JPH11295846A - Processing method for heat developable photosensitive material and processor therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the change of the surface gloss of a photographic image and to ensure excellent preservability by exposing a specified heat developable photosensitive material and coating it with a soln. contg. a nitrogen-contg heterocyclic compd. hydrobromic salt and a specified compd. SOLUTION: A heat developable photosensitive material contg. photosensitive silver halide particles, a nonphotosensitive reducible silver source, a reducing agent and a binder on the substrate is exposed and coated with a soln. contg. at least one selected from a mercapto compd., a disulfide compd., hydrobromic salt of a nitrogen-contg. heterocyclic compd. with an added bromine atom pair and a compd. represented by the formula or a UV absorbent in an amt. of 1-500 mg/m<2> , preferably 5-100 mg/m<2> . In the formula, Het is a heterocyclic group and X<1> -X<3> are each halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for processing a photothermographic material, and more particularly to a method for processing a photothermographic material which gives an image having excellent gloss stability on a photographic surface, particularly a black and white image. And a processing device.

[0002]

2. Description of the Related Art Conventionally, in the printing plate making and medical fields, waste liquids caused by wet processing of image forming materials have been a problem in terms of workability. Weight loss is strongly desired.

Therefore, there is a need for a technique of a heat-developable silver halide photosensitive material capable of efficiently exposing with a laser image setter or a laser imager and forming a high-resolution and clear black-and-white image. .

The photothermographic material according to the present invention basically contains a photosensitive silver halide, a non-photosensitive reducible silver source, and a reducing agent for the silver source. To form a photographic image.

For details of photothermographic materials, see, for example, US Pat. Nos. 3,152,904 and 3,457,075;
And D. Morgan (Dry Silver Photogr)
aphic Material) "and D.A. Morgan (M
organ) and B.C. "The Silver System Treated by Heat (Thermally)" by Shelly
ProcessedSilverSystems) "
(Imaging Processes and Materials
materials) Neblette Eighth Edition, Sturge, V.A. Walworth
rth), A. Shepp Editing, Page 2,
1969).

[0006]

In general, photographic images are often stored for a long period of time. Particularly, medical diagnostic images are stored for more than 2 years, and in the case of a long time, more than 10 years, and are often observed again. Accordingly, it is desired that the medical diagnostic images obtained from the photothermographic materials have good image storability as well as the conventional silver halide photographic materials using a developing solution.

However, since the photothermographic material contains a photosensitive silver halide, a non-photosensitive reducible silver source, and a reducing agent for the silver source, the photothermographic material is not developed after image formation after exposure. Photosensitive silver halide was susceptible to the phenomenon that the photosensitive silver halide was gradually reduced and blackened during storage due to the presence of a non-photosensitive reducing silver source and a reducing agent. Various improvement measures are being considered.

Further, the photothermographic material tends to change its surface gloss when stored at a high temperature or in a bright room, and the photothermographic material has poor image density and poor contact due to areas where there is no contact on the photographic surface. It may change uniformly, and when the photograph is re-observed after storage, the image quality of the photograph may be degraded.

An object of the present invention is to provide a photographic image obtained by using a photothermographic material, in which the gloss of the surface of the photographic image hardly changes and which has excellent storage stability.

[0010]

The above objects of the present invention have been attained by the following constitutions.

(1) After exposing a photothermographic material containing at least photosensitive silver halide grains, a non-photosensitive reducible silver source, a reducing agent and a binder on a support, a mercapto compound, a disulfide compound, a bromine atom A photothermographic material characterized by applying a liquid containing at least one selected from a nitrogen-containing heterocyclic compound hydrobromide salt to which a pair has been added and a compound represented by the following general formula (1): Processing method.

[0012]

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[Wherein Het represents a heterocyclic group, X ₁ ,
X ₂ and X ₃ each independently represent a halogen atom. (2) After exposure of a photothermographic material containing at least photosensitive silver halide grains, a non-photosensitive reducible silver source, a reducing agent and a binder, a solution containing an ultraviolet absorber is coated on a support. A method for processing a photothermographic material, comprising:

(3) An apparatus for processing a photothermographic material, which is used in the method for processing a photothermographic material in which a liquid is applied after the exposure of the photothermographic material according to the above (1) or (2).

The present invention will be described in more detail. After exposing the photothermographic material containing at least the photosensitive silver halide grains, the non-photosensitive reducible silver source, the reducing agent and the binder on the support, there is no particular limitation on the method of applying the liquid, but The coating amount is preferably in the range of 1 ml to 500 ml per m ² , more preferably in the range of 3 ml to 50 ml.

As a method of applying the liquid, there are an ink jet method, a method of applying the liquid with a roller to which the liquid is adhered or impregnated,
Although there is no particular limitation such as dipping a tank for storing the liquid, an ink jet method is preferable because a small amount of the liquid can be uniformly applied and maintenance is reduced.

A mercapto compound, a disulfide compound, a nitrogen-containing heterocyclic compound to which a bromine atom pair is added, a hydrogen bromide salt of the present invention, which are contained in a solution to be coated after exposure, a general formula (1)
The coating liquid containing the compound represented by the formula (1) or an ultraviolet absorber preferably contains water, various alcohols, methyl ethyl ketone, acetone, toluene, dimethylformaldehyde, ethyl acetate and the like as main components.

The mercapto compound of the present invention, a disulfide compound, a nitrogen-containing heterocyclic compound to which a bromine atom pair has been added, and a hydrogen bromide salt of the general formula (1) to be contained in a solution to be applied after exposure.
Compound or ultraviolet absorber represented in the, 1 m ² per
The range is preferably from mg to 500 mg, preferably from 5 mg to 100 mg.

In the apparatus for exposing and developing the photographic light-sensitive material according to the present invention, a substance such as activated carbon, silica gel or the like which absorbs the evaporation of the coating solution may be incorporated therein. This is effective in preventing deterioration of the indoor environment.

The mercapto compound and the disulfide compound of the present invention to be contained in the solution to be coated after exposure may have any structure, but may be ArSM, Ar-SS
Those represented by -Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, Ar is one or more nitrogen,
A heteroaromatic ring having a sulfur, oxygen, selenium or tellurium atom, or an aromatic ring or a condensed aromatic ring.

The group represented by Ar is preferably a heteroaromatic ring, and includes benzimidazole, naphthoimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole,
Benzoterzole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine,
Examples include pyridine, purine, quinoline or quinazolinone.

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

The mercapto compound used in the present invention includes 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole ,
2,2'-dithiobisbenzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-
2-imidazole thiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole,
2-mercaptoquinoline, 8-mercaptopurine, 2-mercaptopurine
Mercapto-4- (3H) quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-
Tetrachloro-4-pyridinethiol, 4-amino-6
-Hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-
Triazole, 4-hydroxy-2-mercaptopyrimidine, 21-mercaptopyrimidine, 4,6-diamino-
2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-
Examples include 4-phenyloxazole, but the present invention is not limited thereto.

As the disulfide compound used in the present invention, the disulfide form of the above-mentioned mercapto compound or the disulfide form of the aromatic mercapto compound can be mentioned. As the aromatic mercapto compound, the aromatic ring, for example, a benzene ring, a naphthalene ring and the like preferably have a substituent, and examples of the substituent include a halogen atom, a hydroxy group, an amino group, a carboxy group, an alkyl group, and an alkoxy group. Group, carboamide group, sulfamoyl group, sulfamide group and the like. Specifically, 4,
4'-dinonyl diphenyl disulfide, 4,4'-dioctyl sulfamide diphenyl disulfide and the like.

The nitrogen-containing heterocyclic compound hydrobromide having a bromine atom pair used in the present invention includes a compound represented by the following general formula (2).

[0026]

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In the formula, Z represents a 2H-pyrrole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyridazine ring,
Represents a group of atoms forming a pyrrolidone ring, a 2-pyridone ring or a 1-phthalazone ring, and these rings may be substituted with a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an allyl group or the like. Specific examples include pyridinium hydrobromide perbromide, β-picolinium hydrobromide perbromide, and quinolinium hydrobromide perbromide.

In the compound represented by the general formula (1) of the present invention, the heterocyclic group represented by Het is preferably a nitrogen-containing heterocyclic group, and a halogen represented by X ₁ , X ₂ or X _3. The atom is preferably a bromine atom or a chlorine atom. Specific examples of the compound represented by the general formula (1) are shown below.

[0029]

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[0030]

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Next, the ultraviolet absorbent preferably used in the present invention will be described. The ultraviolet absorbent used in the present invention has spectral absorption characteristics in an ultraviolet region (200 to 400 nm).

A preferred compound of the ultraviolet absorber used in the present invention is a benzotriazole compound. The ultraviolet absorbers used may be used alone or in combination of two or more.

The typical basic skeleton of this compound and examples of the compound are shown below.

[0034]

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However, EWG is an electron-withdrawing substituent (for example, cyano group, ester group, amide group, sulfonyl group,
Carbonyl group).

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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The photothermographic material according to the present invention basically contains a photosensitive silver halide, a non-photosensitive reducible silver source (preferably an organic silver salt), and a reducing agent for the silver source. And forming a photographic image using a heat development method. The details of the photothermographic material are disclosed in the above-mentioned known publications, and any photothermographic material can be used.

Among them, the photosensitive material used in the present invention is preferably a photosensitive material which forms an image without performing fixing only by thermal development at a temperature of 80 to 250 ° C. Since the fixing is not performed, the silver halide and the organic silver salt remaining in the unexposed areas remain in the photosensitive material without being removed.

The photosensitive silver salt (silver halide particles) in the present invention functions as an optical sensor. In the present invention, in order to suppress the white turbidity after image formation, and to obtain good image quality, the average particle size is preferably smaller, specifically, the average particle size is preferably 0.1 μm or less,
More preferably 0.01 μm to 0.1 μm, especially 0.0 μm
2 μm to 0.08 μm is preferred. When the silver halide grains are so-called normal crystals having a cubic or octahedral shape, the average grain size refers to the length of the edges of the silver halide grains. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The silver halide grains are preferably monodisperse grains. The monodisperse particles referred to herein are particles having a degree of monodispersity of 40% or less, more preferably 30% or less, particularly preferably 0.1% or more and 20% or less.
% Or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of silver halide grains is cubic, octahedral, tabular, spherical, rod-like, potato-like. In the present invention, cubic grains and tabular grains are particularly preferred. When tabular silver halide grains are used, the average aspect ratio is preferably 2 or more and 10 or more.
It is preferably 0 or less, more preferably 3 or more and 50 or less. These are disclosed in U.S. Patent Nos. 5,264,337 and 5,314,7.
No. 98, No. 5,320,958, etc.,
The desired tabular grains can be easily obtained. Further, grains having rounded corners of silver halide grains can also be preferably used. The outer surface of the silver halide grains is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, more preferably 70% or more, and especially 80% or more. preferable. The ratio of the [100] plane of the Miller index is determined by the T.V. method using the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tani, J .; Imaging Sci. , 29,
165 (1985).

The composition of silver halide 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 P by Glafkids
hysique Photographique (Pa
ul Montel, 1967); F. Du
Photographic Emulsi by fin
on Chemistry (The Focal Pr
ess, 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (The
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. In order to form a solution by reacting a soluble silver salt and a soluble halide, a one-side mixing method, a double-mixing method, a combination thereof and the like are used. Either may be used.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to a non-photosensitive reducible silver source (for example, an organic silver salt).

The silver halide may be prepared by converting part or all of the silver in the organic silver salt to silver halide by reacting the organic silver salt with a halogen ion.
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. Generally, silver halide is 0.75 to 30% by weight based on the organic silver salt.
Is preferably contained in an amount of

The silver halide grains used in the present invention preferably contain a complex of a metal selected from the group consisting of Fe, Co, Ru, Rh, Re, Os, and Ir. May be used in combination of two or more. One of these metal ions or complex ions may be used, or two or more of the same metal and different metals may be used in combination. The content of these metal ions or complex ions is generally from 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol, preferably from 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per mol of silver halide. × 10 ^-4 mol.

It is preferable that the compound which provides these metal ions or complex ions is added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation and growth , Physical aging,
Although it may be added at any stage before and after chemical sensitization, it is particularly preferable to add at the stage of nucleation, growth, and physical ripening,
Further, it is preferably added at the stage of nucleation and growth, most preferably at the stage of nucleation.

In the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added in the form of JP-A-63-29603 and JP-A-2-30.
No. 6236, No. 3-167545, No. 4-76534
No. 6,110-146, 5-273683 and the like, the particles can be contained in the particles with a distribution.

These metal compounds can be added by dissolving 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 particle formation and placed, or a silver salt solution and a halide solution are used. When mixed simultaneously, a third aqueous solution is added 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 halogen is added. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance at the time of preparing 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. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains can be desalted by a known desalting method such as a noodle method, flocculation method, ultrafiltration method, and electrodialysis method.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. Examples of the sensitization method include known methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization, and reduction sensitization. A sensitization method can be used. These sensitization methods can be used in combination of two or more. For sulfur sensitization, thiosulfates, thiourea compounds, inorganic sulfur and the like can be used. Compounds preferably used for selenium sensitization and tellurium sensitization are described in JP-A-9-2.
The compounds described in No. 30527 can be mentioned. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide. As the shell-like compound in the reduction sensitization method, ascorbic acid, thiourea dioxide, stannous chloride, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. 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.

In the photothermographic material of the present invention, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye,
A holopolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure.
Item 17643 IV-A (December 1978, p.
23), Item 1831X (p. Aug. 1978, p.
437) or in the literature cited.

The non-photosensitive reducible silver source of the present invention includes organic silver salts. Silver salts of organic and heteroorganic acids containing reducible silver ion sources, especially long chains (10-3
Silver salts of aliphatic carboxylic acids having 0, preferably 15 to 28 carbon atoms) are preferred. The ligand is 4.0 to 10.0
Organic or inorganic silver salt complexes having a complex stability constant with respect to silver ions are also useful. Examples include: silver salts of organic acids such as gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, oleic acid, caproic acid, myristic acid, maleic acid, linoleic acid, and the like. Salt); a carboxyalkylthiourea salt of silver (eg, 1- (3-carboxypropyl) thiourea,
1- (3-carboxypropyl) -3,3-dimethylthiourea); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid (for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.); Hydroxy-substituted acids (e.g., 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,
Complexes or salts of silver with a nitrogen acid selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptides. Examples of suitable silver salts include Research Disclosure No. 170
29 and 299963, a particularly preferred silver source is silver behenate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but a needle crystal having a short axis and a long axis is preferable. As is well known in photosensitive silver halide photosensitive materials, the inverse relationship between the size of silver salt crystal grains and their covering power also holds in the photothermographic material of the present invention. When the size of the organic silver salt particles as the image forming portion is large, it means that the covering power is small and the image density is low. Therefore, it is necessary to reduce the size of the organic silver salt. In the present invention, the minor axis is 0.01
4 μm or more and 0.20 μm or less, major axis 0.10 μm or more5.
0 μm or less, preferably short axis 0.01 μm or more and 0.15
μm or less, and the major axis is more preferably 0.10 μm or more and 4.0 μm or less. The particle size distribution of the organic silver salt is preferably monodispersed. The monodispersion means that the percentage of the value obtained by dividing the standard deviation of the length of each of the minor axis and major axis by the minor axis and major axis is preferably 100% or less, more preferably 80% or less,
More preferably, it is 50% or less. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method for measuring the monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, and the percentage (coefficient of variation) divided by the volume-weighted average diameter is preferably 100% or less, more preferably Preferably 8
0% or less, more preferably 50% or less. As a measuring method, for example, an organic silver salt dispersed in a liquid is irradiated with a laser beam, and the autocorrelation coefficient with respect to the time change of the fluctuation of the scattered light is obtained from the particle size (volume weight average diameter) obtained. be able to. The coating amount of the organic silver salt, in particular, the organic acid silver in the light-sensitive material of the present invention is preferably 0.3 to 5.0 g, more preferably 0.5 to 5.0 g per m < ² > of the light-sensitive material.
~ 3.0 g is preferred.

Examples of the reducing agent suitable for the photothermographic material of the present invention are described in US Pat. Nos. 3,770,448 and 3,77.
No. 3,512, No. 3,593,863, and Res
Ear Disclosure No. 17029 and 2
9963, and includes the following.

Aminohydroxycycloalkenone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfohydroxamic acid); sulfonamidoanilines (e.g., 4- (N-methane 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (for example, 1,2,3,4-tetrahydroquinoxaline) Amides; azines (for example, a combination of an arylcarboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxanoic acids Combinations of azines and 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 (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, 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.

Binders suitable for the photothermographic material of the present invention 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, and polystyrene. (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), 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 (vinylacetal) s (eg, poly (vinylformal) and poly (vinylbutyral)), poly (ester) Kind, poly ( Urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). It may be hydrophilic or non-hydrophilic.

In the present invention, the amount of binder in the photosensitive layer is 1.5 to 10 for the purpose of preventing dimensional fluctuation after thermal development.
g / m ² . More preferably 1.7
８8 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. The matting agent is preferably contained in a weight ratio of 0.5 to 10% with respect to all binders on the emulsion layer side.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. The shape of the matting agent may be either a fixed shape or an irregular shape, but is preferably a fixed shape, and a spherical shape is preferably used. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere.
In the present invention, the particle diameter 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 matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. The matting agent can be contained in any constituent layer, but is preferably a constituent layer other than the photosensitive layer, and more preferably the outermost layer as viewed from the support.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (for example, 80 ° C. 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.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a 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 as or opposite to the photosensitive layer to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or pigment. . The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

It is preferable to add a color tone agent to the photothermographic material of the present invention. Toning agents are disclosed in US Pat.
0,254, 3,847,612 and 4,
As shown in 123,282, it is a material well known in the photographic art. Examples of suitable toning agents are Research.
h Disclosure No. 17029, which includes:

Imides (for example, phthalimide); cyclic imides, pyrazolin-5-ones and quinazolinones (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2 , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); combinations of blocked pyrazoles, isothiuronium derivatives and certain photobleaches (eg, N, N'-hexamethylene (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 (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 + benzenesulfin) Acid sodium salt or 8-methylphthalazinone + p-
Sodium trisulfonate); phthalazine + phthalic acid combination; phthalazine (including phthalazine adducts)
And maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) Quinazolinediones, benzoxazines, naltoxazine derivatives; benzoxazine-2,4-diones (for example,
1,3-benzoxazine-2,4-dione); 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). Preferred toning agents are phthalazone or phthalazine.

In the present invention, known inhibitors such as mercapto compounds and disulfide compounds are used to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. Can be contained.

What is known as the most effective antifoggant is mercury ion. The use of a mercury compound as an antifoggant in a light-sensitive material is disclosed in, for example, US Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly. Examples of the non-mercury antifoggant include U.S. Pat. Nos. 4,546,075 and 4,452,885 and JP-A-59-572.
No. 34 is preferred.

Particularly preferred non-mercury antifoggants are described in US Pat. Nos. 3,874,946 and 4,756,99.
No. 9 heterocyclic compounds.

In the photosensitive layer according to the present invention, a polyhydric alcohol (for example, US Pat.
Glycerin and diols of the type described in U.S. Pat. Nos. 60,404), U.S. Pat.
Fatty acids or esters described in U.S. Pat. No. 121,060 and silicone resins described in British Patent No. 955,061 can be used.

A hardener may be used for each layer such as the photosensitive layer, the protective layer and the back layer of the present invention. Examples of hardeners include isocyanate compounds, US Pat. No. 4,791,042.
Epoxy compounds described in JP-A No.
For example, vinyl sulfone compounds described in JP-A-89048 and the like can be used.

In the present invention, a surfactant may be used for the purpose of improving coating properties and charging. As an example of the surfactant, any of anionic, cationic, betaine, nonionic, and fluorine-based surfactants can be appropriately used. Specifically, fluoropolymer surfactants described in JP-A-62-170950, JP-A-60-244945,
Fluorinated surfactants described in JP-A-63-188135, polysiloxane-based surfactants described in U.S. Pat. No. 3,885,965, JP-A-6-301140
And polyalkylene oxides and anionic surfactants.

The photographic emulsion for thermal development in the present invention can be applied by various coating methods including a dip coating method, an air knife coating method, a flow coating method, and an extrusion coating method using a hopper. If necessary, two or more layers can be applied simultaneously.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) in order to obtain a predetermined optical density after development and to prevent image deformation after development. , Polyethylene naphthalate).

Among them, preferred supports include plastics containing polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene naphthalate (hereinafter abbreviated as PEN), and a styrene polymer having a syndiotactic structure (hereinafter abbreviated as SPS). Support.
The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

A plastic support which has been heat-treated can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is applied, at a temperature higher than the glass transition point of the support by 30 ° C. or more,
Preferably at a temperature higher than 35 ° C., more preferably 40 ° C.
It is preferable to heat at a temperature higher than ℃. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

For the method of forming a support and the method of producing an undercoat according to the present invention, known methods can be used, but preferably, paragraphs [0030] to [0] of JP-A-9-50094 are used.
070].

According to the image recording method of the present invention, the above-mentioned photothermographic material is written by exposure for 10 ^-2 seconds or less (hereinafter, referred to as short exposure if necessary), and the developing temperature is from 80 ° C. to 250 ° C.
It is preferred to heat at a temperature of not more than ° C.

As the light source for short exposure, a glow lamp, a xenon lamp, a mercury lamp, a light emitting diode, He-N
e laser, argon laser, He-Cd laser,
Although a semiconductor laser is mentioned, a laser beam is preferable.

As an example of a method for making short exposure, He-N
With gas lasers such as e-lasers, short exposures of 10 ^-2 seconds or less can be achieved by passing the laser light through an optical component such as an AO modulator that acts as a shutter. In addition, since the semiconductor laser itself has an ON-OFF function, short exposure can be easily achieved.

In the present invention, the sensitivity is significantly improved by short exposure of 10 ⁻² seconds or less, preferably 10 ^{−9 to} 10 ⁻⁵ seconds.

The developing method may be any type as long as it is heat development, and the heating means may be heating between a hot plate or contact with the hot plate (see, for example, JP-A-50-62635), a hot drum, a hot roller, (For example, see Japanese Patent Publication No. 43-10791), heating by passing through hot air (for example, see Japanese Patent Application Laid-Open No. 53-32737),
Heating by passing through an inert liquid maintained at a constant temperature, or heating by passing along a heat source by a roller, belt or guide member (for example, Japanese Patent Publication No. 44-25 / 1972)
No. 46) can be used.

The heating temperature is not lower than 80 ° C. and not higher than 250 ° C. If it is lower than 80 ° C., an image cannot be formed.
When the temperature exceeds 0 ° C., fogging of an image is extremely impractical.
A preferable selection range of the heating temperature is 100 ° C to 200 ° C.

FIG. 1 is a schematic view of a photothermographic material processing apparatus of the present invention. In FIG. 1, the photothermographic material stored in a film cartridge 1 is taken out one by one by a film transport device 2, enters a film transport unit 3, is transported in the direction of arrow 4, and is further transported to an exposure unit 5. Can be The film is vacuum-adsorbed in the exposure section 5 as shown by a dotted line, and then is exposed from a laser imager equipped with a semiconductor laser, enters the film transport section again, and the arrow 6
And is thermally developed by the thermal development unit 8. The thermally developed film is coated with a stabilizer or the like by an ink jet nozzle 9, checked for density by a densitometer 10, and then stocked on a receiving tray 11. If the density is extremely high or low, it is fed back to the exposure unit 5 and is exposed to an appropriate density. The solvent such as a stabilizer applied by the inkjet nozzle 9 is adsorbed by the activated carbon deodorizing device 7 and does not go out of the exposure device.

[0089]

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

Example 1 Preparation of Subbed Photographic Support <Preparation of PET Subbed Photographic Support> A commercially available biaxially stretched heat-fixed PET film having a thickness of 100 μm was coated on both sides with 8 w / m ^2. For one minute, and apply the following undercoating coating solution a-1 on one surface so as to have a dry film thickness of 0.8 μm, and dry to form an undercoating layer A-1. The following undercoating coating solution b-1 was applied so as to have a dry film thickness of 0.8 μm, and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) Copolymer latex liquid of 2-hydroxyethyl acrylate (25% by weight) (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.

<< Undercoat Coating Solution b-1 >> Butyl acrylate (40% by weight) Styrene (20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Make up 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 Subbing Upper Layer >> Gelatin 0.4 g / m ² Weight (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 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.

[0096]

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[0097]

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

(Preparation of Photosensitive Silver Halide Emulsion A) Water 9
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 00 ml and adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and (98%) were added.
/ 2) An aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 2/2) and the above-mentioned iridium compound (26) in a controlled double jet method while maintaining 1 × 10 ⁻⁶ mol per mol of silver at a pAg of 7.7. Added over 10 minutes. Thereafter, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazindene 0.3 g was added, and the pH was adjusted to 5 with NaOH to obtain a cubic iodobromide having an average grain size of 0.06 μm, a variation coefficient of the projected diameter area of 8%, and a [100] face ratio of 87%. Silver particles were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 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.

Next, 5.0 × 10 ⁻⁵ mol / mol Ag of 1-ethyl, 3- (2-thiazolyl) thiourea was added as a sulfur sensitizer to this silver halide emulsion, and chloroauric acid was further added. 1.0 × 10 ⁻⁶ mol / mol Ag was added and reacted at 55 ° C. for 60 minutes to perform compound sensitization. Thereafter, the temperature of the silver halide emulsion was lowered to room temperature, and then an additive such as an antifoggant described below was added to prepare a photosensitive silver halide emulsion.

(Preparation of Silver Behenate) Preparation of Na Behenate Solution 34 g of behenic acid was added to 340 ml of isopropanol for 65 days.
Dissolved at ° C. Next, while stirring, a 0.25N aqueous sodium hydroxide solution was added so as to have a pH of 8.7. At this time, about 400 ml of the sodium hydroxide aqueous solution was required.
Next, the aqueous sodium behenate solution was concentrated under reduced pressure to adjust the concentration of sodium behenate to 8.9% by weight.

Preparation of Silver Behenate A 2.94 M silver nitrate solution was added to a solution of 30 g of ossein gelatin dissolved in 750 ml of distilled water, and the silver potential was adjusted to 4%.
00 mV. To this, 374 ml of the above sodium behenate solution was added at a speed of 44.6 ml / min at a temperature of 78 ° C. by using a controlled double jet method, and simultaneously a 2.94 M silver nitrate aqueous solution was supplied with a silver potential of 400 mV.
It was added so that it became. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.092 mol and 0.101 mol, respectively.
Mole. After the addition was completed, the mixture was further stirred for 30 minutes, and the water-soluble salts were removed by ultrafiltration.

Preparation of Photosensitive Emulsion To this silver behenate dispersion, 0.01 mol of the above-described photosensitive silver halide emulsion was added, and 100 g of a solution of polyvinyl acetate in n-butyl acetate (1.2 wt%) was further stirred.
Is gradually added to form a floc of the dispersion, water is removed, water is further washed twice and water is removed, and polyvinyl butyral (average molecular weight 3000) is used as a binder.
60 g of a 1: 2 mixed solution of 2.5 wt% of butyl acetate and isopropyl alcohol was added with stirring, and polyvinyl butyral (average molecular weight 4000) as a binder was added to the thus obtained mixture of behenic acid and silver halide. ) And isopropyl alcohol. The following layers were sequentially formed on a PET support to prepare a sample. The drying was performed at 75 ° C. for 5 minutes.

Back side coating: A solution having the following composition was applied to a wet thickness of 80 μm.

Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-B 70 mg Dye-C 70 mg

[0106]

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Photosensitive layer surface side coating Photosensitive layer: A solution having the following composition was applied.
m ² , polyvinyl butyral as a binder.
The coating was performed so as to be 5 g / m ² .

Photosensitive Silver Halide Emulsion A Amount of 3 g / m ² in terms of silver sensitizing dye-1 (0.1% DMF solution) 2 mg Antifoggant-1 (0.01% methanol solution) 3 ml Antifogging Agent-2 (1.5% methanol solution) 8 ml Antifoggant-3 (2.4% DMF solution) 5 ml Phthalazone (4.5% DMF solution) 8 ml Developer-1 (10% acetone solution) 13 ml Hardening agent H (1% methanol / DMF = 4: 1 solution) 2 ml

[0109]

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[0110]

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Surface protective layer: A solution having the following composition was wetted to a thickness of 1
It was applied on each photosensitive layer so as to have a thickness of 00 μm.

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 0.5 g matting agent (average particle size 4 μm 2g << Evaluation of Performance >> The above sample was prepared with a short side of 356 mm and a long side of 43 mm.
The sheet was cut into a 2 mm sheet, and in the exposure unit 5 using the apparatus shown in FIG. 1, grayscale exposure was performed using a laser imager equipped with a 760 nm semiconductor laser to provide 30 levels of density gradation from the fog to the highest density. After that, in the heat developing section 8, the sample subjected to the heat development processing at 130 ° C. for 12 seconds, and the ink jet method following the heat development processing,
The coating solutions shown in Table 1 were applied. Each coating solution was applied in an amount of 12 ml per 1 m ² by a method of multiple application using three inkjet nozzles 9 to obtain Samples 0 to 10 shown in Table 2.

[0113]

[Table 1]

In each of the obtained samples, the concentration of each gray scale was within the range of plus and minus 0.03.
Practical photographic performance was obtained.

Using a 40 W straight tube fluorescent lamp, a change in the glossiness of the developed sample surface due to the fluorescent lamp light exposure was confirmed. Place the developed sample on a white paper-covered desk in an environment of 23 ° C. and 55%, set the distance from the center of the sample to the fluorescent lamp to 20 cm, and irradiate the fluorescent light for 200 hours continuously to shine the surface. And the results of ranking as described below are shown in Table 2.

A: There is no difference in gloss between the center and the periphery of the sample. B: The difference in gloss is very small between the center and the periphery of the sample, and there is no sense of incongruity in photographic observation. C: Difference in gloss between the center and the periphery of the sample. D: The difference in gloss between the center and the periphery of the sample is large, and the photographic observation feels strange.

[0117]

[Table 2]

As shown in Table 2, it can be seen that the sample of the present invention has a small change in surface gloss and does not hinder the observation of a photographic image.

[0119]

According to the present invention, it has been possible to provide a photographic image obtained from a photothermographic material, in which the gloss of the surface of the photographic image hardly changes and which has excellent storage stability.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus for processing a photothermographic material according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Film cartridge 2 Film conveyance device 3 Film conveyance part 5 Exposure part 7 Activated carbon deodorizing device 8 Thermal development part 9 Inkjet nozzle 10 Densitometer 11 Receive tray

Claims (3)

[Claims] 1. A photothermographic material comprising at least a photosensitive silver halide grain, a non-photosensitive reducible silver source, a reducing agent and a binder on a support, after exposure, a mercapto compound, a disulfide compound and a bromine atom pair. Processing of a photothermographic material characterized by applying a solution containing a nitrogen-containing heterocyclic compound hydrobromide added with a compound represented by the formula (1) and at least one compound selected from the compounds represented by the following general formula (1): Method. Embedded image [Wherein, Het represents a heterocyclic group, and X ₁ , X ₂ , and X ₃ each independently represent a halogen atom. ] 2. A photothermographic material containing at least photosensitive silver halide grains, a non-photosensitive reducible silver source, a reducing agent and a binder is exposed on a support, and then a solution containing an ultraviolet absorber is applied. A method for processing a photothermographic material. 3. An apparatus for processing a photothermographic material, which is used in the method for processing a photothermographic material according to claim 1 or 2, wherein a liquid is applied after the photothermographic material is exposed.