JPH09281640A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce fog and to improve the storage stabilities of the photosensitive material and an image without deteriorating color tone and sensitivity by incorporating a specified compound. SOLUTION: The heat-developable photosensitive material contains at least one of the compounds represented by the formula in which X is a halogen atom; each of R1 -R5 is an alkyl group, (preferably, such as a 1-20C alkyl group, for example, methyl or ethyl group), or an alkenyl, alkynyl, or aryl group, and each may combine with each other to form a ring, such as a cyclopentene or cyclohexene, and a ring condensed with another ring; and X is a halogen atom, such as F, Cl, Br, or I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a technique for improving fog reduction, photosensitive material storability, and image storability without deteriorating sensitivity or color tone.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat. No. 3,152,904.
No. 3457075 and D.C. Morgan and B.A. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials Neblette 8
Edition, Sturge, V. Walworth
th), A. Edited by Shepp, page 2, 1969
Year).

Such a photothermographic material has 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 dispersed in a usual (organic) binder matrix. Contained in. The photothermographic material is stable at room temperature, but at a high temperature (for example, 8
When heated to 0 ° C. or higher), silver is produced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and forms the image. A toning agent for controlling the silver tone of this silver image is optionally used in the light-sensitive material.

The most effective conventional fog prevention technique has been a method using a mercury compound as an antifoggant. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat. No. 3,589,990.
No. 3. However, mercury compounds are not environmentally preferable, and development of a non-mercury antifoggant has been desired. As non-mercury antifoggants, various polyhalogen compounds have hitherto been disclosed (for example, US Pat. No. 3,874,946).
No. 4,452,885, No. 4546075, No. 47
56999, 5340712, and European Patent No. 605.
981A1, 622666A1, 631176
A1, Japanese Patent Publication No. 54-165, Japanese Patent Laid-Open No. 50-371
No. 26, JP-A-7-2781). However, these compounds have problems that the effect of preventing fogging is low and that the color tone of silver is deteriorated. Further, those having a high antifogging effect have problems such as lowering of sensitivity, and thus need to be improved. Further, there is a problem that the fog in the unexposed area increases when exposed and developed after the photosensitive materials are laminated and subjected to forced conditions of humidification and heating, and development of an antifoggant without these problems is desired. It was rare.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material which is free from deterioration in color tone and sensitivity and has reduced fog, storability of photosensitive material and image storability.

[0006]

The above-mentioned objects can be achieved by the following means. (1) A photothermographic material containing at least one compound represented by the following general formula (I). General formula (I)

[0007]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Each represent a hydrogen atom or a substituent. X represents a halogen atom. )

(2) (a) Reducible silver source, (b) photocatalyst, (c) reducing agent, (d) binder and (e) (1)
A photothermographic material containing at least one compound represented by the general formula (I).

(3) (a) an organic silver salt, (b) a photosensitive silver halide and / or a photosensitive silver halide-forming component,
A photothermographic material comprising (c) a reducing agent, (d) a binder, and (e) at least one compound represented by formula (I) described in (1).

(4) The photothermographic material as described in (1), (2) or (3), which is infrared-sensitized for infrared laser exposure.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound represented by formula (I) of the present invention will be explained in detail. R ₁ , R ₂ , R
Examples of the substituent represented by ₃ , R ₄ and R ₅ include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms,
For example, methyl, ethyl, iso-propyl, tert-
Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, such as vinyl, allyl, and 2).
-Butenyl, 3-pentenyl and the like can be mentioned. ), An alkynyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, particularly preferably a carbon number of 2 to 8, and examples thereof include propargyl and 3-pentynyl), and an aryl group (preferably). Has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 carbon atoms.
To 12 such as phenyl, p-methylphenyl,
Examples include naphthyl. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, etc.), aryloxy. A group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy), and an acyl group (preferably). 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 1 carbon atoms.
12 such as acetyl, benzoyl, formyl,
Examples include pivaloyl. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), Aryloxycarbonyl A group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, such as phenyloxycarbonyl), and an acyloxy group (preferably having 2 to 2 carbon atoms). 20, more preferably 2 carbon atoms
-16, particularly preferably 2-10 carbon atoms, such as acetoxy and benzoyloxy. ),
An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, for example, acetylamino, benzoylamino and the like.), An alkoxycarbonylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 1 carbon atoms
6, particularly preferably having 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 2 carbon atoms)
It has 0, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl) Carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.) ), And
Alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms)
And examples thereof include methylthio, ethylthio and the like. ), An arylthio group (preferably having 6 to 20 carbon atoms,
More preferably, it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and particularly preferably having 1 carbon atoms.
To 12, for example, mesyl, tosyl and the like. ), A sulfinyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), Ureido group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoric acid amide and phenylphosphoric acid amide. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, etc.) )). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

The substituent represented by R ₁ is preferably
Alkyl group, aralkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group,
It is a sulfamoyl group, a carbamoyl group, a halogen atom, a cyano group, a nitro group or a heterocyclic group, more preferably an aryl group, a halogen atom, a cyano group, a nitro group or a heterocyclic group, and further preferably a halogen atom.

The substituent represented by R ₂ , R ₃ , R ₄ and R ₅ is preferably an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl. Base,
Acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group,
Ureido group, phosphoric acid amide group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group, more preferably alkyl group, aralkyl group, aryl group , An alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Acyloxy group, halogen atom, cyano group, nitro group,
A heterocyclic group, more preferably an alkyl group, an aryl group, an acyl group, a halogen atom, a cyano group, a nitro group,
A heterocyclic group, particularly preferably an aryl group, a halogen atom or a heterocyclic group.

Further, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are
If possible, they may be linked to form a ring. Examples of the ring formed include cyclopentene, cyclohexene, cyclohexadiene, benzene, and heterocycle (for example, pyrroline, imidazoline, pyrazoline, pyrrole, pyrazole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, furan, thiophene, thiazole, isothiazole, Oxazole, isoxazole, pyran, dihydropyran, etc.), and these rings may form a condensed ring with another ring. R ₁ , R ₂ ,
The ring formed by connecting R ₃ , R ₄ and R ₅ is preferably benzene, pyridine or phthalazine, and more preferably benzene.

R ₁ is particularly preferably a hydrogen atom, a halogen atom or an optionally substituted phenyl group.
Particularly preferred as R ₂ , R ₃ , R ₄ and R ₅ are a hydrogen atom, a halogen atom, an optionally substituted phenyl group and R.
_{This is the case where 2} and R ₃ , and R ₄ and R ₅ are connected to each other to form a benzene ring.

The halogen atom represented by X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom, Particularly preferred is a bromine atom.

Among the compounds represented by the general formula (I), the general formula (Ia), (Ib) or (Ic) is preferable.
It is a compound represented by these. General formula (Ia)

[0019]

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In the formula, X has the same meaning as in formula (I), and the preferred range is also the same. R _a1 ,
R _a2 , R _a3 , R _a4, and R _a5 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or a halogen atom, and the preferred ranges are the same as those in the description of the substituent of the general formula (I). R _a1 is the same as R ₁ and R _{a2 to} R _a5 are the same as those described in R _{2 to} R ₅ . R _a1 , R _a2 , R _a3 , R _a4 and R _a5 are preferably a hydrogen atom, a phenyl group or a halogen atom. General formula (Ib)

[0021]

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In the formula, X has the same meaning as in formula (I), and the preferred range is also the same. R _b1 ,
R _b2 , R _b3 , R _b4 , R _b5 , R _b6 and R _b7 each represent a hydrogen atom or a substituent. The substituents represented by R _{b1 to} R _b7 are the description of the substituent of the general formula (I), where R _b1 is R ₁ ,
R _{b2 to} R _b7 have the same _{meanings as} described for R ₂ , and the preferred ranges are also the same. General formula (I-c)

[0023]

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In the formula, X has the same meaning as in formula (I), and the preferred range is also the same. R _c1 ,
R _c2 , R _c3 , R _c4 , R _c5 , R _c6 , R _c7 , R _c8 and R
_b9 represents a hydrogen atom or a substituent, respectively. R _{c1 to} R _c9
In represented substituent is, R _c1 part of the description of the substituents of general formula (I) R _1, R _c2 ~R _c9 have the same meanings as those mentioned in R _2, also a preferred range is also the same is there.

Among the compounds represented by the general formula (I), more preferred are the compounds represented by the general formula (Ia) or (Ic).

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

[0027]

[Chemical 6]

[0028]

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[0029]

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[0030]

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[0031]

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As the compound represented by the general formula (I) of the present invention, a commercially available compound may be used, and for example, Berich
te der Deuchtschen Chemishen Gesellschaft, vol3
9, 3061 (1906), ibid, vol 41, 3340
(1908), ibid, vol 55, 2302 (1922)
), Ibid, vol 58, 2231 (1925), Journal
of the Chemical Society, vol 87, 1251 (190
5), ibid, vol132, 2358 (1929), Just
us Liebigs Annalen der Chemie, vol445,278,
Vol. 445, 280, Vol. 473, 192, and the like.

Specific examples of the synthesis of the compound represented by formula (I) of the present invention are shown below. Synthesis example. Synthesis of Exemplified Compound 22 15.0 g (0.082 mol) of 9-hydroxyfluorene was dissolved in a minimum amount of glacial acetic acid at 30 to 35 ° C., and an equal amount of a solution of hydrogen bromide in glacial acetic acid ( 600 g /
l) was added dropwise. After completion of the dropwise addition, the mixture was allowed to stand at room temperature overnight, then the precipitated solid was collected by filtration and recrystallized from acetonitrile to obtain 17.2 g (0.070) of the target compound 22.
Mol). Yield 85% Melting point 103 to 105 ° C. The compound represented by the general formula (I) of the present invention can be added in either the photosensitive layer or the non-photosensitive layer. It is preferably a photosensitive layer. The compound represented by the general formula (I) of the present invention may be added in an amount of 10 ⁻⁴ mol to 1 mol / Ag, preferably 10 ⁻³ mol to 0.3 mol / Ag, though it varies depending on the desired purpose. It is preferable that any compound be dissolved in an organic solvent and added.

The photothermographic material of the present invention is preferably a mono-sheet type (a type in which all the materials donated to form an image are completed as an image sheet to be observed) because of its gentleness to the earth. is there. Further, it is preferably a photothermographic material for infrared laser exposure. Further, the infrared laser exposure wavelength is 750 nm or more, more preferably 8
It is preferable that the thickness is 00 nm or more. In order to be compatible with a laser in such a wavelength range, it is necessary to be spectrally sensitized so as to have sensitivity in these wavelength ranges, that is, in the infrared range.
Known infrared spectral sensitizing dyes may be used.

The photothermographic material of the present invention forms a photographic image by using the photothermographic processing method. As such a photothermographic material, as described above, for example, US Pat.
52904, 3457075, and D. Morgan and B. Sh
ely "The Silver System Heat Treated (Thermal
ly Processed Silver Systems) ”(ImagingProces
ses and Materials, Neblette 8th Edition, Sturge, V.Wa
Lworth, edited by A. Shepp, page 2, 1969) and the like.

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

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

The support applicable to the photothermographic material of the present invention includes, for example, paper, polyethylene-coated paper, polypropylene-coated paper, parchment, cloth and the like materials; for example, aluminum, copper, magnesium and zinc. Metal sheaths or thin films; glass or chrome alloys,
Glass coated with metals such as steel, silver, gold, platinum; poly (alkylmethacrylates), (eg poly (methylmethacrylate)), poly (esters)
(Eg, poly (ethylene terephthalate)), poly (vinyl acetals), poly (amides) (eg,
There are synthetic polymeric materials such as nylon) and cellulose esters (eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate). For the photothermographic material of the present invention, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like may be used.

Each binder layer (eg, synthetic polymer) together with the chemical agent in the photothermographic material of the present invention may form a self-supporting film. The support is provided with known auxiliaries such as vinylidene chloride, acrylic acid monomers (eg acrylonitrile or methyl acrylate) and unsaturated dicarboxylic acids (eg itaconic acid, acrylic acid), carboxymethylcellulose, copolymers of poly (acrylamide) and terpolymers. Polymers; and similar polymeric materials may additionally be coated.

Suitable binders are transparent or translucent,
Generally colorless, natural polymers 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 (vinyl). Pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylate), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene) -Butadiene), poly (vinyl acetal) s (eg poly (vinyl formal) and poly (vinyl butyral)), poly (esters),
There are poly (urethane) s, phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate) s, cellulose esters, poly (amides). 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 quinazolines (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides ( For example, N-hydroxy-1,8-naphthalimide); cobalt complex (for example, hexamine trifluoroacetate of cobalt), mercaptans (for example, 3-mercapto-1,2,4-triazole); N
-(Aminomethyl) aryldicarbonoxyimides (eg N- (dimethylaminomethyl) phthalimide); Blocked pyrazoles, isothiuronium derivatives and certain photobleaching combinations (eg N, N '). -Hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
(Combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole); merocyanine dye (for example, 3-ethyl-5-((3-ethyl -2-benzothiazolinyliden
e) -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-phthalazinone); phthalazone; a combination of phthalazinone and a sulfinic acid derivative (eg, 6-chlorophthalazinone + sodium benzenesulfinate) Or 8-methylphthalazinone + sodium p-toluenesulfinate); a combination of phthalazine + phthalic acid; phthalazine (including a phthalazine adduct) and maleic acid, and phthalic acid, 2,3-
Combination with at least one compound selected from naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazo Lysinediones, benzoxazines, naltoxazine derivatives; benzoxazine-2,4-diones (eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg
2,4-dihydroxypyrimidine), and tetrazapentalene derivatives (eg, 3,6-dimercapto-1,4)
-Diphenyl-1H, 4H-2,3a, 5,6a-tetrazapentalene). As a preferable color tone agent,

[0042]

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And more preferably phthalazine. The reducing agent may contain so-called photographic developers such as phenidone, hydroquinones, catechol and the like, but hindered phenol is preferable. A color light-sensitive material as disclosed in U.S. Pat. No. 4,460,681 is also conceivable in the realization of the present invention.

Examples of suitable reducing agents are described in US Pat. No. 3,770.
448, 3773512, 3593863, and Research Disclosure 17029 and 2
9963 and include the following: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, piperidines) as precursors for developers. Nohexose reductone monoacetate); N-hydroxyurea derivative (eg, Np
-Methylphenyl-N-hydroxyurea); aldehyde or ketone hydrazones (eg, anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-). Hydroquinone, isopropylhydroquinone and (2,5-
Dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamideanilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Tetrahydroquinoxaline); amidooxins; azines (for example, aryl carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzene and hydroxylamine combinations, reductones and / or hydrazines; hydroxy acids; azines and sulfones Combination with amidophenols; α-cyanophenylacetic acid derivative; bis-β-naphthol and 1,3-
Combinations of dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1,3-diones; chromanes; 1,4-dihydropyridines (eg 2,6-dimethoxy-3 , 5-dicarboethoxy-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); UV-sensitive ascorbic acid derivatives and 3-pyrazolidones. A preferred reducing agent is a hindered phenol of general formula (A):

[0045]

[Chemical 12]

Where; R ₄ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, —C ₄ H ₉ , 2, 2
4,4-trimethylpentyl), and R ₅ and R _{6 each} represent an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, t-butyl).

A silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, chloroiodobromide). It may be silver or the like), but preferably contains iodide ions. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. The silver halide may be prepared by conversion of the silver soap part by reaction with halogen ions, may be preformed and added at the generation of soap, and combinations of these methods are possible. The latter is preferred.

The reducible silver source can be any material containing a source of reducible silver ions. Silver salts of organic and heteroorganic acids, especially long chains (10-30, preferably 15-25
) Aliphatic carboxylic acids are preferred. Organic or inorganic silver salt complexes in which 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 found in Research Disclosure No. 1
7029 and 29963, and include: salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkyl thiourea salts ( For example, 1
-(3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.);
Silver complexes of polymer reaction products of aldehydes with hydroxy-substituted aromatic carboxylic acids (eg aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (eg salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), a silver salt or complex of thioene (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 a nitric acid selected from benzotriazole with silver; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are stearic acid and silver behenate, with behenic acid being especially preferred. The reducible silver source preferably has a silver amount of 3 g / m ² or less.
It is more preferably 2 g / m ² or less.

The photothermographic material of the present invention includes, for example, JP-A-63-159841, JP-A-60-140335,
No. 63-23147, No. 63-259651, No. 6
3-394242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455 and 4741.
The sensitizing dyes described in Nos. 966, 475117 and 4835096 can be used. General formula (I) of the present invention
The compound represented by can be used in ordinary silver halide light-sensitive materials. For silver halide light-sensitive materials,
Any material may be used as long as it has a photosensitive silver halide emulsion layer on a support.

The present invention will now be described based on examples, but the present invention is not limited thereto.

[0051]

【Example】

Example 1 << Preparation of Photosensitive Emulsion A >> Solution (1) Stearic acid 135 g Behenic acid 635 g Distilled water 13 liters 85 ° C. mixed for 15 minutes Solution (2) NaOH 89 g Distilled water 1500 ml Solution (3) Concentrated HNO ₃ 21 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 the solution (1) was kept warm at 85 ° C., the solution (2) was added over 5 minutes with vigorous stirring, and then the solution (3) was added over 25 minutes. After stirring for 20 minutes as it is, the temperature is lowered to 35 ° C. Solution (4) was added over 5 minutes at 35 ° C. with more vigorous stirring, and 90%
Continue stirring for a minute. Then, the solution (5) was added, the stirring was stopped and the mixture was left to stand, the aqueous layer was removed together with the salt contained therein to obtain an oil layer, and the solvent (6) was added after removing the trace water by desolvation. After stirring vigorously at 0 ° C., 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 μ-thick polyethylene terephthalate support (without an undercoat layer) which was colored blue with the color tone adjusting dye (d). Drying was performed at 75 ° C. for 5 minutes each.

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<Back surface coating> ○ Antihalation layer (wet thickness 80 micron) Polyvinyl butyral (10% isopropanol solution) 150 ml Antihalation dye (a) (0.2% DMF solution) 70 ml

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

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

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Cesitometry The photothermographic material prepared above was processed into half-sized pieces, and a laser diode of 830 nm was cut from the vertical plane to 13 mm.
Exposed with a tilted beam. After that, heat development treatment was performed using a heat drum at 120 ° C. for 15 seconds and 125 ° C. for 15 seconds. Then, the fog value at that time was measured. Further, when the maximum concentration of sample No. 1 in Table 1 was set to 100, the maximum concentration of each sample was evaluated by a relative value. The results are shown in Table 1.

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

Table 1 shows the results.

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[Table 1]

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

Example 2 Preparation of Photosensitive Emulsion B Solution Stearic acid 135 g Behenic acid 635 g Distilled water 13 liters 85 ° C. mixed for 15 minutes Solution A CuBgBrI (I = 4 mol%) preformed 0.06 μ (as Ag) 0.22 mole) distilled water 1250ml solution NaOH 89 g distilled water 1500ml solution of concentrated HNO ₃ 19 ml of distilled water 50ml solution AgNO ₃ 365 g distilled water 2500ml solution polyvinylbutyral 86g ethyl acetate 4300ml solution polyvinylbutyral 290g isopropanol 3580ml

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

A test was conducted in the same manner as in Example 1 (however, the antihalation layer was provided below the photosensitive layer on the side of the photosensitive layer). The sample using the compound of the present invention had low fog as in Example 1. Example 3 << Preparation of Silver Halide Grain A >> 16 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at 35 ° C., followed by silver nitrate 18.
159 ml of an aqueous solution containing 6 g and an aqueous solution containing potassium bromide and potassium iodide (92/8) were added by the control double jet method over 10 minutes while keeping the pAg at 7.7. Then, an aqueous solution 47 containing 55.4 g of silver nitrate
An aqueous solution containing 6 ml and potassium bromide was added over 30 minutes while keeping the pAg at 7.7, and the pH was lowered to cause aggregation and sedimentation for desalting, and then 0.1 g of phenoxyethanol was added to adjust the pH to 7.9 and pAg 8.2. Adjusted silver iodobromide grains A (core 8 mol%, average 2 mol%, 0.05 μ cube, projected diameter area variation coefficient 8%, (100) plane ratio 88
%) Was completed.

The silver halide grain A was heated 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 minute, it was rapidly cooled to 35 ° C. to terminate the chemical sensitization to prepare silver halide grains. The added amount was as follows. Sodium thiosulfate 8.5 × 10 ^-5 mol / silver mol Selenium compound S-1 1.1 × 10 ^-5 mol / silver mol Tellurium compound T-1 1.5 × 10 ^-5 mol / silver mol Chloroauric acid 3 0.5 × 10 ^-6 mol / silver mol Potassium thiocyanate 2.7 × 10 ^-4 mol / silver mol

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<< Preparation of Organic Fatty Acid Silver Emulsion B >> 300 m of water
10.6 g of behenic acid was added to 1 l and dissolved by heating at 90 ° C.,
31.1m of 1N sodium hydroxide with sufficient stirring
1 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 0.01 g of N-bromosuccinimide was added with sufficient stirring.
Was added. Thereafter, 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 left stirring for 1 hour.

While stirring, 37 g of a 1.2 wt% butyl acetate solution of polyvinyl acetate was gradually added to this aqueous mixture to form flocs of the dispersion. After that, the water was removed, and the water was washed twice more. (Washing water conductivity 30μ
S · cm) Next, polyvinyl butyral (molecular weight 300
2.5 cc of 2-butanone solution of 0) (20 cc) was added and stirred at a sufficient speed for 10 minutes. Next, 40 g of 2-butanone and 6.0 g of polyvinyl butyral (molecular weight 4000) were added to the following compounds and stirred at a sufficient speed for 1 hour to complete the preparation of the organic fatty acid silver emulsion B.

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

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

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[Chemical 21]

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

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

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

<< Evaluation of Photographic Performance >> Cesitometry After processing the photothermographic material prepared above into a half-cut size, the FCR7000 manufactured by Fuji Photo Film Co., Ltd. was modified and imagewise exposed using a semiconductor laser of 810 nm. did. The angle between the exposed surface of the coated sample and the exposure laser beam is 80 de
g. Moreover, the output of the laser is 150 mW,
However, high frequency superimposition was performed and output was performed in vertical multi-mode. The heat development is performed by uniformly heating with a heat drum at 120 ° C.
Two types were performed: x15 seconds and 125 ° C x15 seconds. Then, the fog value at that time was measured. Further, when the maximum concentration of sample No. 1 in Table 2 was set to 100, the maximum concentration of each sample was evaluated by a relative value. Table 2 shows the results.

Evaluation of storability As in Example 1, three coated samples were placed in a closed container whose inside was kept at 55% at 25 ° C., and then stored at 50 ° C. for 7 days (forced aging). The second sample of these and the sample for comparison aged (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for evaluation of photographic properties, and the density of the fog portion was measured. (Increase in fog) = (fog during forced aging) − (fog during comparative aging)

The results are shown in Table 2.

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[Table 2]

It can be seen from Table 2 that the sample of the present invention has sufficient sensitivity and low fog as in Example 1.
Further, it can be seen that the storage stability of the light-sensitive material is also good.

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

Claims (4)

[Claims] 1. A photothermographic material comprising at least one compound represented by the following general formula (I). General formula (I) (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent. X represents a halogen atom.) 2. (a) a reducible silver source, (b) a photocatalyst,
A photothermographic material comprising (c) a reducing agent, (d) a binder, and (e) at least one compound represented by the general formula (I) described in claim 1. 3. An organic silver salt (a), (b) a photosensitive silver halide and / or a photosensitive silver halide-forming component, (c) a reducing agent, (d) a binder and (e) the method according to claim 1. A photothermographic material comprising at least one compound represented by formula (I). 4. The photothermographic material according to claim 1, wherein the photothermographic material is infrared-sensitized for infrared laser exposure.