JPH11202444A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat-developable photosensitive material low in fog and superior in the storage stability of the photosensitive material and image storage stability without deteriorating sensitivity and color tone by incorporating at least one kind of specified compound. SOLUTION: This heat-developable photosensitive material contains at least one of compounds represented by formulae I-III in which X is an atomic group necessary to form a hetero ring substituted by at least one of -SO3 M, -COOM, and -OM groups; each of A1 and A1' is a -SO3 M, -COOM, or -OM group; M is an H or metal atom or the like; each of (m) and (n) is an integer of 1-10; each of A2 and A2' is an electron with-drawing group; each of A3 and A3' is a functional group having an S, Se or Te atom capable of combining with silver ions; (r) is 0 or 1; each of Y, Y1 and Y2 is an aliphatic, aromatic or heterocyclic groups; Z is an S, Se or Te atom; and (p) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material and, more particularly, to a technique for preventing fog, improving photographic material preservability and improving image preservability without lowering sensitivity or deteriorating 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. 04, 3,457,075 and D.C. Morgan and B.A. "Silver System Treated by Heat (Thermall) by Shelly
y Processed Silver System
s) "(Imaging Processes and Materials)
Materials) Neblette Eighth Edition, Sturge, V.M. Wallworth
or)). Shepp Editing, 2nd
Pp. 1969). Such a photothermographic material comprises a reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), a color tone controlling agent for controlling the color tone of silver, and a reducing agent, usually using an (organic) binder. It is contained in a dispersed state in the matrix. The photothermographic material is stable at room temperature, but is exposed to high temperature (for example, 80
When heated to above (° C. or more), silver is generated through a redox reaction between a reducible silver source (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

The most effective antifoggant as a conventional antifogging technique has been mercury ion. Regarding the use of mercury compounds as antifoggants in photosensitive materials,
For example, it is disclosed in U.S. Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly. Non-mercury antifoggants are disclosed in U.S. Pat. No. 3,874,946.
And -C (X ¹ ) (X ² ) (X ³ ) wherein X ¹ and X ² are halogen (eg, F, Cl, X ³ with Br and I)
Is a heterocyclic compound having one or more substituents represented by hydrogen or halogen), but when used as it is, it has problems such as remarkably deteriorating the color tone of silver and lowering the sensitivity, and needs to be improved. Met. Further, there is a problem that when the photosensitive material is laminated and subjected to aging under forced conditions of over-humidification and heating, and then exposed and developed, fog in an unexposed portion increases.

Japanese Patent Application Laid-Open No. 9-5926 discloses the use of a disulfide compound as a technique for preventing fog and improving the storage stability of a photosensitive material without deteriorating color tone in a photothermographic material. . Certainly, the storage stability before exposure can be improved to some extent by these compounds, but the image storage stability after exposure and development is not yet sufficient, and further improvement in image storage stability has been desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material having reduced fog, improved photographic material preservability and improved image preservability without lowering the sensitivity or deteriorating the color tone.

[0006]

The above object has been attained by the following constitutions.

(1) A photothermographic material comprising at least one compound represented by the following general formula (1), (2) or (3).

[0008]

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In the formula, X represents an atom group capable of forming a heterocycle having at least one of —SO ₃ M, —COOM and —OM. M represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group. However, it does not have a partial structure represented by -NH-C (= S)-in the heterocyclic structure.

[0010]

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[0011] In the formula, A1 and A1 'is -SO ₃ M, -C
Represents OOM or -OM, and M represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group. A1 and A1 'may be the same or different. m is 1
Represents an integer of 10.

A2 and A2 'each represent an electron-withdrawing group;
2 and A2 'may be the same or different. n
Represents an integer of 1 to 10.

A3 and A3 'represent a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion, and A3 and A3' may be the same or different. r represents 0 or 1.

Y, Y1 and Y2 each represent an aliphatic group, an aromatic group or a heterocyclic group. Z represents a sulfur atom, a selenium atom or a tellurium atom. p represents 1 or 2.

(2) The photothermographic material as described in (1) above, further comprising a compound represented by the following general formula (4).

[0016]

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In the formula, Q represents an aryl group or a heterocyclic group. X1 and X2 each represent a halogen atom. Y3
-C (O) is -, - SO- or -SO ₂ - represents a. A represents a hydrogen atom, a halogen atom or an electron-withdrawing group. q represents an integer of 2 to 6.

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

The inhibitors represented by the general formulas (1) to (3) of the present invention have little effect on the adsorption and desorption of the dye, that is, little influence on the sensitivity. Excellent silver color tone can be obtained with low fog while maintaining.

Further, it is particularly excellent in preservability before exposure and image preservability after heat development.

Hereinafter, the present invention will be described in detail.

First, the compound represented by the formula (1) will be described.

X in the general formula (1) is -SO ₃ M,
Represents a group of atoms capable of forming a hetero ring having at least one of -COOM or -OM, and examples of the formed hetero ring group include an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, and a tetrazole ring; Thiadiazole ring, oxadiazole ring, pentazole ring, pyrimidine ring, thiazine ring, triazine ring, thiodiazine ring, or a ring bonded to another carbon ring or hetero ring, for example, benzothiazole ring, benzotriazole ring, benzimidazole ring, A benzoxazole ring, a benzoselenazole ring, a naphthooxazole ring, a triazaindolizine ring, a diazaindolizine ring, or a tetraazaindolizine ring, and these heterocyclic groups may have a substituent; Is an aliphatic group, an aromatic group or a heterocyclic group That.

Preferred are an imidazole ring,
Examples of the substituent include a tetrazole ring, a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, and a triazole ring. The substituent is preferably an aliphatic group (eg, a lower alkyl group such as a methyl group, an ethyl group, an aralkyl group). Groups, such as a benzyl group), and an aromatic group (eg, a phenyl group).

M in the general formula (1) represents a hydrogen atom, a metal atom, for example, a transition metal atom such as an alkali metal, silver, gold or palladium, an ammonium group or a quaternary phosphonium group.

Specific examples of the compound represented by formula (1) used in the present invention are shown below, but the present invention is not limited thereto.

[0027]

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[0028]

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The compound of the above general formula (1) can be synthesized by a general method, and some of the compounds are commercially available as chemical reagents.

The compound of the general formula (1) may be added at any time during chemical ripening. If added before the completion of chemical ripening, the effect may be high, but if added separately before and after the completion, the effect may be further enhanced. The compounds may be used in combination of two or more kinds, or may be used in combination with other additives.

As the addition method, the powder may be added as it is, or a solution dissolved in a low-boiling organic solvent such as methanol, ethanol or ethyl acetate, water or a mixed solvent of a low-boiling organic solvent and water may be added. It does not matter. At this time, if necessary, a regulator for changing the pH may be used to enhance the solubility. Further, when added as an added particulate solid dispersion, higher effects may be obtained. In each case, the amount of addition was 1 × 10 ⁻⁸ mol to 5 × per mol of silver.
10 ⁻² mol, preferably 1 × 10 ⁻⁶ mol to 3 × 1
0 ^-3 .

Next, the compounds represented by formulas (2) and (3) will be described.

[0033] In the general formula (2) and (3), A1 and A1 'represent -SO ₃ M, or -COOM-OM,
M is a hydrogen atom, a metal atom (for example, an alkali metal, silver,
A transition metal capable of forming a bond with sulfur or selenium such as gold or palladium is preferable), or a quaternary ammonium group or a phosphonium group. The structures of A1 and A1 'may be the same or different. Here, m is an integer of 1 to 10.

A2 and A2 'are electron-withdrawing groups (for example,
Fluorine atom, a trifluoromethyl group, a cyano group, a nitro group, -SOCF ₃ group, -SO ₂ NH ₂ group, -SO ₂ CH ₂ group and the like are preferred) represents the structure of A2 and A2 'are the same May also be different. Note that n is an integer of 1 to 10.

A3 and A3 'represent a functional group containing a sulfur or selenium atom capable of binding to a silver ion (for example, a mercapto group, a thione group, a -SeH group, and a = Se group are preferable). The structure may be the same or different. Note that r represents 1 or 2.

Y is an aliphatic hydrocarbon (for example, having 4 carbon atoms)
Represents an aliphatic hydrocarbon of 20 to 20 or less, or an aromatic hydrocarbon (for example, preferably a benzene ring or a naphthalene ring). Z represents a sulfur or selenium atom.

A1, A1 ', A2, A2', A3, A
In addition to the substituent such as 3 ', the compound may have the following substituent. That is, a halogen atom other than fluorine, a hydroxyl group, an amino group, an acylamino group, an alkylamino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an alkoxycarbonyl group, and a carbamoyl group , An alkoxyalkyl group, an aminoalkyl group, an acylaminoalkyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group, and an alkylsulfonamide group.

These compounds are available from Journal of the Chemical Society (C) (J. Chem. So
c. Sect. C), p. 626, 1965, the same magazine, 1
347, 1971, Journal of Organic Chemistry (J. Org. Chem.), 34
Volume, 534 pages, 1969, JP-A-60-184057.
And the method described in JP-A-60-204742, or a method analogous thereto. Some compounds are commercially available as chemical reagents.

Specific examples of the compounds represented by formulas (2) and (3) of the present invention are shown below, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The compounds of the above general formulas (2) and (3)
It may be added at any time during chemical ripening. If added before the completion of chemical ripening, the effect may be high, but if added separately before and after completion, the effect may be even higher. The compounds may be used in combination of two or more,
Moreover, you may use together with another inhibitor.

As the addition method, the powder may be added as it is, or a solution dissolved in a low-boiling organic solvent such as methanol, ethanol, ethyl acetate or the like, water or a mixed solvent of a low-boiling organic solvent and water may be added. It does not matter. At this time, if necessary, a regulator for changing the pH may be used to enhance the solubility. Further, when added as an added particulate solid dispersion, an even higher effect may be obtained. In each case, the amount of addition was 0.01 g to 0.5 g per mole of silver.
g, preferably 0.02 g to 0.2 g.

When used, the compounds represented by formulas (1), (2) and (3) may be separately added to the silver halide emulsion and the hydrophilic colloid solution, respectively. You may mix and add.

Next, the compound represented by formula (4) will be described in detail. As the aryl group represented by Q,
It preferably has 6 to 30 carbon atoms, more preferably a monocyclic or condensed aryl group having 6 to 20 carbon atoms, such as phenyl and naphthyl, and particularly preferably phenyl. The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic group having 1 to 30 carbon atoms and containing at least one of N, O and S atoms. And a condensed ring may be formed with another ring.

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

Q is preferably an aromatic nitrogen-containing heterocyclic group.

The halogen atoms represented by X1 and X2 may be the same or different, and may be a fluorine atom, a chlorine atom,
Bromine atom, iodine atom, preferably chlorine atom, bromine atom, iodine atom, more preferably chlorine atom,
It is a bromine atom, particularly preferably a bromine atom.

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

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

The electron-withdrawing group represented by A is preferably a substituent having a σ _p value of from 0.01 to 1.0, more preferably a substituent of from 0.1 to 1.0. Examples of the electron-withdrawing group include a trihalomethyl group (CBr
₃ (0.29), CCl ₃ (0.33), CF ₃ (0.5
4)), cyano group (0.66), nitro group (0.7
8), a sulfonyl group having 1 to 10 carbon atoms (methanesulfonyl (0.72)), an acyl group having 2 to 10 carbon atoms (acetyl (0.50)), an alkynyl group having 2 to 10 carbon atoms (C
≡CH (0.23)), an alkoxycarbonyl group having 2 to 10 carbon atoms (methoxycarbonyl (0.45)), an aryloxycarbonyl group having 7 to 12 carbon atoms (phenoxycarbonyl (0.44)), 1 to 10 carbamoyl groups (carbamoyl (0.36)), 0 to 10 carbon atoms
(Sulfamoyl (0.57)) and the like, and preferably a sulfonyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

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

Among the compounds represented by the general formula (4), a compound represented by the following general formula (4-a) is preferable.

[0057]

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(Wherein, X1, X2, A, and n have the same meanings as those in formula (4), and the preferred ranges are also the same. Q 'represents an aromatic nitrogen-containing heterocyclic group.) The aromatic nitrogen-containing heterocyclic group represented by Q 'is preferably a 5- or 6-membered aromatic heterocyclic ring containing 1 to 3 nitrogen atoms, for example, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine , Triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,
Cinnoline, buteridine, acridine, phenanthrolen, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzosazole, benzthiazole, indolenine and the like, more preferably pyridine, triazole, triazine, thiadiazole, oxadiazole, quinoline, tetrazole, Thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole and indolenine.

Of the compounds represented by formula (4-a), A is preferably a halogen atom.

The halogen atom is preferably a chlorine, bromine or iodine atom, more preferably a chlorine or bromine atom, particularly preferably a bromine atom. Specific examples of the compound represented by the general formula (4) are shown below, but the present invention is not limited thereto.

[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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The above compounds may be used in the form of a salt when possible. The compound represented by the general formula (4) of the present invention can be synthesized according to a method described in, for example, US Pat. No. 3,874,946, European Patent Publication 605,981 and the like.

The compounds represented by the above general formulas (1) to (4) can be added to a photosensitive layer or a non-photosensitive layer. Preferably, it is a photosensitive layer. The compounds represented by the general formulas (1) to (4) are different depending on the desired purpose, but may be 10 ^-4 mol or ^less .
1 mol / Ag mol, preferably 10 ^-3 mol to 0.3 mol / Ag mol is added. It is preferable to add any of the compounds by dissolving them in an organic solvent.

The photothermographic material of the present invention is preferably a mono-sheet type photothermographic material (a type in which all materials provided for forming an image are completed as an image sheet to be observed), because of its easiness on the earth. is there. The wavelength of the laser light for exposure can be changed as necessary depending on the type of the spectral sensitizing dye in the light-sensitive material. As a usual method, a photothermographic material for infrared laser exposure is preferably used. Further, the wavelength of the infrared laser exposure is preferably 750 nm or more, more preferably 800 nm or more. In order to correspond to a laser in such a wavelength range, it is necessary to spectrally sensitize the laser to have sensitivity in these wavelength ranges, that is, in the infrared range. Known infrared spectral sensitizing dyes may be used.

The photothermographic material of the present invention may be any as long as it can form a photographic image using a heat development process. A reducible silver source (for example, an organic silver salt), a photocatalyst having a catalytically active amount (for example, a halogen) It is preferable that the photothermographic material contains silver halide) and a reducing agent usually in a state of being dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but is exposed to high temperature (for example, 80 ° C.).
Heating is developed. Heating produces silver through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter layer may be formed on the same side as or opposite to the photosensitive layer, or a dye or pigment may be included in the photosensitive layer. The photosensitive layer may be composed of a plurality of layers.
It may be a low-sensitive layer or a low-sensitive layer / high-sensitive layer. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers.

Examples of the support applicable to the photothermographic material of the present invention include materials such as paper, polyethylene-coated paper, polypropylene-coated paper, parchment and cloth;
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). In the photothermographic material of the present invention, for example,
Surfactants, antioxidants, stabilizers, plasticizers, ultraviolet absorbers, coating aids and the like may be used.

The respective binder layers (for example, synthetic polymers) together with the chemicals 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
-(3aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide); combinations of blocked pyrazoles, isothiuronium derivatives and certain photobleaches (eg, N, N '-Hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2-
(Tribromomethylsulfonyl) benzothiazole combinations); merocyanine dyes (e.g., 3-ethyl-
5-((3-ethyl-2-benzothiazolinylidene (b
Enzothiazolinylidene))-1-
Methylethylidene) -2-thio-2,4-oxazolidinedione), phthalazinone, phthalazinone derivatives or metal salts of these derivatives (eg, 4- (1-naphthyl) phthalazinone,
6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione); phthalazine; 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-naphthalene A combination with at least one compound selected from dicarboxylic acids or o-phenylene derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinediones, Benzoxazine, naloxazine derivative; benzoxazine-2,4
-Diones (for example, 1,3-benzoxazine-2,
Pyrimidines and asymmetric triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2) , 3a,
5,6a-tetraazapentalene), and a preferred toning agent is phthalazone or phthalazine.

The reducing agent may contain a so-called photographic developer, for example, phenidone, hydroquinones, catechol, etc., but hindered phenol is preferred. Color light-sensitive materials such as those disclosed in U.S. Pat. No. 4,460,681 are also contemplated for realizing the present invention.

Examples of suitable reducing agents are described in US Pat.
No. 0,448, No. 3,773,512, No. 3,5
No. 93,863 and an investigation report (Research D
is described in Nos. 17029 and 29996, and includes the following: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones as precursors of the developer ) Esters (e.g., piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (e.g., Np-
Methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfhydroxams); sulfonamidoanilines (e.g., 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Amides (for example, a combination of an arylcarboxylic acid hydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxanoic acids; Combinations of sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamidophenol reducing agents; 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 , 4,4-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Preferred reducing agents are hindered phenols of the general formula (A).

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Wherein R is a hydrogen atom or a carbon atom of 1
10 alkyl group (e.g., -C ₄ H _9, 2,4,4- trimethylpentyl) represents, R ⁵ and R ⁶ are C 1 -C
To 5 alkyl groups (for example, methyl, ethyl, t-butyl).

Silver halide useful as a catalytically active amount of photocatalyst can be any photosensitive silver halide (eg, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, chloroiodobromide). Silver or the like), but preferably contains iodine ions. The silver halide may be added to the image-forming layer by any method, wherein the silver halide is arranged close to the reducible silver source. Generally, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver. The silver halide may be prepared by conversion of the silver salt by reaction with a halide ion, may be preformed and added during the formation of the silver salt, or a combination of these methods is possible.

The reducible silver source can be any material containing a reducible silver ion source. 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 (Research Disclosure).
Sure) Nos. 17029 and 29996, and include: 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, etc.); silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids) (Eg, salicylic acid,
Benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 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-triazole And a complex or salt of silver and a nitrogen acid selected from benzotriazole; 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 particularly preferred. The reducible silver source preferably has a silver amount of 3 g / m ² or less. More preferably, it is 2 g / m ² .

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 and 4,740,455,
Nos. 4,741,966 and 4,751,175
No. 4,835,096.

[0083]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Photosensitive Emulsion A Solution 1 Stearic acid 135 g Behenic acid 635 g Distilled water 13 liters mixed at 85 ° C. for 15 minutes Solution 2 NaOH 89 g Distilled water 1500 ml Solution 3 Concentrated HNO ₃ 19 ml Distilled water 50 ml Solution 4 AgNO ₃ 365 g distilled water 2500 ml solution 5 polyvinyl butyral 86 g ethyl acetate 4300 ml solution 6 polyvinyl butyral 290 g isopropanol 3580 ml solution 7 N-bromosuccinimide 9.7 g acetone 700 ml While maintaining the solution 1 at 85 ° C., the solution 2 is stirred for 5 minutes. And then add Solution 3 over 25 minutes. After stirring for 20 minutes as it is, the temperature is lowered to 35 ° C. Add solution 4 over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes. Thereafter, the solution 5 was added, the stirring was stopped, and the mixture was left to stand. The aqueous phase was removed together with the contained salt to obtain an oil phase, and the solvent was removed to remove traces of water.
Solution 6 was added and stirred vigorously at 50 ° C., and then Solution 7 was added over 20 minutes and stirred for 105 minutes to obtain photosensitive emulsion A.

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

<Back side coating> Antihalation layer (wet thickness 80 microns) Polyvinyl butyral (10% isopropanol solution) 150 ml Dye C (solvent is DMF) 70 mg <photosensitive layer side coating> Photosensitive layer (wet thickness 140 microns) ) Photosensitive emulsion A 73 g Sensitizing dye-1 (0.1% DMF solution) 2 ml Antifoggant-1 (0.01% methanol solution) 3 ml Phthalazone (4.5% DMF solution) 8 ml Reducing agent-1 (10 % Acetone solution) 13 ml Compounds 1, 2, 3, 4 listed in Table 1 Surface protective layer (wet thickness 100 microns) acetone 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g phthalazine 1.0 g 4-methylphthalic acid 72 g tetrachlorophthalic acid 0.22 g tetraclo Phthalic anhydride 0.5g

[0087]

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Sensitometry The photothermographic material prepared above is processed into half-cut sizes,
An 830 nm laser diode was exposed with a beam tilted 13 ° from the vertical. Then use a heat drum for 1
Heat development was performed at 20 ° C. for 5 seconds and at 125 ° C. for 10 seconds. At that time, the fog value was measured and the color tone was visually evaluated.
For fog, the sample No. 1 was expressed as a relative value when the fog at 120 ° C. × 5 seconds was taken as 100.

[0089]

[Table 1]

[0090]

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Table 1 shows that the sample of the present invention has low fog and a good black color tone.

Example 2 Preparation of Photosensitive Emulsion B Solution 135 g of stearic acid 635 g of behenic acid Distilled water 13 liters Mixed at 85 ° C. for 15 minutes Solution A CuBr AgI prepared in advance (I = 4 mol%) 0.06 μ (Ag as was kept 0.22 mol) of distilled water 1250ml solution NaOH 89 g distilled water 1500ml solution concentrated NHO 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 to 85 ° C. The solution A is added over 10 minutes with vigorous stirring in the state, followed by the solution over 5 minutes and then the solution 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 allowed to stand. The aqueous phase was removed together with the contained salt to obtain an oily phase. The solvent was removed to remove traces of water. Then, the solution was added and the mixture was stirred vigorously at 50 ° C. Thereafter, the mixture was stirred for 105 minutes to obtain Emulsion B.

A test was conducted in the same manner as in Example 1 except that an antihalation layer was provided below the photosensitive layer on both sides of the photosensitive layer. The sample using the compound of the present invention had a low fog and a good black tone as in Example 1.

Example 3 << Preparation of Silver Halide Particles A >> 16 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at a temperature of 35 ° C .;
An aqueous solution containing 159 ml of an aqueous solution containing 6 g and an aqueous solution containing potassium bromide and potassium iodide (92/8) were added over 10 minutes by a control double jet method while keeping the pAg at 7.7. Then, an aqueous solution 47 containing 55.4 g of silver nitrate.
6 ml and an aqueous solution containing potassium bromide were added over 30 minutes while maintaining the pAg at 7.7, and the pH was lowered to cause coagulation sedimentation and desalting treatment. Adjusted silver halide grains A (core 8 mol%, average 2 mol%, 0.05 μ cube, projected diameter area variation coefficient 8%, (100) face ratio 88
%) Was completed.

The temperature of the silver halide grains A was raised to 60 ° C., and sodium thiosulfate, selenium compound II-1, tellurium compound a-1, chloroauric acid and potassium thiocyanate were added.
After ripening for 0 minutes, the mixture was rapidly cooled to 35 ° C. to terminate the chemical sensitization to prepare silver halide grains. The amount added 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 Chloride Goldic acid 3.5 × 10 ^-4 mol / silver mol Potassium thiocyanate 2.7 × 10 ^-4 mol / silver mol

[0097]

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<< Preparation of Organic Fatty Acid Silver Emulsion B >> Water 300 m
Then, 10.6 g of behenic acid was put in 1 l of the mixture and dissolved by heating at 90 ° C.
1 ml was added, and left as it was for 1 hour. Thereafter, the mixture was cooled to 30 ° C., 7.0 ml of 1N phosphoric acid was added, and N-bromosuccinimide 0.0
1 g was added. Thereafter, the silver halide grains A prepared in advance were added with stirring while heating at 40 ° C. so that the silver amount was 10 mol% with respect to behenic acid. Further, 25 ml of a 1N silver nitrate aqueous solution was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

While stirring, 37 g of a 1.2 wt% solution of polyvinyl acetate in butyl acetate was gradually added to the aqueous mixture to form flocs of the dispersion. Thereafter, the water was removed, and washing was performed twice more (washing water conductivity 30 μS ·
cm). Next, polyvinyl butyral (molecular weight 3000)
Of 2-butanone solution of 2.5 wt% 20cc
Stir at sufficient speed for 0 minutes. Next, the following compound and 2-
40 g of butanone and polyvinyl butyral (molecular weight 40
00) Add 6.0 g and stir at full speed for 1 hour,
The preparation of the organic fatty acid silver emulsion B was completed.

[0100]

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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 obtain an emulsion coating solution (hereinafter, added amount per mole of silver).

Isocyanate (N3300 manufactured by Desmodule) 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 Reduction Agent-1 0.27mmol Tetrachlorophthalic acid 10.8mmol Coating aid-1 0.001mmol Compounds 1,2,3 Listed in Table 2

[0103]

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[0104]

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<< Preparation of Coating Solution for Surface Protective Layer >> A coating solution for surface protective layer 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

[0107]

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<< Preparation of Backing Layer Coating Solution >> A backing layer coating solution was prepared as follows.

Polyvinyl butyral (10% 2-butanone solution) 30 ml Cellulose acetate butyrate (10% ethyl acetate solution) 30 ml Antihalation dye (a) 0.05 g Antihalation dye (b) 0.06 g 0.1 g Color tone adjusting dye (d) 0.002 g Silica matting agent (Syloid 162) 0.1 g Isocyanate (N3300 manufactured by Desmodur Co.) 0.8 g Ethyl acetate 140 ml Coating aid-1 0.1 g

[0110]

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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 and having an absorbance at 810 nm higher than that of a 1.2 polyethylene terephthalate film.

(Preparation of Coated Sample) The prepared coating solution was coated on the opposite side of the polyethylene terephthalate backing layer so that the coated silver amount was 2.0 g / m ² and dried. Thereafter, the coating solution for the surface protective layer 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 The photothermographic material prepared above was processed into a half-cut size, and then imagewise exposed using a semiconductor laser of 810 nm. The angle between the exposed surface of the coated sample and the exposed laser beam is 80d
eg. The output of the laser is 150mW,
However, the signals were superimposed at a high frequency and output in a vertical multi-mode. In the heat development process, uniform heating is performed using a heat drum, and 120 ° C.
× 15 seconds and 125 ° C. × 15 seconds. Then, the fog value at that time was measured. When the maximum concentration of Sample 12 in Table 2 was set to 100, the maximum concentration of each sample was evaluated as a relative value. Table 2 shows the results.

Evaluation of preservability After putting three coated samples in a closed container whose inside was kept at 55% at 25 ° C., it was aged at 50 ° C. for 7 days (forced aging). The second sample among these and a sample for comparison with time (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.

Storage property before exposure: (increase in fog) = (fog after forced aging) − (fogging after comparative aging) Storage property after exposure and heat treatment: 55 ° C. at 25 ° C. after heat development processing
% For 10 days.

(Increase in fog) = (fog after storage for 10 days) − (fog immediately after heat development) Sample 12 is defined as a reference 100 and expressed as a relative value.

Table 2 shows the results.

[0118]

[Table 2]

[0119]

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Table 2 shows that the sample of the present invention has sufficient sensitivity and low fog. Further, it can be seen that the storage stability of the photographic material is also good.

Example 4 A sample was prepared in the same manner as in Example 3. However, sensitizing dye-
2,3 were changed to the following sensitizing dyes-4,5.

[0122]

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The exposure was performed using a 550 nm semiconductor laser.

Table 3 shows the results. 100 based on sample 22
As a relative value.

[0125]

[Table 3]

Table 3 shows that the sample of the present invention has sufficient sensitivity, low fog, high maximum density, and good storage stability.

[0127]

The photothermographic material of the present invention has low fog and good color tone. Also, the storage stability and image storage of the photographic material are good.

Claims (3)

[Claims] 1. A photothermographic material comprising at least one compound represented by the following general formula (1), (2) or (3). Embedded image [Wherein, X represents -SO ₃ M, having at least one -COOM or -OM, heterocyclic formable atomic group. M represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group. However, in the heterocyclic structure, -N
It does not have the partial structure represented by HC (= S)-. [Chemical formula 2] [In the formula, A1 and A1 ′ represent —SO ₃ M, —COOM, or —OM, and M represents a hydrogen atom, a metal atom, a quaternary ammonium group, or a phosphonium group. A1 and A1 'may be the same or different. m represents an integer of 1 to 10. A2 and A2 'represent an electron-withdrawing group, and A2 and A2' may be the same or different. n is 1
Represents an integer of 10 to 10. A3 and A3 'represent a functional group containing a sulfur atom, a selenium atom or a tellurium atom capable of binding to a silver ion, and A3 and A3' may be the same or different. r represents 0 or 1. Y, Y1 and Y2 each represent an aliphatic group, an aromatic group or a heterocyclic group. Z represents a sulfur atom, a selenium atom or a tellurium atom. p is 1 or 2
Represents ] 2. The photothermographic material according to claim 1, further comprising a compound represented by the following general formula (4). Embedded image [In the formula, Q represents an aryl group or a heterocyclic group. X1 and X2 each represent a halogen atom. Y3 is -C
(O) -, - SO- or -SO ₂ - represents a. A represents a hydrogen atom, a halogen atom or an electron-withdrawing group. q is 2-6
Represents an integer. ] 3. The photothermographic material according to claim 1, wherein the photothermographic material is used for laser exposure.