JP2000227649A - Processing method for heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a very stable processing method for a heat developable phbtosensitive material. SOLUTION: A heat developable photosensitive material having at least an organic silver salt a silver halide and a reducing agent on the substrate is imagewise exposed and processed with an automatic processing machine. The development temperature and development time are determined as functions of the amount of a residual solvent in the photosensitive material and a processing area developed per unit time or as functions of light exposure on the photosensitive material and a processing area developed per unit time and control is carried out.

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 particular, the processing stability of the photothermographic material is remarkably changed by changing a developing temperature and a developing time of an automatic developing machine used for processing the photothermographic material. It relates to an improved processing method.

[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 been a problem in terms of workability. There is a strong demand for weight loss. Therefore, there has been a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image.

As a technique for this purpose, a photothermographic material for forming a photographic image by using a heat development processing method is disclosed in, for example, US Pat. Nos. 3,152,904 and 3,457,075.
And D. Morgan and B.M. Shelley (S
hely), “Thermally Processed Silver.
er Systems) "(Imaging Pros and Materials (Imaging Pro)
cesses and Materials) Nebl
ette 8th edition, Sturge, V.E. Walworth, A .; Shepp (S
hepp), ed., page 2, 1969).

[0004] However, when the heat development processing is performed by an automatic developing machine, if the development processing is performed by controlling the development temperature and the development time only by the processing area of the heat-developable photographic photosensitive material as in the related art, the development processing conditions Is subjected to development processing under unstable conditions, which greatly affects photographic performance and the like.

Therefore, there has been a strong demand for the development of a method for developing a photothermographic material having significantly improved processing stability.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an extremely stable developing method of a photothermographic material.

[0007]

An object of the present invention is to provide a photothermographic material having at least an organic silver salt, a silver halide and a reducing agent on a support, imagewise exposing the same to an image, and developing the resulting image by using an automatic developing machine. Temperature and development time are determined as a function of the amount of residual solvent in the light-sensitive material and the processing area to be processed in a unit time, and a method for processing the heat-developable light-sensitive material, wherein at least an organic silver salt and a halogen are provided on a support. After imagewise exposing the photothermographic material having silver halide and a reducing agent, the developing temperature and the developing time are determined as a function of the exposure amount of the photosensitive material and the processing area to be developed per unit time using an automatic developing machine. This is achieved by a method for controlling a photothermographic material, wherein the photothermographic material to be processed contains the hydrazine compound represented by the general formula [H].

Hereinafter, the present invention will be described in detail.

Details of the photothermographic material are described in, for example, US Pat. Nos. 3,152,904 and 3,457,0.
No. 75; Morgan (Dry Silver Pho)
Graphic Material) "and D.C. Morgan and B.M. "The Silver System Treated by Heat (Therma)" by Shelly
llly Processed SilverSystem
ms) "(Imaging Processes and Materials
nd Materials) Neblette No. 8
Plate, Sturge, V.S. Walworth, A .; Shepp, 2nd page, 1969) and the like. Among them, the present invention is characterized in that an image is formed by thermally developing a photosensitive material at 80 to 140 ° C., and no fixing is performed. Therefore, the silver halide and the organic silver salt remaining in the unexposed area remain in the photosensitive material without being removed.

The developing apparatus for carrying out the developing method of the present invention has a computer which calculates and supplies a developing temperature and a developing time based on information received on the exposure amount and the residual solvent amount of the photothermographic material. Comprising a chemical management system. Since information is transmitted between the imagesetter and the processing device, it is possible to supply information on the amount of exposure and the amount of residual solvent to the chemical system. The information on the average amount of the photothermographic material processed in the unit time is generated in the developing device from a sensor that detects the number of sheets having a predetermined area passing through the developing device in a predetermined time. Can be done. According to the present invention, the developing temperature and the developing time of the automatic developing machine are determined according to the change of the signal of the exposure amount and the residual solvent amount of the photothermographic material to be processed.

The photosensitive material to be processed preferably contains a hydrazine derivative represented by the above general formula [H].

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, such as 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, imidazole ring, tetrahydrofuran ring, morpholine ring, pyridine ring, 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. Particularly preferred as A ₀ are an aryl group and a heterocyclic group, and the aromatic group and the heterocyclic group of A ₀ may have a substituent. Particularly preferred groups include an acidic group having a pKa of 7 to 11. Specific examples of the substituents include a sulfonamide group, a hydroxyl group, and a mercapto group.

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

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, 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)
(G ₁ D ₁ ) — group, and preferred G ₀ is —CO—
Group, particularly preferably at -COCO- group -COCO- group and the like, G ₁ is a single bond, -O- group, -S- group, or -N (D ₁₎ - represents a group, D ₁ is an aliphatic Group, aromatic group,
Represents a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the molecule, 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, Examples include an amino group, and more preferably an alkyl group and an amino group substituted with fluorine. 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.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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Other hydrazine derivatives that can be preferably used include compounds H-1 to H-2 described in columns 11 to 20 of US Pat. No. 5,545,505.
9, compounds 1 to 12 described in columns 9 to 11 of U.S. Pat. No. 5,464,738.

These hydrazine derivatives can be synthesized by a known method.

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

The silver halide grains in the present invention function as a light sensor. In the present invention, in order to suppress white turbidity after image formation and to obtain good image quality, it is preferable that the average particle size is small, and the average particle size is 0.1 μm or less, more preferably 0.01 μm or less.
m to 0.1 μm, particularly preferably 0.02 μm to 0.08 μm. 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 formula is 40% or less. More preferably 30%
Or less, particularly preferably 0.1% or more and 20% or less.

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. The term "tabular grain" as used herein means a vertical thickness h μm where the square root of the projected area is a particle size r μm.
Means that the aspect ratio = r / h is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or less. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention may be prepared by any method such as an acidic method, a neutral method, and an ammonia method. The formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed by any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. 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, silver halide is 0.75 to 30 with respect to the organic silver salt.
It is preferably contained in an amount of% by weight.

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

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method or a flocculation method, but in the present invention, they may or may not be desalted. .

The photosensitive silver halide grains in the present invention 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. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds 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
And salts thereof: organic acid salts (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (Eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); 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 (eg, salicylic acid, benzoic acid, 3,5
-Dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-
Carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thioene and 3-carboxymethyl-
4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H
-Tetrazole, 3-amino-5-benzylthio-1,
Complexes or salts of silver with a nitrogen acid selected from 2,4-triazole and benzotriazole; saccharin, 5-
Silver salts such as chlorosalicylaldoxime; and silver salts of mercaptides. 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 described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate and sodium arachidate, the above-mentioned soap and silver nitrate are added by a control double jet to prepare crystals of an organic silver salt. At that time, silver halide grains may be mixed.

In the present invention, the organic silver salt has an average particle size of 2
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.05 μm to 1.5 μm, particularly 0.05 μm
~ 1.0 µm is preferred. Monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.
It is. In the present invention, the organic silver salt preferably has tabular grains having 60% or more of the total organic silver. In the present invention, the tabular grains mean those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between the average particle diameter and the thickness, that is, the following formula.

AR = average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, the organic silver crystals are obtained by dispersing and pulverizing a binder, a surfactant and the like with a ball mill or the like. Can be Within this range, the density of the formed image is high and the image storability is excellent.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably from 0.5 g to 2.2 g per m ² in terms of silver. . With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is at most 50% by weight, preferably at most 25%, more preferably between 0.1% and 15%.

The photothermographic material of the present invention contains a reducing agent. Examples of suitable reducing agents are described in US Pat.
No. 448, No. 3,773, 512, No. 3,59
No. 3,863, and Research Disclos
ures 17029 and 29996, particularly preferred reducing agents are hindered phenols. As the hindered phenols, the following general formula (A)
The compound represented by these is mentioned.

[0039]

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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.

[0042]

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[0043]

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The amount of the reducing agent including the compound represented by the 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.

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 (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), 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, cellulose acetate butyrate, and polyester are particularly preferably used.

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

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

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

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The particle diameter of the matting agent is a diameter converted into a sphere, and the average particle diameter is preferably 0.5 μm to 10 μm,
More preferably, it is 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.

Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (Average value of particle size) × 100 The photothermographic material of the 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. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer, may be formed on the opposite side. A dye or a pigment may be included in the active layer. Any dye may be used as long as it has a desired absorption in a desired wavelength range.

The non-photosensitive layer preferably contains the binder or matting agent described above, and may further contain a slip agent such as a polysiloxane compound, wax or liquid paraffin.

In the photothermographic material, 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 light-sensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

The photothermographic material of the present invention, which forms a photographic image by heat development, comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, silver. Is usually contained in a (organic) binder matrix in a dispersed state. This is stable at normal temperature, but is high after exposure (for example,
(° C.). Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

Examples of suitable toning agents used in the present invention are R
essearch Disclosure No. 17029.

Further, a mercapto compound, a disulfide compound, and a thione compound can be contained in order to suppress or promote the development to control the development, to improve the spectral sensitization efficiency, and to improve the storage stability before and after the development. .

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. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078 and JP-A-9-54409
And compounds described in JP-A-9-80679 are preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. In the photothermographic material of the present invention, for example, a surfactant, an antioxidant,
Stabilizers, plasticizers, ultraviolet absorbers, coating aids, and the like may be used. These additives and the other additives mentioned above are Research Disclosure Item 1
Compounds described in No. 7029 (pp. 9-15, June 1978) 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 deformation of the image after development. , Polyethylene naphthalate). Among them, preferred supports include plastics (hereinafter SPS) containing polyethylene terephthalate (hereinafter abbreviated as PET) and a styrene-based polymer having a syndiotactic structure.
Abbreviated). The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm. A heat-treated plastic support can also be used.

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability.

[0063]

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 corona discharge treatment of 8 W / m ² · min. Was performed on both sides of a commercially available biaxially stretched and heat-fixed 175 μm thick blue colored PET film. On one surface, the following undercoating coating solution a-1 is applied so as to have a dry film thickness of 0.8 μm and dried to form an undercoating layer A-1. The solution b-1 was applied so as to have a dry film thickness of 0.8 μm and dried to obtain an antistatic-processed undercoat 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 Finish to 1 L with water << Subtraction 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 Finish to 1L with water Then, on the upper surface of the undercoat layer A-1 and the 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 undercoating layer A-2, the undercoating layer B-1 is coated with the following undercoating upper 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 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 Finished to 1 L with water << Lower upper coating liquid b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5g (C-6) 12g Polyethylene glycol (weight average molecular weight 600) 6g Finish to 1L with water

[0067]

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[0068]

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(Heat Treatment of Support) In the above-described undercoat drying step of the 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 potassium bromide and potassium iodide in a molar ratio of (98/2) and [Ir (N
O) Cl ₅ ] salt was added in an amount of 1 × 10 ^-6 mole per silver mole and rhodium chloride salt in an amount of 1 × 10 ^-6 mole per silver mole, pA
After the addition by the controlled double jet method while maintaining the g at 7.7, reduction sensitization was performed at pH 8.7 and pAg 6.5. Thereafter, 4-hydroxy-6-methyl-1,
Add 3,3a, 7-tetrazaindene and add NaOH to p.
By adjusting H to 5, cubic silver iodobromide grains having an average grain size of 0.06 μm, a monodispersity of 10%, a variation coefficient of projected diameter area of 8%, and a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, followed by addition of 0.1 g of phenoxyethanol, pH 5.9 and pAg7.
Adjusted to 5 to obtain a silver halide emulsion A.

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

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

(Preparation of Photosensitive Emulsion) Polybutyral (average molecular weight: 300
544 g of 0) methyl ethyl ketone solution (17 wt%)
And 107 g of toluene were gradually added and mixed.
Dispersed at 000 psi.

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

Back layer coating solution: cellulose acetate butyrate (10% methyl ethyl ketone solution) 15 ml / m ² dye-B 7 mg / m ² dye-C 7 mg / m ² Matting agent: monodispersity 15%, average particle size 8 μm monodisperse silica _{^{30mg / m 2 C 9 F 17}} -C 6 H 4 -SO 3 Na 10mg / m 2

[0076]

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

Photosensitive layer coating solution: Preform emulsion 240 g Sensitizing dye-1 (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Antifoggant-2 (10% methanol solution) 1.2 ml Hydrazine compound-described in Table 1 (5% methanol solution) 2 ml 2-Chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2 -Mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml A-2 (20% methanol solution) 29.5 ml phthalazine 0.6 g 4-methylphthalic acid 0.25 g tetrachlorophthalic acid 0.2g Surface protective layer coating solution: Acetone 5 l / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 g / m ² methanol 7 ml / m ² phthalazine 250 mg / m ² Matting agent: monodisperse degree of 10% monodisperse silica having an average particle size 4 [mu] m 70 mg / m ² CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH ＝ CH ₂ 35 mg / m ² Spot inhibitor 50 mg / m ² C ₉ H ₁₇ -C ₆ H ₄ -SO ₃ Na 10 mg / m ²

[0079]

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<< Exposure and Development Processing >> Processing Method A: 810 n was added to the photothermographic material prepared above.
Exposure was performed with an imager having a m semiconductor laser.
Then, using an automatic developing machine having a heat drum, regardless of the exposure amount of the photothermographic material and the amount of residual solvent, 11
The film was thermally developed at 0 ° C. for 15 seconds. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

Processing method B: In comparison with processing method A, the processing temperature was changed as follows by the signal of the exposure amount of the imager. At this time, the processing time was fixed at 15 seconds. The automatic developing machine was modified so that it could be processed under the following conditions.

[0082] Processing method C: The processing time was changed as follows with respect to processing method A by the signal of the exposure amount of the imager. At this time, the processing temperature was kept constant at 110 ° C. The automatic developing machine was modified so that it could be processed under the following conditions.

[0083] The photothermographic material prepared as described above was subjected to thermal development running processing of 200 sheets continuously in the order of blackening ratio 5, 20, 30, 40, and 50% by the respective processing methods, and before and after running. The difference in performance was evaluated.

<< Evaluation of Photographic Performance >> The obtained images were evaluated with a densitometer. Evaluation of sensitivity is fog density +3.0
The reciprocal of the exposure amount that gives the transmission density of
o. The relative sensitivity when the sensitivity of 1 was 100. The fog density here refers to the density of a portion where halftone dots are exposed to 0%, and the smaller the value, the better. Also, the gradient of a straight line connecting the points of density 0.3 and 3.0 on the characteristic curve is shown as gradation γ.

Table 1 shows the results.

[0086]

[Table 1]

Thus, when the processing temperature and the processing time are changed in accordance with the blackening ratio of the photothermographic material, the change in performance before and after running is small.

Example 2 A photothermographic material prepared in the same manner as in Example 1 was subjected to heat development by the following processing method, and the sensitivity, fog and γ were evaluated in the same manner as in Example 1.

Processing method D: The processing temperature and the processing time were changed as follows in accordance with the exposure amount signal of the imager. The automatic developing machine was modified so that it could be processed under the following conditions.

[0090] Table 2 shows the results of the evaluation.

[0091]

[Table 2]

Thus, when both the processing temperature and the processing time are changed in accordance with the blackening ratio of the photothermographic material, the change in performance before and after running is further reduced.

Example 3 A photothermographic material prepared in the same manner as in Example 1 was subjected to a heat development treatment by the following processing method, and the sensitivity, fog and γ were evaluated in the same manner as in Example 1.

Processing method E: In comparison with processing method A, the processing temperature was changed as follows by changing the signal of the residual solvent amount of the imager. At this time, the processing time was fixed at 15 seconds. The automatic developing machine was modified so that it could be processed under the following conditions.

Residual solvent amount (mg / m ² ) Processing temperature Processing time 30 90 ° C. 15 seconds 50 100 ° C. 15 seconds 100 110 ° C. 15 seconds 150 120 ° C. 15 seconds 200 130 ° C. 15 seconds Processing method F: For processing method A The processing time was changed as follows according to the signal of the residual solvent amount of the imager.
At this time, the processing temperature was kept constant at 110 ° C. The automatic developing machine was modified so that it could be processed under the following conditions.

Residual solvent amount (mg / m ² ) Treatment temperature Treatment time 30 110 ° C. 10 seconds 50 110 ° C. 12 seconds 100 110 ° C. 15 seconds 150 110 ° C. 18 seconds 200 110 ° C. 20 seconds The results are shown in Table 3.

[0097]

[Table 3]

Thus, when the processing temperature and the processing time are changed in accordance with the amount of the residual solvent in the photothermographic material, the change in performance before and after running is small.

Example 4 A photothermographic material produced in the same manner as in Example 1 was subjected to heat development by the following processing method, and the sensitivity, fog and γ were evaluated in the same manner as in Example 1.

Processing method G: The processing temperature and the processing time were changed as follows from the processing method A by the signal of the residual solvent amount of the imager. The automatic developing machine was modified so that it could be processed under the following conditions.

Residual solvent amount (mg / m ² ) Processing temperature Processing time 30 90 ° C. 10 seconds 50 100 ° C. 12 seconds 100 110 ° C. 15 seconds 150 120 ° C. 18 seconds 200 130 ° C. 20 seconds The results are shown in Table 4.

[0102]

[Table 4]

Thus, it can be seen that by changing both the processing temperature and the processing time according to the amount of the residual solvent in the photothermographic material, the change in performance before and after running is further reduced.

[0104]

According to the present invention, a photothermographic material can be extremely stably developed.

Claims (3)

[Claims] An imagewise exposure of a photothermographic material having at least an organic silver salt, silver halide and a reducing agent on a support,
Processing of a photothermographic material, wherein an automatic developing machine is used to determine and control a developing temperature and a developing time as a function of a residual solvent amount of the photosensitive material and a processing area developed in a unit time. Method. 2. A photothermographic material having at least an organic silver salt, a silver halide and a reducing agent on a support after imagewise exposure,
A method for processing a photothermographic material, comprising determining and controlling a developing temperature and a developing time as a function of an exposure amount of the photosensitive material and a processing area to be developed in a unit time by using an automatic developing machine. . 3. The method for processing a photothermographic material according to claim 1, wherein the photothermographic material to be processed contains a hydrazine compound represented by the following general formula [H]. Embedded image [In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group which may have a substituent, B ₀ represents a blocking group, and A ₁ and A ₂ Each represents a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. G ₀ is a -CO- group, -COCO-
Group, -CS- group, -C (= NG ₁ D ₁ )-group, -SO-
A —SO ₂ — group or —P (O) (G ₁ D ₁ ) — group, where G ₁ is a mere bond, a —O— group, a —S— group, or a —N
Represents a (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 a molecule, they may be the same or different. Is also good. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group,
Represents an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. ]