction in the amount of processing waste liquids has been strongly desired from the viewpoint of environmental conservation and space saving. Therefore, there has been a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution and clear black image.

A photothermographic material for forming a photographic image by using a heat development method as a technique for this purpose is disclosed in, for example, US Pat. Nos. 3,152,904 and 3,457,075 and D.C.
Morgan and B.A. Shelley
y) "Heat treated silver system (The
rally Processed Silver S
systems) "(Imaging Processes and Materials)
es and Materials) Neblett
e, 8th edition, Sturge, V.E. Walworth, A .; Shep
p) Edit, page 2, 1969).

In such a photothermographic material, a reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), and a reducing agent are usually dispersed in a (organic) binder matrix. It is contained in a state. The photothermographic material is stable at room temperature, but generates silver through an oxidation-reduction reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent when heated to a high temperature after exposure.

[0005] This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by 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. An antifoggant for controlling the fogging of this image is used as necessary in the light-sensitive material. The most effective method as a conventional antifogging 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. 89,903. However, the use of mercury compounds is environmentally unfavorable, and the development of non-mercury antifoggants has been desired.

As the non-mercury-based anti-fogging agent, various polyhalogen compounds (for example, US Pat.
4,96, 4,756,999, 5,340,
No. 712, European Patent Nos. 605, 981 A1, 62
2,666 A1, 631, 176 A1, No. 5
4-165, JP-A-7-2781) are disclosed.

However, these compounds have problems that the fogging effect is low and the color tone of silver is deteriorated. In addition, those having a high antifogging effect have problems such as lowering the sensitivity, and thus need to be improved.

Further, there is a problem that fogging in unexposed areas increases when exposed and developed after aging under forced conditions of humidification and heating in the form of laminated photosensitive materials. Was desired.

As a method for solving these problems, Japanese Patent Application Laid-Open No.
No. 60164, No. 9-244178, No. 9-2583
No. 67, No. 9-265150, No. 9-281640
And JP-A-9-319022 disclose polyhalogen compounds in which the above-mentioned disadvantages are improved. However, in particular, when these compounds are applied to a photothermographic material for output of a printing imagesetter containing a high contrast agent and having an oscillation wavelength of 600 to 800 nm, the above disadvantages are considerably improved, It is not enough.

In the case of performing color printing, a photosensitive material for printing plate making usually uses a plurality of films separated for each color, prints them on the respective printing plates, and prints them one upon another. Therefore, when films separated for each color are overlapped, if they do not overlap exactly, a phenomenon occurs in which colors are shifted when printed. Therefore, in the photosensitive material for printing plate making, the dimensions do not change after development, that is, dimensional stability is important.

However, when the photothermographic material as described above is developed at a temperature of 80 ° C. or higher, the dimensional stability described above is insufficient, and the material is practically usable when used in color printing. It was not something.

Further, many techniques have been known for the color tone improving agent for silver images since ancient times, and for example, a method of adding a specific mercapto compound to a silver halide emulsion layer or a layer adjacent thereto is known.

However, the above method has a drawback that the color tone cannot be improved unless the photosensitive material is used in a region that significantly impairs the sensitivity and developability.

Accordingly, there has been a demand for a photothermographic material which has improved dimensional stability and silver tone, and has no fog over time.

[0016]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material which is excellent in dimensional stability and silver tone of the photothermographic material, and which does not cause an increase in fog over time.

[0017]

The above object of the present invention is attained by the following constitutions.

1. A photosensitive layer containing an organic silver salt, photosensitive silver halide particles and a reducing agent on a polyester support derived from a cycloaliphatic diol and an aromatic dicarboxylic acid; A photosensitive layer having a silver content of 0.03 to 0.03;
A heat-developable photographic light-sensitive material, characterized in that the photographic light-sensitive material is 0.3 g / m ² .

2. A photosensitive layer containing an organic silver salt, photosensitive silver halide particles and a reducing agent on a copolyester support derived from a cycloaliphatic diol, an alkylene glycol and an aromatic dicarboxylic acid; It has a non-photosensitive layer from the support farther, and heat-developable photographic material, wherein the silver amount of the photosensitive silver halide grains is 0.03 to 0.3 g / m ^2.

3. 3. The photothermographic material according to item 1 or 2, wherein the photothermographic material contains a compound represented by the following general formula (1).

Formula (1) Ar- (SO ₂ ) _y —CX _{3 In the} formula, Ar represents an aromatic group or a heterocyclic group, X represents a halogen atom, and y is 0 or 1.

4. 4. The photothermographic material according to any one of the above items 1 to 3, wherein the photothermographic material contains a compound represented by the following general formula [H].

[0023]

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Where A₀May each have a substituent
Aliphatic group, aromatic group, heterocyclic group or G₀-D₀Table
Then B₀Represents a blocking group;₁, A_TwoAre both water
A hydrogen atom or one of them is a hydrogen atom and the other is an acyl group,
And an oxalyl group. G ₀Is a -CO- group, -CO
CO- group, -CS- group, -C (= NG₁D₁) -Group, -S
O-group, -SO_Two-Group or -P (O) (G₁D₁)-Group
Represents, G₁Is a mere bond -O- group, -S- group or -N
(D₁) Represents a group, D₁Is an aliphatic group, an aromatic group, a heterocyclic group
Or a hydrogen atom, and a plurality of D₁Where there is
If so, they can be the same or different. D₀Is
Hydrogen atom, aliphatic group, aromatic group, heterocyclic group, amino group,
Alkoxy group, aryloxy group, alkylthio group,
Represents a reelthio group.

Hereinafter, the present invention will be described in more detail. The polyester derived from the cycloaliphatic diol and the aromatic dicarboxylic acid of the present invention is obtained, for example, by condensing a cis- or trans-form of 1,4-cyclohexanedimethanol (or a mixture thereof) with an aromatic dicarboxylic acid. A polyester having the following repeating unit.

[0026]

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Here, 1,4-cyclohexanedimethanol is selected from its cis form and trans form, and R ₁
Represents an aryl group containing 6 to 20 carbon atoms,
A decarboxylated residue derived from an aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid represented by R ₁ in the above formula include isophthalic acid, terephthalic acid, 1,2-
There are di (p-carboxyphenyl) ethane, 4,4-dicarboxydiphenyl ether and mixtures thereof.
All of these acids have at least one aromatic ring. Compounds such as 1,4- or 1,5-naphthalenedicarboxylic acid are also included. The preferred dicarboxylic acid is terephthalic acid or a mixture of terephthalic acid and isophthalic acid.

Specific examples of the polyester derived from a cycloaliphatic diol and an aromatic dicarboxylic acid are shown below, but the present invention is not limited thereto.

[0029]

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[0030]

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The process for producing a copolyester derived from the cycloaliphatic diol, alkylene glycol and aromatic dicarboxylic acid of the present invention can be carried out, for example, by using the cis or trans isomer of 1,4-cyclohexanedimethanol (or a trans isomer thereof). Mixture) and an alkylene glycol with an aromatic dicarboxylic acid to produce a copolyester having the following repeating units.

[0032]

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Here, 1,4-cyclohexanedimethanol is selected from its cis form and trans form, and R ₂
Has the same meaning as R ₁ , n represents an integer of 2 to 4, c represents about 10 to about 90% by mass, and d represents about 10 to about 90% by mass.

Specific examples of the copolyester derived from the cycloaliphatic diol, alkylene glycol and aromatic dicarboxylic acid of the present invention are shown below, but the present invention is not limited thereto.

[0035]

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[0036]

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The thickness of the support is about 50 to 300 μm, preferably about 70 to 180 μm. A heat-treated plastic support can also be used.

The heat treatment of the support refers to a temperature which is usually higher than the glass transition point of the support by at least 30 ° C., preferably 35 ° C., after the formation of the support and before the photosensitive layer is coated.
The support is heated at a temperature higher than 0 ° C., more preferably at a temperature higher than 40 ° C., and not exceeding the melting point of the support.

As the method of forming a film and the method of producing an undercoat of the support of the present invention, known methods can be used, but preferably, paragraphs [0030]-[0] of JP-A-9-50994.
070].

In the present invention, the devitrification of the photosensitive material is prevented.
For example, the silver amount of silver halide is 1m ^Two0.03 per
0.3 g, preferably 0.05-0.2 g
More preferably, there is.

When the amount of silver exceeds 0.3 g, the performance during running is greatly deteriorated, and when the amount of silver is less than 0.03 g, a sufficient density cannot be obtained. Further, the amount of silver halide based on the total amount of silver halide and organic silver salt is preferably 50% or less, more preferably 25% or less, and further preferably 0.1 to 15% by mass ratio.

The compound represented by the general formula (1) of the present invention improves the fog stability during the storage period of a photothermographic system.

In the above general formula (1), Ar represents an aromatic group or a heterocyclic group, X represents a halogen atom, and y is 0 or 1.

The details of the compound represented by the general formula (1)
U.S. Pat. Nos. 4,546,075 and 4,756,9
No. 99, No. 4,452,885, No. 3,874,
946 and 3,955,982.

The compound represented by the general formula (1) of the present invention is usually contained in silver or a top coat layer in an amount of 5 × per mole of silver.
10 ^{-4 to} 0.5 mol, preferably 5 × 10 ^{-3 to} 5 × 10
^-2 mol.

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

[0047]

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[0048]

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[0049]

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In the present invention, the compound represented by the above general formula (1) is used as an isocyanate compound described in JP-A-6-208193, US Pat. No. 3,017,280,
When used in combination with an epoxy compound described in JP-A-9-5916, the fog prevention effect can be further improved.

Further, the carbodiimide compound described in US Pat. No. 3,100,704 is also used in combination to obtain an antifogging effect.

Representative examples of these compounds preferably used in the present invention are described below. Preferred isocyanate compounds that can be used in combination with the compound represented by the general formula (1) of the present invention include the following general formula (2)
The compound represented by these is mentioned.

General formula (2) O = C = NL- (N = C = O) _{v In the} general formula (2), L represents a linking group which is an alkylene group, alkenylene group, arylene group or aralkylene group. , V is 0, 1 or 2.

These isocyanate compounds have been found to increase the fog stability of a photothermographic emulsion of a photothermographic material. Preferred substituents on the arylene group are selected from halogen atoms (for example, bromine, chlorine and the like), hydroxy groups, amino groups, carboxy groups, alkyl groups and alkoxy groups.

The following are examples of commercially available isocyanate compounds preferably used in the present invention, but the present invention is not limited to these.

IC-1 Desmodu
r) N100, Mobay, aliphatic isocyanate IC-2 Desmodu N3300, Mobay, aliphatic isocyanate IC-3 Mondur TD-80, Mobay, aromatic isocyanate IC-4 Mondue M, Mobay, aromatic Isocyanate IC-5 Montdue MRS, Mobay, Polymer Isocyanate IC-6 Desmodu W, Mobay, Aliphatic Isocyanate IC-7 Papi 27, Dow, Polymer Isocyanate IC-8 Isocyanate T1890, Huls (Hu)
els), aliphatic isocyanate IC-9 octadecyl isocyanate, Aldrich, aliphatic isocyanate Next, a compound having an aziridine group that can be preferably used in the present invention will be described.

The compound having an aziridine group can be arbitrarily used as long as it has a hardening action. Preferred compounds include the following compounds.

[0058]

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Next, epoxy compounds that can be preferably used in the present invention will be described.

The epoxy compound can be arbitrarily used as long as it has an epoxy group and exhibits a hardening action.
Preferred compounds have a hydroxy group or an ether condensation. The specific compounds are described below.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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The above epoxy compounds are almost commercially available and can be easily obtained. The method of adding the epoxy compound may be such that the compound is dissolved in an organic solvent such as alcohol, acetone, or toluene or water, and may be added as it is, or a surfactant such as dodecylbenzenesulfonate or nonylphenoxyalkylene oxide may be used. You may add after dispersing using an agent.

In the present invention, carbodiimide compounds other than those described above are also used. Preferred carbodiimide compounds are compounds represented by the following general formulas (3) and (4).

[0070]

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In the general formulas (3) and (4), A is an aliphatic group such as a methyl group, an ethyl group, an isopropyl group, n
-Butyl group, isobutyl group, t-butyl group, allyl group,
Organic groups such as crotyl group, β-hydroxyethyl group, methoxymethyl-β-bromoallyl group, aromatic groups such as phenyl group, tolyl group, xylyl group, naphthyl group, chlorophenyl group, bromophenyl group, iodophenyl group And cycloaliphatic groups such as cyclohexyl, bornyl and menthyl, and heterocyclic groups such as pyridyl and quinolyl.

R ₁ and R _{2 each} represent a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and B and B ₁ (which may be the same or different) are It represents an alkylene group, an arylene group or an aralkylene group, for example, a propylene group, a phenylene group, a tolylene group, a propylphenylene group and the like.

These di-substituted carbodiimides can be obtained by converting N, N'-di-substituted symmetric or asymmetric thioureas having at least one tertiary amino group into Berichte,
Vol. 71, 1512-1521, Vol. 7
3,467-477 pages, 1114-1123 pages, Vo
l. 75, pp. 100-105, Annalen, Vo.
l. As described on pages 560, 222-231, etc., it can be obtained by treating with a desulfurizing agent such as a heavy metal oxide such as lead or mercury.

The following are representative compounds. N-isopropyl-N '-(4-dimethylaminophenyl) carbodiimide N-phenyl-N'-(4-dimethylaminophenyl)
Carbodiimide N, N'-di (4-dimethylaminophenyl) carbodiimide N, N'-di (4-dipropylaminotolyl) carbodiimide N-bornyl-N '-(4-dimethylaminophenyl)
Carbodiimide N-menthyl-N '-(4-dimethylaminophenyl)
Carbodiimide N- (β-bromoallyl) -N ′-(γ-dimethylaminophenyl) carbodiimide N- (t-butyl) -N ′-(γ-dimethylaminophenyl) carbodiimide N-cyclohexyl-N ′-(4-dimethyl Aminophenyl) carbodiimide N-isopropyl-N ′-(γ-dimethylaminopropyl) carbodiimide N-methoxymethyl-N ′-(γ-dimethylaminopropyl) carbodiimide N, N′-di (γ-pyridyl) carbodiimide N, N'-disubstituted carbodiimides having a tertiary amine can be used directly or in the presence of ethyl acetate, chloroform, benzene or toluene or a mixed solvent thereof with a suitable quaternizing agent such as methyl bromide, Ethyl iodide, methyl iodide, ethyl iodide, dimethyl sulfate, die Le sulfuric, p- toluenesulfonic acid methyl, p
-It can be converted to a quaternary ammonium salt by reacting with ethyl toluenesulfonate or the like, whereby the solubility can be controlled. Moreover, you may add in the form of a quaternary salt.

The following are quaternized N, N'-disubstituted carbodiimides. N-isopropyl-N '-(4-dimethylaminophenyl) carbodiimideethyl p-toluenesulfonate N-phenyl-N'-(4-dimethylaminophenyl)
Carbodiimide ethyl-p-toluenesulfonate N, N'-di (4-dimethylaminophenyl) carbodiimide monoethobromide N, N'-di (4-dipropylaminotolyl) carbodiimideethyl p-toluenesulfonate N-bornyl-N ' -(4-dimethylaminophenyl)
Carbodiimide methosulfate N-menthyl-N '-(4-dimethylaminophenyl)
Carbodiimide ethosulfate N- (β-bromoallyl) -N ′-(γ-dimethylaminophenyl) carbodiimide ethosulfate N- (t-butyl) -N ′-(γ-dimethylaminophenyl) carbodiimideethyl-p-toluenesulfonate N -Cyclohexyl-N '-(4-dimethylaminophenyl) carbodiimideethyl-p-toluenesulfonate N-isopropyl-N'-([gamma] -dimethylaminopropyl) carbodiimideethyl-p-toluenesulfonate N-methoxymethyl-N '-( [gamma] -dimethylaminopropyl) carbodiimide ethyl p-toluenesulfonate N, N'-di ([gamma] pyridyl) carbodiimide monomethosulfate In general, fogs such as isocyanates and epoxy compounds which are preferably used in the present invention. The inhibitor compound is used in an amount of at least 0.002 mole per mole of silver. Usually, it is 0.002 to 2 mol, preferably 0.03 to 0.3 mol, per mol of silver.

Next, the compound represented by formula (H), which is preferably used in the present invention, will be described.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms.
Particularly, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, and a benzyl group. (For example, an aryl group,
Alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamido, sulfamoyl, acylamino, ureido, etc.).

In the formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, for example, a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring, and, in -G ₀ -D ₀ group represented by A _0, G ₀ is -CO
Group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — represents a group. G ₁ is a mere bond, -O-
A group, —S— group or —N (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the molecule, They can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferable D ₀ includes a hydrogen atom, an alkyl group, an alkoxy group, an amino group, and the like.

A ₀ is particularly preferably an aryl group or a heterocyclic group, and the aromatic group and the heterocyclic group of A ₀ may have a substituent.
Specific examples of the substituent having an acidic group of Ka 7 to 11 include a sulfonamide group, a hydroxyl group, and a mercapto group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, a photographically inert alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, Examples thereof include a phenoxy group and an alkylphenoxy group, and the total number of carbon atoms in the substituent is preferably 8 or more.

The thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — group, and preferred G ₀ is —CO—
Group, in -COCO- group, especially preferably -COCO- group, and the like, G ₁ is a single bond, -O- group, -S- group, or -N (D ₁₎ - represents a group, D ₁ is aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ represents a hydrogen atom, a substituted or unsubstituted aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl Group, alkoxy group,
Examples thereof include an amino group, and more preferably an alkyl group substituted with a fluorine atom. A ₁ and A ₂ are each a hydrogen atom or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.) or an oxalyl group (ethoxalyl) Group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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Other hydrazine derivatives that can be preferably used include US Pat. No. 5,545,505.
Nos. H-1 to H- described in Columns 11 to 20
Compounds 1 to 12 described in columns 9 to 11 of Nos. 29 and 5,464, 738 can be mentioned. These hydrazine derivatives can be synthesized by a known method.

The hydrazine derivative-added layer is a photosensitive layer containing a silver halide emulsion and / or a layer adjacent to the photosensitive layer. The optimum amount is not uniform depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like, but is preferably 10 ^-6 to 10 per mol of silver halide.
^The preferred range is about ^-1 mol, particularly 10 ^-5 to 10 ^-2 mol.

In the present invention, silver halide grains function as an optical sensor. The silver halide grains preferably have a small average grain size in order to suppress white turbidity after image formation and obtain good image quality, and the average grain size is preferably 0.1 μm or less, more preferably 0.01 to 0. 0.1 μm, especially 0.02 to 0.08 μm.

The grain size as used herein refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. The particle size is more preferably 30% or less, and particularly preferably 0.1 to 20%.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 In the present invention, the silver halide particles have an average particle size of 0.1.
μm or less and more preferably monodisperse particles,
By setting it in this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is preferably high, and this proportion is preferably 50% or more, more preferably 7% or more.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by the T.M. Tani, J .; Imaging Sci. , 29,
165 (1985).

Another preferred form of silver halide is tabular grains. The term "tabular grain" as used herein means that the square root of the projected area is defined as a particle size rμm, and the thickness in the vertical direction is defined as hμ.
It means that the aspect ratio = r / h when m is 3 or more. Among them, the aspect ratio is preferably 3 to 50 or less. The particle size is preferably 0.1 μm or less, and more preferably 0.01 to 0.08 μm. These are disclosed in U.S. Patent Nos. 5,264,337 and 5,314,134.
No. 798, 5,320,958, etc., and the desired tabular grains can be easily obtained.

When these tabular grains are used in the present invention, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. May be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide,
Silver halide may be prepared in advance and added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred.

In general, the silver halide is preferably contained in an amount of 0.75 to 30% by mass based on the organic silver salt.

The silver halide used in the present invention preferably contains an ion or a complex ion of a metal belonging to Group 6 to Group 10 of the Periodic Table of the Elements for the purpose of improving illuminance failure and adjusting gradation. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred.

These metal ions can be introduced into silver halide in the form of a metal complex or a metal complex ion. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 11 of the periodic table, L is a ligand, and m is 0,-, 2-, 3- or 4-
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

The following are specific examples of transition metal complex ions, but the present invention is not limited to these.

[0106] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2-11 : [Re (NO) Cl ₅ ] ^2-12 : [Re (NO) (CN) ₅ ] ^2-13 : [Re (NO) Cl (CN) ₄ ] ^2-14 : [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) (CN) _5] ^2- 17: [Fe (CN) _6] ^3- 18 : [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN)] ^{2 -} 23: [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl ₅ ] ^2-27 : [Ir (NS) Cl ₅ ] ^2- These metal ions, metal complexes or metal complex ions may be used alone or in combination of two or more of the same and different metals. Good. The content of these metal ions, metal complexes or metal complex ions, generally is suitably 1 × 10 ^-9 ~1 × 10 ^-2 mol per mol of silver halide, preferably 1 × 10 ^{- It is 8} to 1 × 10 ^-4 mol.

The compounds providing these metals are preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical ripening Although it may be added at any stage before and after sensitization, it is particularly preferable to add at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, and most preferably. It is added at the stage of nucleation.

In the addition, the compound may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added uniformly to the silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are used. When they are mixed simultaneously, they are added as a third aqueous solution to prepare silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or a method in which halogen is added. There is a method in which another silver halide grain doped with metal ions or complex ions in advance during the preparation of silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution.

At the time of addition to the particle surface, a required amount of an aqueous solution of a metal compound may be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

In the present invention, the photosensitive silver halide grains may or may not be desalted after grain formation, but when desalting is performed, it is known in the art such as a noodle method and a flocculation method. Can be desalted by washing with water.

The photosensitive silver halide grains used in the present invention are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used.

As the compound preferably used in the above-described sulfur sensitization method, selenium sensitization method, and tellurium sensitization method, known compounds can be used.
Compounds described in No. 8 and the like can be used.

Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, Compounds having a P = Te bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, having a P-Te bond Compounds, Te-containing heterocycles,
Tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and US Pat.
No. 48,060 and British Patent No. 618,061 can be preferably used.

As specific compounds for the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like are used. be able to. Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

Also, in the present invention, as described in Research Disclosure No. 17029 of June 1978 and US Pat. No. 3,700,458,
A method of forming a photosensitive silver halide by a method of converting a part of the silver of the organic silver salt into a photosensitive silver halide by adding a halogen-containing compound to the organic silver salt is also preferably used.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid and a heteroorganic acid containing a reducible silver ion source, especially a long chain (usually 10 to 30, preferably 15 to 15) Aliphatic carboxylic acids having 25 carbon atoms) and nitrogen-containing heterocycles are preferred. The ligand is 4.0 to 10.0
An organic or inorganic silver salt complex having a total stability constant with respect to silver ions is also useful. An example of a suitable silver salt is Resea
rc Disclosure No. 17029 and 29
No. 963, and include: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthio Urea salts (eg, 1
-(3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.);
Silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid) , 5,5-thiodisalicylic acid), silver salts or complexes of thiones (e.g., 3-
(2-carboxyethyl) -4-hydroxymethyl-4
-Thiazoline-2-thione) and 3-carboxymethyl-4-thiazoline-2-thione), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H
-Tetrazole, 3-amino-5-benzylthio-1,
Complexes or salts of silver and a nitrogen acid selected from 2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, silver arachidate, silver stearate and silver palmitate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, but a forward mixing method, a reverse mixing method, a simultaneous mixing method and the like are preferably used. Further, it is also possible to use a controlled double jet method as described in JP-A-9-127463. Specifically, after adding an alkali metal salt (for example, sodium hydroxide, potassium hydroxide, etc.) to an organic acid to prepare an organic acid alkali metal salt soap (for example, sodium behenate, sodium arachidate, etc.),
Silver nitrate is added to the soap to produce organic silver salt crystals. At that time, silver halide grains may be mixed,
The above series of reaction steps need to be performed while stirring sufficiently using a suitable stirring member so that the inside of the reaction tank becomes uniform.

In the present invention, the organic silver salt has an average particle size of 1
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.01 μm to 0.8 μm, particularly 0.05 μm
０．５0.5 μm is preferred. Monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.
%. In the present invention, the organic silver salt has an average particle size of 1 μm.
It is more preferable that the particles be monodisperse particles having a particle size of m or less. Further, the organic silver salt preferably has tabular grains having 60% or more of the total organic silver. In the present invention, the term “tabular grains” refers to a ratio of an average particle diameter to a thickness, that is, an aspect ratio (AR) represented by the following formula.
Abbreviation) means three or more.

AR = average particle size (μm) / thickness (μm) The organic silver having these shapes can be obtained by dispersing and pulverizing the organic silver crystal with a binder, a surfactant and the like using a ball mill or the like. Within this range, a photosensitive material having a high density and excellent image storability can be obtained.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448 and 3,773,512.
No. 3,593,863 and RD No. 17029
And 299963, and include the following. Aminohydroxycycloalkenone compounds (for example, 2-
Hydroxypiperidino-2-cyclohexenone); aminoreductones (reducto) as precursors of reducing agents
nes) esters (e.g., piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (e.g., Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (e.g.,
Phosphoramidophenols; Phosphoramidoanilines; Polyhydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); Fuhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg,
2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydroquinoxaline);
Amidoxins; Azines (for example, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids; Combination; α-cyanophenylacetic acid derivative; bis-β
A combination of -naphthol and a 1,3-dihydroxybenzene derivative; 5-pyrazolone; a sulfonamide phenol reducing agent; 2-phenylindane-1,3-dione and the like; chroman; 1,4-dihydropyridines (for example,
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 , 4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0122]

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In the general formula (A), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, butyl group, 2,4,4-trimethylpentyl group);
And R ″ represent an alkyl group having 1 to 5 carbon atoms (for example, each group such as methyl, ethyl and t-butyl).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0125]

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[0126]

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The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × 10 ^-2 to 10 mol, more preferably 1 × 10 ^{-2 to} 1.5 mol per mol of silver. Molar is preferred.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymers, synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic. , Polyvinyl alcohol, hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinyl chloride, polymethacrylic acid, copoly (styrene-maleic anhydride), copoly (Styrene-acrylonitrile), copoly (styrene-butadiene), polyvinyl acetal (eg, polyvinyl formal, polyvinyl butyral), polyesters, polyurethanes, phenoxy resin, polychlorinated Vinylidene, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, and polyamides. Although it may be hydrophilic or hydrophobic, in the present invention, in order to reduce fog after thermal development, it is preferable to use a hydrophobic transparent binder, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, and polycarbonate. , Polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, and polyester are particularly preferably used.

In order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer may be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, the amount of the binder in the photosensitive layer is preferably 1.5 to 10 g / m ² in order to increase the speed of thermal development. More preferably, 1.7 to 8 g /
m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side. In order to prevent the image after thermal development from being damaged, it is preferable to provide a matting agent on the surface of the photosensitive material. It is preferable that the composition contains the agent in an amount of 0.5 to 30% by mass based on all binders on the photosensitive layer side.
When a non-photosensitive layer is provided on the opposite side of the photosensitive layer with the support interposed therebetween, it is preferable that at least one layer on the non-photosensitive layer side contains a matting agent to prevent slippage of the photosensitive material and prevention of fingerprint adhesion. Also, it is preferable to provide a matting agent on the surface of the photosensitive material, and it is preferable that the matting agent is contained in a mass ratio of 0.5 to 40% with respect to all binders in the layer on the side opposite to the photosensitive layer side.

The material of the matting agent may be either an organic substance or an inorganic substance. For example, as the inorganic substance, silica described in Swiss Patent No. 330,158 and the like, and French Patent Nos. 1 and 2,
No. 96,995, glass powder described in British Patent No. 117
And alkaline earth metals or carbonates such as cadmium and zinc described in No. 3181 and the like. Examples of the organic substance include starch described in U.S. Pat. No. 2,322,037, Belgian Patent No. 625,451, and British Patent No. 9
81, 198, etc .;
-3643, polystyrene or polymethacrylate described in Swiss Patent No. 330,158, and US Pat. No. 3,079,257.
And the like, U.S. Pat.
Organic matting agents such as polycarbonates described in JP-A No. 22,169 or the like can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. The particle size of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The variation coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. The coefficient of variation is a value represented by (standard deviation of particle size) / (average value of particle size) × 100.

The matting agent can be contained in any constituent layer, but is preferably a constituent layer other than the photosensitive layer.
More preferably, it is the outermost layer as viewed from the support.

The method of applying the matting agent may be a method of dispersing in a coating solution in advance and applying it, or a method of applying the coating solution and spraying the matting agent before drying is completed. Is also good. When a plurality of types of matting agents are added, both methods may be used in combination.

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. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer on the opposite side, a so-called backing layer, may be formed. Dyes or pigments may be included. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range.
Nos. 9-6481 and 59-182436, U.S. Pat. Nos. 4,271,263 and 4,594,312, European Patent Publications 533,008, 652,473, and JP-A-2-216140. Nos. 4-348339 and 7
Compounds described in JP-A-191432, JP-A-7-301890 and the like are preferably used.

These non-photosensitive layers preferably contain the binder or matting agent described above, and may further contain a sliding agent such as a polysiloxane compound, wax or liquid paraffin.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

The heat-developable photographic light-sensitive material of the present invention forms a photographic image by heat-development processing, and includes a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, It is preferable that the color tone agent which suppresses the color tone of silver is contained in a state usually dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (for example, 80 to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon 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. This reaction process proceeds without supplying a processing liquid such as water from the outside.

Examples of suitable toning agents used in the present invention are R
D-17029, which includes the following:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 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 (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by -SS-Ar are preferred. M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthoimidazole,
Benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole,
Triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone.

These heteroaromatic rings include, for example, a halogen atom (for example, Br atom and Cl atom), a hydroxy, amino group, carboxy group and an alkyl group (for example, one or more carbon atoms, preferably 1 to 4 carbon atoms). And alkoxy (eg, having one or more carbon atoms,
And a group selected from those having preferably 1 to 4 carbon atoms).

Specific mercapto-substituted heteroaromatic compounds include, for example, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto- 1,2,4-triazole, 2-mercaptoquinoline, 8-mercaptopurine, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-hydroxy-2-mercaptopyrimidine,
-Mercapto-4-phenyloxazole and the like, but the present invention is not limited thereto.

The photothermographic materials of the present invention include, for example, JP-A-63-159814, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175, and 4,835. No. 096 can be used. Useful sensitizing dyes for use in the present invention are, for example, the aforementioned R
D-17643, IV-A (p.2 December 1978)
3) No. 1831, Item X (p. 43, August 1978)
It is described in the literature described or cited in 7).
In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-54409
The compounds described in No. 80679 are preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers.

The photothermographic material of the present invention includes, for example,
Surfactants, antioxidants, stabilizers, plasticizers, ultraviolet absorbers, coating aids and the like may be used. These additives and the other additives described above are the same as those described in RD No. 17029 (1).
June 978, p. Compounds described in 9 to 15) can be preferably used.

In the present invention, at least one conductive compound selected from metal oxides and conductive polymers can be included in the constituent layers in order to improve the chargeability.

These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat layer, and the like. In the present invention, conductive compounds described in U.S. Pat. No. 5,244,773, columns 14 to 20, are preferably used.

[0152]

EXAMPLES The present invention will be described in detail below with reference to examples, but embodiments of the present invention are not limited to these examples.

Example 1 (Preparation of Subbed Photographic Support) A commercially available biaxially stretched, heat-fixed, 175 μm-thick, blue-colored support having a repeating unit having the structure shown in Table 1 and having 8 w / subjected to corona discharge treatment in m ² · min, following under引塗coating solution a-1 on one side
Is applied to a dry film thickness of 0.8 μm and dried to form an undercoat layer A-1. On the other side, the following antistatic undercoat coating solution b-1 is dried to a dry film thickness of 0.8 μm. And dried to obtain an antistatic subbing layer B-1.

<< Undercoating Coating Solution a-1 >> 270 g of a copolymer latex liquid (solid content 30%) of butyl acrylate 30 mass% t-butyl acrylate 20 mass% styrene 25 mass% 2-hydroxyethyl acrylate 25 mass% C-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finished to 1 liter with water.

<< Undercoating Coating Solution b-1 >> Copolymer latex liquid of butyl acrylate 40 mass% styrene 20 mass% glycidyl acrylate 40 mass% (solid content 30%) 270 g (C-1) 0.6 g hexamethylene- 1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A corona discharge of 8 w / m ² · min is applied to the upper surface of the lower layer, and the lower layer upper layer coating solution a-2 is coated on the lower layer A-1 so as to have a dry film thickness of 0.1 μm. Sublayer B as Layer A-2
-1 is coated with the following undercoating layer coating solution b-2 having a dry film thickness of 0.
Coating was performed as a subbing upper layer B-2 having an antistatic function so as to have a thickness of 8 μm.

<< Coating solution a-2 for lower undercoat >> Gelatin 0.4 g / m ² Mass (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finish to 1 liter with water.

<< Lower Coating Upper Layer Coating Solution b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g (C-6) 12 g Polyethylene glycol ( (Weight average molecular weight: 600) 6 g Finished to 1 liter with water.

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(Heat Treatment of Support) In the above-mentioned undercoat drying step of the support, the support was heated at 140 ° C.
Thereafter, it was gradually cooled.

(Preparation of silver halide emulsion A) 900 m of water
7.5 g of inert gelatin and 10 ml of potassium bromide
mg, and adjusted to a temperature of 35 ° C. and a pH of 3.0, and then 370 ml of an aqueous solution containing 74 g of silver nitrate (98/98).
An aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 2) and [Ir (NO) Cl ₅ ] salt were added at a concentration of 1 × per mole of silver.
10 ^-6 mol and rhodium chloride at 1 × 1 per mol of silver
0 ^-6 mole, was added by the controlled double jet method while maintaining the pAg 7.7, pH 8.7, pAg
The reduction sensitization was performed at 6.5. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the pH was adjusted to 5 with NaOH to change the projected diameter area with an average particle size of 0.06 μm and a monodispersity of 10%. Cubic silver iodobromide grains having a coefficient of 8% and a [100] face ratio of 87% were obtained.

This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalted, and then 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5 to obtain a silver halide emulsion A.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide Emulsion A) 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. Later, 1M silver nitrate solution 14
7 ml was added over 7 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion has formed, the water is removed and an additional 6
After washing with water and removing water several times, it was dried.

(Preparation of photosensitive emulsion) Polyvinyl butyral (average molecular weight: 300
544 g of a methyl ethyl ketone solution (0%) (17% by mass)
And 107 g of toluene were gradually added and mixed.
Dispersed at 000 psi.

(Back side coating) A back layer coating solution having the following composition was applied by an extrusion coater to a wet film thickness of 30 μm, and dried at 60 ° C. for 3 minutes.

Back layer coating solution: Cellulose acetate butyrate (10% methyl ethyl ketone solution) 15 ml / m ² dye-B 7 mg / m ² dye-C 7 mg / m ² Monodispersity 15%, monodisperse silica having an average particle size of 8 μm Matting agent 30 mg / m ² C ₉ F ₁₇ —C ₆ H ₄ —SO ₃ Na 10 mg / m ²

[0169]

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(Coating of photosensitive layer side) A coating solution of a photosensitive layer having the following composition and a coating solution of a protective layer were coated thereon in an extrusion coater at a speed of 20 m / min. At this time, the silver was applied such that the amount of silver applied was 2.4 g / m ² . afterwards,
Drying was performed at 55 ° C. for 15 minutes.

Photosensitive layer coating solution: Preform emulsion 240 g Sensitizing dye-1 (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml of the compound represented by the general formula (1); described in Table 1 (10% methanol solution) 1.2 ml hydrazine compound-Exemplified H-7 (5% methanol solution) 2 ml 2-4-chlorobenzoylbenzoic acid ( 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml Developer-1 (20% methanol solution) 29.5 ml phthalazine 0.6 g 4 -Methylphthalic acid 0.25g Tetrachlorophthalic acid 0.2g Surface Protective layer coating solution: acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² methanol 7 ml / m ² phthalazine 250 mg / m ² monodispersity 10%, monodisperse silica matting average particle size 4μm 70 mg / m ² CH ₂ ＣＨCH ² —SO ₂ — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —SO ₂ —CH ₂ —CH ₂ 35 mg / m ² Spot inhibitor 50 mg / m ² C ₉ H ₁₇ — C ₆ H ₄ —SO ₃ Na 10 mg / m ²

[0172]

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<< Measurement of Dimension Repeatability >> Two thin lines were exposed on the photothermographic material prepared above at an interval of 500 mm with an imager having a semiconductor laser of 810 nm. Thereafter, heat development was performed at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.
This operation was repeated four times, and the distance between the two fine wires was accurately measured. In that case, the difference between the maximum value and the minimum value was defined as R (mm), and the dimensional repetition accuracy T was determined according to the following equation.

T = (R / W) × 100% W: Length (mm) of sample before development Less than 1% is a practically acceptable level.

<< Evaluation of Discoloration of Silver Tone >> One of the above-mentioned photothermographic materials was exposed to an imager having an 810 nm semiconductor laser. After that, using an automatic developing machine having a heat drum,
Heat development was performed for 5 seconds. The treated sample is divided into two equal parts, and one is left under conditions of 40 ° C. and 80% RH for 3 days,
The discoloration of the image area was evaluated as follows in comparison with the other sample.

：: No discoloration (still black) Δ: Slightly discolored brown (a level that can be used somehow) X: Discolored brown (unusable) << Change in fog density of unexposed portion of treated sample >> After being left for 3 days at 40 ° C. and 80% RH, the unexposed portion of the treated sample was measured for density and compared with the other sample. The difference in fog density at that time was defined as fog density change. Table 1 shows the obtained results.

[0177]

[Table 1]

As comparative supports, the following P-1 and P-2
A support having a repeating unit having a structure represented by the following formula was used.

[0179]

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It was found that the sample of the present invention had better dimensional repetition accuracy than the comparative sample, had no discoloration during storage of image silver, and had little change in fog density.

Example 2 Sample No. 1 of Example 1 Sample Nos. 3 and 6 were the same except that the hydrazine compound was omitted. 9, 1
0 and sample no. Antifoggant was added to AF-
Sample No. 7 was the same except that it was changed to Sample No. 7. 1
Nos. 1 and 12 were produced, and the same evaluation was performed. Table 2 shows the obtained results.

[0182]

[Table 2]

It can be seen that the effects of the present invention are more exhibited when the compound of the general formula (1) or the compound of the general formula [H] is used.

[0184]

The photothermographic material according to the present invention has excellent dimensional stability and silver tone, and has an excellent effect with no increase in fog over time.

Claims (4)

[Claims] An organic silver salt on a polyester support derived from a cycloaliphatic diol and an aromatic dicarboxylic acid,
A photosensitive layer containing photosensitive silver halide grains and a reducing agent, having a non-photosensitive layer on the support side adjacent to the photosensitive layer,
Further, the silver content of the photosensitive silver halide grains is 0.03 to 0.3.
A heat-developable photographic light-sensitive material characterized by having a weight of 3 g / m ² . 2. A photosensitive layer containing an organic silver salt, photosensitive silver halide particles and a reducing agent on a copolyester support derived from a cycloaliphatic diol, an alkylene glycol and an aromatic dicarboxylic acid; A heat-insensitive layer having a non-photosensitive layer adjacent to the layer and remote from the support, wherein the silver content of the photosensitive silver halide grains is 0.03 to 0.3 g / m ^2. Photosensitive material. 3. The photothermographic material according to claim 1, wherein the photothermographic material contains a compound represented by the following general formula (1). General formula (1) Ar— (SO ₂ ) _y —CX ₃ [wherein, Ar represents an aromatic group or a heterocyclic group, X represents a halogen atom, and y is 0 or 1. ] 4. The photothermographic material according to claim 1, wherein
A process characterized by containing a compound represented by [H].
The photothermographic material according to any one of claims 1 to 3. Embedded image[Where A₀Is an aliphatic which may have a substituent
Group, aromatic group, heterocyclic group or G₀-D₀Represents a group, B₀Is
Represents a blocking group;₁, A_TwoAre both hydrogen atoms or
One is a hydrogen atom and the other is an acyl group, a sulfonyl group,
Represents a zaryl group. G ₀Is a -CO- group, a -COCO- group,
-CS- group, -C (= NG₁D₁)-Group, -SO- group,-
SO_Two-Group or -P (O) (G₁D₁)-Group;₁Is
A mere bond, -O- group, -S- group or -N (D₁) Group
And D₁Represents an aliphatic group, an aromatic group, a heterocyclic group, or hydrogen
Represents an atom, and multiple D₁If there is,
They may be the same or different. D₀Is hydrogen field
Child, aliphatic group, aromatic group, heterocyclic group, amino group, alcohol
Xy, aryloxy, alkylthio, aryl
Represents a thio group. ]