JP2001092098A - Method for processing heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problems of uneven development, low image reproducibility and transport failure due to a change of heat transfer coefficient and the inflow of air when a heat developable photosensitive material is processed. SOLUTION: A heat developable photosensitive material containing photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrast enhancer and a binder is processed with a heat developing device in which the void ratio (the ratio of the internal void volume (cm3) of a heating part to the internal volume (cm3) of the heating part) is in the range of 0.002-0.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a photothermographic material in which the problems of uneven development, image reproducibility, and poor conveyance due to a change in heat transfer coefficient or air flow are improved.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquids caused by wet processing of image forming materials have become a problem in terms of workability. Weight loss is strongly desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image. As this technique, for example, US Pat. Nos. 3,152,904 and 3,487,075
And D. "Dry Silver Photog" by Morgan
graphic Materials) "(Handbo
ok of Imaging Materials, M
arcelDekker, Inc. 48, 199
As described in 1) etc., an organic silver salt on a support,
Thermal developing materials containing photosensitive silver halide grains, a reducing agent and a binder are known.

[0003] These heat-developable materials are stable at room temperature, but are developed by heating to a high temperature (for example, 80 ° C to 140 ° C) after exposure. That is, heating produces silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent.

As a conventional automatic thermal developing machine for thermal development, Japanese Patent Application Laid-Open No. 08-211547 discloses a heat-developed image forming method for developing at 100 to 150 ° C.
No. 95 has a medical image with a heating temperature of 120 ± 10 ° C., ±
Methods of processing with a 3 ° C. width accuracy and a development time of 5 to 30 seconds, respectively, are disclosed. JP-A-09-297
Nos. 386, 09-297385 and 09-2973
No. 84 discloses a method for controlling the outer peripheral surface temperature of a heater drum. Japanese Patent Publication No. 10-500496 discloses a method of developing by heating a drum.
No. 497 describes a method of heating and developing with multiple rollers.
No. 10-500506 discloses a device for controlling the temperature of an electrically heated rotatable drum and a device for detecting the temperature of the surface of a cylindrical drum and outputting a temperature signal.

[0005]

A photothermographic material containing a high contrast agent such as a hydrazine derivative or a quaternary onium salt is exposed to light when there is a delicate flow of air in the heat development section of a heat development processor. There is a problem in that the heat transfer coefficient of the material itself changes, causing uneven development and a large change in image reproducibility. If the porosity of the heating section of the heat development processing apparatus is large, air often flows into the heating section, and the leading end of the film or the like becomes violent, which often causes transport failure.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object the object of processing a photothermographic material by developing unevenness, image reproducibility, and the like due to a change in heat transfer coefficient and air flow. An object of the present invention is to solve the problem of poor conveyance.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder. The porosity in the part (= void volume in heating part (cm ³ ) / volume in heating part (cm ³ )) is 0.
A method for processing a photothermographic material using a photothermographic processing apparatus having a range of 002 to 0.3, a temperature of a heating section of the photothermographic processing apparatus being in a range of 100 ° C to 150 ° C; In processing a photothermographic material containing an organic silver salt, a reducing agent for silver ions, a contrast agent, and a binder, a developing section having a temperature in the range of 110 ° C. to 150 ° C. and a temperature lower by 5 ° C. or more than the temperature of the developing section. A method for processing a photothermographic material using a thermal development processing apparatus having a preheating section in a temperature range, wherein the porosity in the developing section is 0.006 to less than the porosity in the heating section having the developing section and the preheating section.
1.8, when processing a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrast agent, and a binder, the porosity in the developing part (= development of the void volume (cm ³⁾ / volume of the heat developing section (cm ³⁾⁾ is processing method of a photothermographic material using the thermal development apparatus is in the range of 0.002 to 0.5, thermal development apparatus The temperature of the developing section is in the range of 110 ° C. to 150 ° C., the pre-heating section having a temperature lower than the developing section temperature by 5 ° C. or more before the developing section of the thermal development processing apparatus, photosensitive silver halide, organic silver salt In processing a photothermographic material containing a reducing agent for silver ions, a contrast agent and a binder, the distance between the surface of the photothermographic material conveyed into the heating section and the heating member facing the same is 0 to 1.8 cm.
A method for processing a photothermographic material using a photothermographic processing apparatus which is in the range of: In processing a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrast agent and a binder, A processing method of a photothermographic material using a photothermographic processing apparatus in which a distance between a conveying member and a heating member in the developing unit is in a range of 0 to 1.8 cm;
In the above, it is a thermal development processing apparatus that transports in a plane, and the thickness of the support of the thermal development photosensitive material is 110 to 150 μm.
Is achieved.

That is, the inventor of the present invention intends to solve the problems of development unevenness, image reproducibility, and poor transport due to a change in heat transfer coefficient and air flow by setting the porosity of the heating section of the heat development processing apparatus. The present invention was found to be more effective if the development was carried out through preheating.

In the present invention, the heating section refers to a section heated to a temperature of 30 ° C. or higher by a heating member, and includes a preheating section and a developing section. The developing unit is the maximum density (Dm) measured with an optical densitometer (manufactured by Konica Corporation, PDA-65) when the exposed photosensitive material is inserted and processed for 10 seconds.
ax) is a heating part where the temperature is 0.4 or more, and it is preferable that the temperature of the central part is a part heated to a temperature in the range of 100 to 150 ° C. by the heating member. In addition, since there is a difference in temperature between the developing unit and the preheating unit, it is preferable that each room is divided by a sill, a member, or the like. In addition, the preheat section
A heating unit in which the maximum density measured by an optical densitometer (described above) is 0.39 or less when the exposed photosensitive material is inserted and processed for 10 seconds.

Hereinafter, the present invention will be described in detail for each item.

<< Photothermographic Material >> Silver halide functions as an optical sensor. The smaller the average particle size is, the smaller the particle size is, preferably 0.1 μm or less, and more preferably 0.1 μm or less.
01 μm to 0.1 μm, especially 0.02 μm to 0.08 μ
m is preferred. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. 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. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. More preferably, 30
Or less, particularly preferably 0.1 to 20 particles.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is high. It is preferable that this ratio is 50% or more, further 70% or more,
In particular, it is preferably at least 80%. Another preferred form of silver halide is tabular grains. As used herein, the term “tabular grain” refers to an aspect ratio = r where the square root of the projected area is a particle diameter of r μm and the thickness in the vertical direction is h μm.
/ H means 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or less. The particle size is 0.1μ
m, preferably 0.01 μm or less.
0.08 μm is preferred.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion may be prepared by any method such as an acid method, a neutral method, and an ammonia method, and the method of reacting a soluble silver salt and a soluble halide salt includes a one-side mixing method, a simultaneous mixing method, and the like. May be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source.
Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

The photosensitive silver halide grains can be desalted by washing with water using a method known in the art such as a noodle method or flocculation method. The photosensitive silver halide grains are preferably chemically sensitized. Preferred chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization, as is well known in the art. Sensitization can be used.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid or a heteroorganic acid containing a reducible silver ion source, especially a long chain (10 to 30, preferably 15 to 25) And the nitrogen-containing heterocycle is preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are Research
h Disclosure Nos. 17029 and 29963
It is described in. Preferred silver sources are silver behenate, silver arachidate and silver stearate.

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 includes a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method disclosed in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used.

The average particle size of the organic silver particles is 0.2 to 1.2 μm.
m, more preferably 0.35 to
1 μm. The organic silver particles are preferably monodispersed, and preferably have a monodispersity of 1 to 30.

In order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably 0.5 g to 2.2 g per m ² in terms of silver.

Examples of suitable reducing agents are described in US Pat.
No. 0,448, No. 3,773,512, No. 3,5
No. 93,863 and Research Disclo
Sure Nos. 17029 and 29996. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0021]

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In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, t- butyl ).

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

[0024]

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[0025]

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The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

The photothermographic material of the present invention contains a high contrast agent, and the high contrast agent is preferably selected from the following hydrazine derivatives, quaternary onium salts, and vinyl compounds.

As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0029]

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In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group, each of which may have a substituent;
B ₀ represents a blocking group, and A ₁ and A ₂ each represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. Here, G ₀ is -CO-
Group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )
— Group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D
₁ ) represents a group, G ₁ represents a mere bond, an —O— group, —S—
Group or -N (D ₁₎ - represents a group, D ₁ is an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

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

Particularly preferred as A ₀ are an aryl group and a -G ₀ -D ₀ group.

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

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, and 64-9
No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably a -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
A preferred G ₀ representing a (G ₁ D ₁ ) — group is —CO—
Group, -COCO- group, G ₁ is a mere bond,
—O—, —S— or —N (D ₁ ) —, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D ₁ are present in the molecule If so, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or an oxalyl group (Such as an ethoxalyl group).

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

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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More preferred hydrazine derivatives are represented by the following formulas (H-1), (H-2), (H-3) and (H-4)
Or a compound represented by (H-5).

[0045]

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In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ₁₄ represents a heterocyclic oxy group or a heteroarylthio group. A ₁ and A ₂ both represent a hydrogen atom or one is a hydrogen atom and the other is an acyl group, an alkylsulfonyl group or an oxalyl group.

[0047]

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In the formula, R ₂₁ represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. R ₂₂ represents hydrogen, an alkylamino group, an arylamino group, or a heteroarylamino group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0049]

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In the formula, G ₃₁ and G _{32 each} represent a — (CO) p- group,
C (= S)-group, sulfonyl group, sulfoxy group, -P
(＝ O) represents an R ₃₃ — group or an iminomethylene group, and p is 1
Or an integer of 2, and R ₃₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or an amino group. However, when G ₃₁ is a sulfonyl group, G ₃₂ is not a carbonyl group. R ₃₁ and R ₃₂ represent a monovalent substituent. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0051]

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In the formula, R ₄₁ , R ₄₂ and R ₄₃ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ₄₄ and R ₄₅ represent a substituted or unsubstituted alkyl group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0053]

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In the formula, R ₅₁ is an alkyl group, alkenyl group, alkynyl group, aralkyl group, heterocyclic group, substituted amino group, alkylamino group, arylamino group, heterocyclic amino group, hydrazino group, alkoxy group, aryl group Oxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group, heterocyclic thiocarbonyl group, carbamoyl A carbamoyloxy group, a carbamoylthio group, a carbazoyl group, an oxalyl group, an oxamoyl group, an alkoxyureido group, an aryloxyureido group, or a heterocyclic oxyureido group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

In the general formula (H-1), the aryl group represented by R ₁₁ , R ₁₂ and R ₁₃ is a phenyl group,
Examples include a methylphenyl group and a naphthyl group, and examples of the heteroaryl group include a triazole residue, an imidazole residue, a pyridine residue, a furan residue, and a thiophene residue. Further, R ₁₁ , R ₁₂ and R ₁₃ may be bonded via an arbitrary linking group. Examples of the substituent which R ₁₁ , R ₁₂ and R ₁₃ may have include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (a pyridinio group) Etc.), a hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a urethane group, Carboxyl group, imide group, amino group, carboxamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Primary ammonium group, (alkyl, aryl or heterocycle)
Thio, mercapto, (alkyl or aryl) sulfonyl, (alkyl or aryl) sulfinyl,
A sulfo group, a sulfamoyl group, an acylsulfamoyl group, an (alkyl or aryl) sulfonyluureido group,
(Alkyl or aryl) sulfonylcarbamoyl group,
Examples include a halogen atom, a cyano group, a nitro group, and a phosphoric amide group. All of R ₁₁ , R ₁₂ and R ₁₃ are preferably phenyl groups, and more preferably all are unsubstituted phenyl groups.

The heteroaryloxy group represented by R ₁₄ includes a pyridyloxy group, an indolyloxy group, a benzothiazolyloxy group, a benzimidazolyloxy group,
A furyloxy group, a thienyloxy group, a pyrazolyloxy group, an imidazolyloxy group, and the like.Examples of the heteroarylthio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, Examples include a thienylthio group, a pyrazolylthio group, and an imidazolylthio group. R ₁₄ is preferably a pyridyloxy group or a thienyloxy group.

As the acyl group represented by A ₁ or A ₂ ,
Examples include an acetyl group, a trifluoroacetyl group, and a benzoyl group. Examples of the sulfonyl group include a methanesulfonyl group and a toluenesulfonyl group. Examples of the oxalyl group include an ethoxalyl group. Both A ₁ and A ₂ are preferably hydrogen atoms.

In the general formula (H-2), examples of the alkyl group represented by R ₂₁ include a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group and a diphenylmethyl group. And an aryl group, a heteroaryl group, and a substituent which may be present include R
₁₁ is the same as R ₁₂ and R _13. R ₂₁ is preferably an aryl group or a heteroaryl group, and particularly preferably a phenyl group. The alkylamino group represented by R _22, methylamino group, ethylamino group, propylamino group, butylamino group, dimethylamino group, diethylamino group, etc. ethylmethylamino group. Examples of the arylamino group anilino Examples of the group and heteroaryl group include a thiazolylamino group, a benzimidazolylamino group, and a benzthiazolylamino group. Preferably the R ₂₂ is dimethylamino group or diethylamino group.

In formula (H-3), monovalent substituents represented by R ₃₁ and R ₃₂ include R ₁₁ , R ₁₂ and R ₁₃ described in formula (H-1). The substituents may be the same as those described above, but are preferably an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or an amino group, more preferably an aryl group or an alkoxy group, and particularly preferably R ₃₁ is a phenyl group. Wherein _R32 is a tert-butoxycarbonyl group. G ₃₁ and G ₃₂ are preferably -CO-
Group, a -COCO- group, a sulfonyl group or a -CS- group, and more preferably, both are a -CO- group or a sulfonyl group.

In formula (H-4), R ₄₁ , R ₄₂ and R ₄₃ are the same as R ₁₁ , R ₁₂ and R ₁₃ in formula (H-1).
Is synonymous with Preferably, all are phenyl groups, and all are unsubstituted phenyl groups. R ₄₄ , R ₄₅
Examples of the substituted or unsubstituted alkyl group represented by are a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group, a diphenylmethyl group, and the like. Is the case.

Specific examples of the compounds represented by formulas (H-1) to (H-5) are shown below, but the invention is not limited thereto.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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

The layer to which the hydrazine derivative and the vinyl compound described below are added is a photosensitive layer containing silver halide and / or a layer adjacent to the photosensitive layer. The optimum amount of these additives is not uniform depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is preferably 10 ⁻⁶ mol to 10 mol per mol of silver halide. ^-1 mol, especially 1
The range is preferably from 0 ^-5 mol to 10 ^-2 mol.

As the quaternary onium compound, a compound represented by the following formula (P) is preferably used.

[0079]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Incidentally, R _{1 to} R ₄ may be connected to each other to form a ring.

In the general formula (P), substituents represented by R _{1 to} R ₄ include alkyl groups (methyl group, ethyl group,
Propyl group, butyl group, hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (Piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), amino group and the like.

The ring which may be formed by connecting R _{1 to} R ₄ to each other includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are a hydroxyl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0087]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

B _P represents a divalent linking group, m is 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0092] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0093]

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value at the phenyl group has been reported in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, and
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Specific examples of the quaternary onium compound are shown below, but it should not be construed that the invention is limited thereto.

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound is described in Chemical Reviews vol. 55
p. 335-483 can be referred to.

The addition amount of these quaternary onium compounds is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver halide. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

The quaternary onium compound can be used alone or
More than one species may be used in combination. The compound may be added to any of the constituent layers of the photosensitive material, but is preferably added to at least one of the constituent layers on the side having the photosensitive layer, further to the photosensitive layer and / or an adjacent layer thereof.

As the vinyl compound, those represented by the following general formula (G) are preferred.

[0112]

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In the general formula (G), X and R are represented in the form of cis. However, the general formula (G) also includes a trans form of X and R. This is the same in the structural representation of a specific compound.

In the formula, X represents an electron-withdrawing group, and W is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an acyl group, a thioacyl group, an oxalyl group, an oxyoxalyl group. Group, thiooxalyl group, oxamoyl group, oxycarbonyl group, thiocarbonyl group, carbamoyl group, thiocarbamoyl group,
Sulfonyl group, sulfinyl group, oxysulfinyl group, thiosulfinyl group, sulfamoyl group, oxysulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, dicyanoethylene group, ammonium Group, sulfonium group, phosphonium group, pyrylium group,
Represents an immonium group.

R represents a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkenyloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aminocarbonyloxy group, a mercapto group,
Organic or inorganic salts of an alkylthio group, an arylthio group, a heterocyclic thio group, an alkenylthio group, an acylthio group, an alkoxycarbonylthio group, an aminocarbonylthio group, a hydroxy group or a mercapto group (for example, sodium salt, potassium salt, silver salt) Etc.), an amino group, an alkylamino group, a cyclic amino group (for example, a pyrrolidino group), an acylamino group, an oxycarbonylamino group, a heterocyclic group (5-
A 6-membered nitrogen-containing heterocycle, for example, a benztriazolyl group,
Imidazolyl group, triazolyl group, tetrazolyl group, etc.), ureido group, and sulfonamide group. X and W,
X and R may be bonded to each other to form a cyclic structure. Examples of the ring formed by X and W include pyrazolone, pyrazolidinone, cyclopentanedione, β-ketolactone, β-ketolactam and the like.

The general formula (G) will be further described.
Is a substituent whose Hammett's substituent constant σp can take a positive value. Specifically, a substituted alkyl group (eg, halogen-substituted alkyl), a substituted alkenyl group (eg, cyanovinyl), a substituted / unsubstituted alkynyl group (eg, trifluoromethylacetylenyl, cyanoacetylenyl), and a substituted aryl group (eg, cyanovinyl) Phenyl, etc.), substituted / unsubstituted heterocyclic groups (pyridyl, triazinyl, benzoxazolyl, etc.), halogen atoms, cyano groups, acyl groups (acetyl, trifluoroacetyl, formyl, etc.),
Thioacetyl group (thioacetyl, thioformyl, etc.), oxalyl group (methyloxalyl, etc.), oxyoxalyl group (ethoxalyl, etc.), thiooxalyl group (ethylthiooxalyl, etc.), oxamoyl group (methyloxamoyl, etc.), oxycarbonyl group (ethoxycarbonyl, etc.) etc),
Carboxyl group, thiocarbonyl group (such as ethylthiocarbonyl), carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group (such as ethoxysulfonyl), thiosulfonyl group (such as ethylthiosulfonyl), sulfamoyl group, and oxysulfinyl Group (such as methoxysulfinyl), thiosulfinyl group (such as methylthiosulfinyl), sulfinamoyl group,
Sphinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group (N-acetylimino, etc.), N-sulfonylimino group (N-methanesulfonylimino, etc.), dicyanoethylene group, ammonium group, sulfonium group, phosphonium Groups, a pyrylium group, and an immonium group, and a heterocyclic group in which an ammonium group, a sulfonium group, a phosphonium group, an immonium group, and the like form a ring is also included. 0.30 as σp value
The above substituents are particularly preferred.

The alkyl group represented by W is methyl, ethyl, trifluoromethyl and the like, the alkenyl group is vinyl, halogen-substituted vinyl and cyanovinyl, and the alkynyl group is acetylenyl and cyanoacetylenyl. Examples of the group include nitrophenyl, cyanophenyl, and pentafluorophenyl, and examples of the heterocyclic group include pyridyl, pyrimidyl, triazinyl, succinimide, tetrazolyl, triazolyl, imidazolyl, and benzoxazolyl. W is σ
A p-value is preferably a positive electron-withdrawing group, and more preferably, the value is 0.30 or more.

Of the above substituents for R, preferably a hydroxy group, a mercapto group, an alkoxy group, an alkylthio group,
Halogen atom, an organic or inorganic salt of a hydroxy group or a mercapto group, and a heterocyclic group, more preferably a hydroxy group, an alkoxy group, an organic or inorganic salt of a hydroxy group or a mercapto group, a heterocyclic group, Particularly preferred is an organic or inorganic salt of a hydroxy group, a hydroxy group or a mercapto group.

Among the substituents of X and W, those having a thioether bond in the substituent are preferable.

Next, specific examples of the compound represented by formula (G) are shown below, but it should not be construed that the invention is limited thereto.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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The binder suitable for the photothermographic material of the present invention is transparent or translucent, generally colorless, and includes natural polymer synthetic resins, polymers and copolymers, and other film-forming media, for example: gelatin, gum arabic, (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). Although it may be hydrophilic or hydrophobic, in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after thermal development. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, and cellulose acetate butyrate are particularly preferably used.

A layer containing a photosensitive silver halide (hereinafter, referred to as a layer)
The dried film thickness of the photosensitive layer is also preferably 2 to 20 μm, more preferably 5 to 20 μm. If the thickness is 2 μm or less, coating failure occurs, and unevenness and failure on pinholes occur frequently, which is not preferable. If it exceeds 20 μm, the developability will deteriorate. The dry thickness of the surface protective layer on the photosensitive layer side is 0.1 to 1
0.0 μm is preferred, and more preferably 0.1 to 8.0.
μm. The photosensitive layer side may have a protective layer or another layer between the photosensitive layer and the support. The layer thickness other than the photosensitive layer on the photosensitive layer side is preferably thin. If the protective layer is too thick, the heat transfer from the protective layer side to the photosensitive layer is poor, and the heat transfer from the support side to the layer between the support and the photosensitive layer also deteriorates, and the developability deteriorates. The total film thickness on the backing layer side is preferably 2 to 20 μm. It is more preferable that the backing layer is thin because heat is transmitted even from the backing side. However, if the thickness is less than 2 μm, coating unevenness occurs. If it is thicker than 20 μm, the heat transfer will deteriorate.

In the photothermographic material of the present invention, various surfactants can be used as a coating aid. Among them, a fluorine-based surfactant is preferably used for improving charging characteristics and preventing spot-like coating failure.

The photothermographic material of the present invention can contain a color tone agent for suppressing the color tone of silver, if necessary. Examples of suitable toning agents that can be employed are Research Disclosure
re No. 17029. In addition, a mercapto compound, a disulfide compound, and a thione compound can be contained in order to suppress or promote development to control development, to improve spectral sensitization efficiency, to improve storage stability before and after development, and the like.

The photothermographic material of the present invention may contain an antifoggant.

A sensitizing dye can be used in the photothermographic material of the present invention. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item 1
Section 7643 IV-A (p.23, December 1978), I
tem1831X (August 1978, p. 437). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

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, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like. These additives and the other additives mentioned above are
h Disclosure Item 17029 (19
June 1978 p. Compounds described in 9 to 15) can be preferably used.

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). A heat-treated plastic support can also be used.

Among them, a preferred support is a support made of polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene polymer having a syndiotactic structure.

The thickness of the support is preferably 100 to 150 μm. Preferably it is 110 to 130 μm. The thinner the layer, the better the heat transfer from the backing layer side. However, if the thickness is less than 110 μm, the layer is rapidly heated and the development unevenness is deteriorated. If the thickness is more than 150 μm, the heat capacity of the support becomes too high and the development is not sufficiently performed under the desired development conditions.

The support is preferably heat-treated, and the purpose is to shrink it in advance by the heat treatment.
For example, polyethylene phthalate (PET)
190 ° C is good. Since the glass transition point is 80 ° C., there is no meaning below 80 ° C., and when it is 80 ° C. or more and less than 100 ° C., shrinkage is not sufficient. If the temperature exceeds 190 ° C., there is a risk that the softening will be severe and the melting will occur.

<< Heat Development >> For example, a photosensitive material exposed using a laser is developed by heat. As a heating means for heat development, a mode having a conductive heating element layer, a halogen lamp, a heating element described in JP-A-61-145544, and the like can be used.

As a specific form, 1) a method of placing the film in an oven at a constant temperature for a predetermined time, 2) a method of conveying the inside of the oven maintained at a constant temperature at a constant speed, and 3) heating to a constant temperature Media (metal roller, silicone rubber,
There is no particular limitation as long as it is a method of contacting urethane rubber, paper, a fluorinated medium or the like for a predetermined time. In addition, a preheating section may be provided before or after the developing section separately from the developing section. In this case, the conditions described in 1) to 3) are indispensable as in the former case.

In the present invention, a temperature control mechanism is required to control the temperatures of the developing section and the preheating section to be constant.
To control the temperature, it is preferable to control and adjust the temperature using a thermostat or the like.

Further, a temperature feedback system may be provided. It is preferable that the feedback be performed at any time, every hour, or every day, but these may be freely adjusted depending on the operator used.

The preferred temperature during heating is 30 ° C. to 150 ° C.
° C, and the preferred temperature range of the developing section is 100 to 100 ° C.
At 150 ° C, more preferably at 100 to 140 ° C.
In the present invention, it is preferable to perform a heat treatment before the developing section at a temperature lower than the developing temperature by 5 ° C. or more. The temperature range is more preferably 100 to 120 ° C, and 100 to 115 ° C.
Is more preferred. The processing time of the heating section is preferably 1 to 60 seconds, more preferably 5 to 50 seconds. The preferable processing time range of the developing section is 3 to 30 seconds, more preferably 5 to 30 seconds. A preferred processing time range of the preheating section is 3 to 30 seconds, more preferably 5 to 25 seconds.

In the processing method of the present invention, the total processing time is 20 to 8
0 seconds, more preferably 30 to 7 seconds.
0 seconds.

In performing such thermal development, it is preferable not to apply tension to the photosensitive material, but there is no particular limitation as long as it is 10 kg / cm ² or less. Care must be taken because applying too much tension may change the dimensions of the photosensitive material and cause problems.

In the present invention, the porosity in the heating section, the developing section, the preheating section and the like is determined by measuring 1) the void volume (cm ³ ) of the heating section and the like and 2) the volume (cm ³ ) of the heating section and the like.

1) The method of measuring the void volume (cm ³ ) of the heating section, etc. is such that the heating, development, preheating section, etc. are maintained in the form of actual use, and the heating, development, preheating section, etc. are filled with water or gas. Calculate the volume of

2) The method of measuring the volume (cm ³ ) of the heating section and the like is such that all parts such as a transport section, a heating means section, a temperature control section, and wiring in a heating, developing, preheating section and the like are eliminated and heating is performed. ,
Calculate the volume of water or gas in the developing and preheating sections.

In the present invention, the porosity (=
Void volume in heating section (cm ³ ) / volume in heating section (c
m ³ )) is from 0.002 to 0.3, preferably from 0.002 to 0.28. This porosity is 0.002
If it is smaller, the transportability of the photothermographic material is deteriorated.
If it is larger than 3, problems such as uneven development may occur due to the air layer. Porosity in the developing unit (= void volume of the heat developing section (cm ³⁾ / heat volume of the developing unit (cm ³⁾⁾ is 0.00
The range of 2 to 0.5 is preferred, more preferably 0.00
It is in the range of 2 to 0.45. If the porosity is smaller than 0.002, there is a problem that the transportability of the photothermographic material is deteriorated. If the porosity is larger than 0.5, a problem such as uneven development occurs due to the air layer.

In the present invention, the porosity in the developing section / the porosity in the heating section = 0.006 to 1.8 in the thermal development processing apparatus.
Is preferably satisfied, but more preferably 0.006 to 1.6. In this connection, if it is smaller than 0.006, there are problems such as deterioration of the developing conveyance property.
If it is larger than 8, problems such as uneven development may occur due to the air layer.

In order to keep the porosity in a specific range, in the thermal development processing apparatus, the distance between the photothermographic material conveyed in the heating section and the facing heating member may be in the range of 0 to 1.8 cm. Preferably, more preferably 0.015
1.6 cm. In a more preferred embodiment, the distance between the conveying member and the heating member in the developing section is preferably in the range of 0 to 1.8 cm, more preferably 0.015 cm.
１1.6 cm.

The heat development processing apparatus may be integrated with the exposure system, in which case the transport system is integrated with a bridge or the like. As described above, it is also possible to have a preheating section in front of the developing section in addition to the heat developing section. A cooling unit may be provided after the developing unit in order to suppress development progress of the photothermographic material or to control curling of the support. When it has a cooling part, its temperature is preferably in the range of 10 to 80C, more preferably in the range of 20 to 60C.

The line speed is from 1260 mm / min to 30
00 mm / min is preferred. In the present invention, the problem of development unevenness does not occur even at 1,260 mm / min or more. If the speed exceeds 3,000 mm / min, poor conveyance frequently occurs due to the softening of the photosensitive material in the heat developing section. Further, the processing capacity is increased, but the line length becomes too long, the apparatus becomes large, and the manufacturing cost is increased, which is not preferable.

[0171]

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 PET Support) A commercially available biaxially-stretched heat-fixed PET film having a thickness of 120 μm was coated on both surfaces with 8 W /
m ² · m of corona discharge treatment, the following undercoating coating liquid a-1 is applied to one side to a dry film thickness of 0.8 μm, and dried to form an undercoating layer A-1, and vice versa. On the side surface, the following antistatic coating solution b-1 was applied with a dry film thickness of 0.8 μm
And dried to form an antistatic subbing layer B-
It was set to 1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g polystyrene fine particles (average particle diameter 3 μm) 0.05 g colloidal silica (average particle diameter 90 μm) 0 .1 g with water 1 l << Undercoat coating solution b-1 >> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.18 μm) Amount to become 200 mg / m ² Butyl acrylate (30% by weight) Styrene ( 20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g hexa Styrene-1,6-bis subsequently finish 1l in (ethyleneurea) 0.8 g Water, to the undercoat layer A-1 and the upper surface undercoat layer B-1,
A corona discharge of 8 W / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating Solution a-2 for Undercoating >> 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 Finished to 1 liter with water << Lower upper layer coating solution b-2 >> (C-4) 60 g Latex solution containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0175]

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[0176]

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

(Preparation of Emulsion A) In 900 ml of water, 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved and adjusted to a temperature of 35 ° C. and a pH of 3.0.
g of an aqueous solution containing sodium chloride, potassium bromide and potassium iodide in a molar ratio of (60/38/2) and [Ir (NO) Cl ₅ ] salt in an amount of 1 × 10 ⁻⁶ per mole of silver. The mol and rhodium chloride salt were added by the controlled double jet method at 1 × 10 ⁻⁶ mol per mol of silver while keeping the pAg at 7.7. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 8 with NaOH, and the pAg was adjusted to 6.5 to perform reduction sensitization to obtain an average particle size of 0.06 μm.
The coefficient of variation of the projected diameter area with a monodispersity of 10% is 8%, [10
0] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and desalting treatment was performed.

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

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

(Preparation of Photosensitive Emulsion) The preform emulsion thus obtained was divided, and a solution of polyvinyl butyral (number average molecular weight 3000) in methyl ethyl ketone (17) was prepared.
544 g and toluene 107 g were gradually added and mixed, and then at 30 ° C., 1 ° C. and 4000 psi with a media disperser using a 0.5 mm-size ZrO ₂ bead mill.
Dispersion was performed for 0 minutes.

The following layers were simultaneously coated on both sides of the support to prepare a sample. The drying was performed at 60 ° C. for 15 minutes.

(Back side coating) Backing layer 1: A solution having the following composition was coated on layer B-2 of the support so as to have a dry film thickness of 5 μm.

Cellulose acetate butyrate 15 ml / m ² (10% methyl ethyl ketone solution) Dye-A 7 mg / m ² Dye-B 7 mg / m ² Matting agent: monodispersity 15% Average particle size 8 μm monodisperse silica 90 mg / m ² _{C 8 F 17 (CH 2 CH} 2 O) 12 C 8 F 17 50mg / m 2 C 8 F 17 -C 6 H 4 -SO 3 Na 10mg / m 2

[0185]

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(Coating on Photosensitive Layer Surface Side) Photosensitive layer 1: A solution having the following composition was applied on layer A-2 of the support so that the coated silver amount was 1.8 g / m ² at a dry film thickness of 15 μm. .

Preform emulsion 240 g Sensitizing dye (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Oxidizing agent ( 10 ml methanol solution) 1.2 ml 2-4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml hydrazine Derivative H-26 0.4 g Hardening agent P-51 0.3 g Phthalazine 0.6 g 4-Methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g Calcium carbonate with an average particle size of 3 μm 0.1 g A-4 (20% 20.5 ml isocyanate compound 0.5g (Desmodur N3300, manufactured by Mobay Corporation)

[0188]

Embedded image

Surface protective layer: A solution having the following composition was simultaneously coated on the photosensitive layer in a dry film thickness of 2.6 μm.

[0190] Acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 mg / m ² methanol 7 ml / m ² phthalazine ^{250mg / m 2 A-4 (} 20% methanol solution) 10 ml / m ² Matting agent: Single Monodisperse silica having a degree of dispersion of 10% and an average particle size of 4 μm 5 mg / m ² CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH = CH ₂ 35 mg / m ² Fluorine surfactant C ₁₂ F ₂₅ ( CH ₂ CH ₂ O) ₁₀ C ₁₂ F ₂₅ 10 mg / m ² C ₈ F ₁₇ -C ₆ H ₄ —SO ₃ Na 10 mg / m ² << Exposure and development treatment >> Thereafter, an image setter equipped with a 780 nm semiconductor laser Solid exposure was performed using energy of -logE using Dolev 2dry (internal drum method) manufactured by Cytex Corporation.

<< Automatic Thermal Developing Machine >> Evaluation was performed by using an automatic thermal developing machine showing the cross section of the heating section in FIGS. 1 to 4 under the developing conditions shown in the table. Exposure and development were performed at 23 ° C and 50% R.
We went in a room conditioned to H.

FIGS. 1 to 4 are sectional views of examples of the heating unit. 1A to 1C show a horizontal transport type using a transport roller, in which a heat medium 2 is arranged so as to surround the photosensitive material transported in the direction → and the transport roller. Assuming that the distance between the conveyed photothermographic material surface and the heat medium (heating member) facing the surface is the height of the heating section, the height of the preheating section is Dp and the height of the developing section is Dh. FIG. 2A shows a horizontal transport type using a belt conveyor 3, in which a heat medium 2 in which a gap is set only in a region where a photosensitive material is transported is disposed. FIG. 2B shows the same type having a preheating portion. FIG. 2 (c) shows a case where the preheating section is carried by a roller and the heat developing section is carried by a belt conveyor. FIG. 3 (a) shows a case where the photosensitive material is heated by a pair of heat drums. The photosensitive material is conveyed while being sandwiched between guide rollers 61 and 62, and is heated from both sides by being sandwiched between a pair of heat drums 51 and 52. , Once discharged from the heating and developing unit, conveyed in the reverse direction, wound again on the upper heat drum 51 after the double-sided heating again, guided by the guide rollers 4, and discharged through the cooling unit. FIG.
(B) is a combination of preheat drums 81 and 82. FIG. 4A shows an arrangement in which a roller group 91 is arranged around the periphery of the heat drum 53, and the photosensitive material being conveyed is pressed against the heat drum and heated, and the entire surface is covered with the heat medium 2 and the back surface is also heated. It is. FIG. 4 (b)
Further, an intermittent roller group 92 is arranged around the periphery of the preheat drum 83 for preheating.

<< Evaluation of development unevenness >> 440 mm × 610 mm
A photosensitive material having a size was prepared, and the variation rate of Dmin and Dmax at the position of the photosensitive material when one sheet was passed using an exposure machine and a developing machine was evaluated. That is, measurement was performed at nine locations shown in FIG. 5, and the difference between the maximum Dmin value and the minimum Dmin was defined as the Dmin variation rate, and the difference between the maximum Dmax value and the minimum Dmax was defined as the Dmax variation rate. Note that the development tip is on the side of measurement points 1 to 3.

<< Evaluation of transportability >>
Evaluation was made based on the number of transport failures when processing one sheet.

<< Evaluation of Image Reproducibility >>
From the sensitometric image obtained by exposing and developing 0 sheets, the sensitivity was determined by the reciprocal of the exposure amount giving a density of 1.0, and the rate of change was expressed as a percentage and evaluated.

The above conditions and results are shown in Tables 1 to 3.

[0197]

[Table 1]

[0198]

[Table 2]

[0199]

[Table 3]

[0200]

According to the method for processing a photothermographic material of the present invention, it is possible to solve the problems of uneven development, image reproducibility, and poor transport due to a change in heat transfer coefficient or air flow.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a horizontal transfer type heating unit using a transfer roller.

FIG. 2 is a cross-sectional view of an example of a horizontal transfer type heating unit using a belt conveyor.

FIG. 3 is a cross-sectional view of an example of a heating unit that heats with a pair of heat drums.

FIG. 4 is a cross-sectional view of an example of a heating unit that uses both a heat drum and a heat medium.

FIG. 5 is a diagram showing measurement points of development unevenness evaluation.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conveyance roller 2 Heat medium 3 Belt conveyor 4 Guide roller 51, 52, 53 Heat drum 61, 62, 71, 72 Guide roller 81, 82, 83 Preheat drum Dh Developing part height Dp Preheating part height

Claims (11)

[Claims] 1. A method for processing a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder, wherein a porosity in a heated portion (= a void volume in a heated portion) (Cm ³ ) / volume in heating section (c
m ³⁾⁾ is processing method of a photothermographic material, which comprises using the thermal development apparatus is in the range of 0.002 to 0.3. 2. The temperature of a heating section of a thermal development processing apparatus is 100.
The method for processing a photothermographic material according to claim 1, wherein the temperature is in the range of from 150C to 150C. 3. A processing section for processing a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder, wherein the developing section has a temperature in the range of 110 ° C. to 150 ° C. A method of processing a photothermographic material, comprising using a heat development processing apparatus having a preheating section in a temperature range lower than the temperature of the developing section by 5 ° C. or more. 4. A process for processing a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrast agent and a binder, wherein a porosity in a developing section (= a void in a heat developing section) Volume (cm ³ ) / Volume (c
m ³ )) is a photothermographic material processing method using a photothermographic processing apparatus having a range of 0.002 to 0.5. 5. The temperature of the developing section of the thermal developing apparatus is 110.
5. The method for processing a photothermographic material according to claim 4, wherein the temperature is in the range of from 150C to 150C. 6. The method for processing a photothermographic material according to claim 4, further comprising a preheating section having a temperature lower by at least 5 ° C. than the temperature of the developing section before the developing section of the thermal developing apparatus. 7. The porosity in the developing section is from 0.006 to 1.10 relative to the porosity in the heating section having the developing section and the preheating section.
The method for processing a photothermographic material according to claim 3, wherein 8. When a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder is processed, a surface of the photothermographic material conveyed into a heating unit is treated. The distance to the facing heating member is 0 to
A method for processing a photothermographic material, wherein a photothermographic processing apparatus having a range of 1.8 cm is used. 9. In processing a photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder, a distance between a conveying member and a heating member in a developing section is increased. A method for processing a photothermographic material, comprising using a photothermographic processing apparatus having a range of 0 to 1.8 cm. 10. A thermal development processing apparatus for transporting a flat surface, wherein the thermal development processing apparatus is a plane development apparatus.
Or the method for processing a photothermographic material according to item 9. 11. The thickness of the support of the photothermographic material is 110.
3. The method according to claim 1, wherein
13. The method for processing a photothermographic material according to 3, 4, 5, 6, 7, 8, 9, or 10.