JP2001281798A - Method for producing heat developable photographic sensitive material, and heat developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a producing method by which a heat developable photographic sensitive material can stably be produced, and particularly a producing method by which a heat developable photographic sensitive material having little fog and good sensitivity can be stably produced. SOLUTION: In the method for producing a heat developable photographic sensitive material containing an organic silver salt, photosensitive silver halide grains and a reducing agent on the base, a photosensitive liquid is preserved in a stagnant stage at a low temperature, warmed within 3 hr before application and applied. The temperature difference ΔT ( deg.C) between the photosensitive liquid in the low temperature preservation and that after the warming is preferably adjusted to 0-20 deg.C, the temperature TL ( deg.C) of the photosensitive liquid after the warming is preferably TAir-10<=TL<=TAir+10 in relation to the atmospheric temperature TAir ( deg.C) of an application chamber used and the temperature TL ( deg.C) of the photosensitive liquid after the warming is preferably 10<=TL<=30.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photothermographic material, and a photothermographic material produced by the method (hereinafter referred to as "thermosensitive material", or simply "thermosensitive material"). Also referred to).

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical care,
Waste liquids associated with wet processing of image forming materials have become a problem in terms of workability, and in recent years, there has been a strong demand for reduction of processing waste liquids from the viewpoint of environmental conservation and space saving. Therefore, there has been a need for a technique relating to a photothermographic material capable of efficiently exposing with a laser image setter or a laser imager and forming a high-resolution and clear black image.

As a technique for this, a silver halide photographic light-sensitive material which forms a photographic image by heat treatment is known, for example, US Pat. Nos. 3,152,904 and 3,45.
7,075 and D.C. Morgan and B.A.
"Thermally Processed Silver System" by Shelly
Silver Systems), Imaging Processes and Materials (Imaging)
Processes and Materials)
Neblette Eighth Edition, Sturge
e). Walworth, A .;
Shepp, 2nd page, 1969, etc.

[0004] Such a heat-sensitive material is usually prepared by dispersing a reducible silver source (organic silver salt), a catalytically active amount of a photocatalyst (silver halide) and a reducing agent in an organic binder matrix. Contains.

[0005] The heat-sensitive material loses its stability when stored at room temperature for a long time. As a result, fog increases and sensitivity decreases. For this purpose, various additives such as an antifoggant, a reducing agent and the like have been invented, but even if they are added, a sufficient effect cannot be obtained.

Therefore, development of a liquid preparation process for improving the long-term storage stability of a photothermographic material has been desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for stably producing a heat-developable photographic light-sensitive material, and in particular, a method for stably producing a heat-developable photographic light-sensitive material having less fog and good sensitivity. To provide.

[0008]

The above object of the present invention is achieved by the following constitution.

In a method for producing a heat-developable photographic material containing an organic silver salt, photosensitive silver halide particles and a reducing agent on a support, the photographic solution is stagnated and stored at a low temperature within 3 hours before being coated. Heat-developable photographic light-sensitive materials that are heated and applied to
The temperature difference ΔT (° C.) between the temperature of the photosensitive solution at the time of the low temperature stagnation and the temperature of the photosensitive solution after the heating is set to 0 to 20 ° C., and the temperature of the photosensitive solution after the heating T _L (° C.) It is preferable that T _Air −10 ≦ T _L ≦ T _Air +10 with respect to the ambient temperature T _Air (° C.), and that the photosensitive solution temperature _TL (° C.) after heating is 10 ≦ T _L ≦ 30. .

In a method for producing a heat-developable photographic material containing an organic silver salt, photosensitive silver halide particles and a reducing agent on a support, at least one photosensitive layer (image forming layer) and protection of at least one layer are provided. when a layer is applied at the same time, the temperature difference of the coating solution temperature of the photosensitive layer coating solution temperature T _L1 (° C.) and the protective layer coating solution temperature T _L2 (° C.) is -5 ≦ T _L1 -T _L2 ≦ 5 heat A method for producing a developed photographic light-sensitive material.

A heat-developable photographic light-sensitive material produced by the above-mentioned production method. Hereinafter, the present invention will be described in more detail.

The present invention is characterized in that the photosensitive solution is heated and applied within 3 hours after the heating, but is preferably applied within 2 hours. If the time from heating to coating is long, the reducing agent, halogenated antifoggant compound, etc. will react, causing an increase in fog and sensitivity rebound, and the time from heating to coating. When the coating length is long, unevenness and variation in film thickness tend to occur during coating.

Although any heating means may be used immediately before the application, generally, heating in a tank, heating by a heat exchanger in a pipe, heating of a coater, and the like are available. Heat exchangers include double-tube, multi-tube, double-tube and multi-tube heat transfer tubes with a static mixer (static mixer). May be.

In the case of multi-layer coating, if there is a large difference in the temperature of each coating solution, coating unevenness occurs at the time of coating. Therefore, in the present invention, when coating all layers to be coated simultaneously,
Photosensitive layer coating liquid temperature ( _TL1 ) and protective layer coating liquid temperature ( _TL2 )
Is set so that the temperature difference of

[0015] It is sufficient that the coating liquid is supplied within three hours when the temperature of the coating liquid is changed from a low temperature state to the coating liquid temperature, and it is preferable that the coating liquid can be applied within two hours. An example of the "liquid preparation device" which can be preferably used in the present invention is shown.

FIG. 1 is an explanatory diagram according to claim 1 of the present invention. The coating liquid in the stagnation tank 1 (maintained at a low temperature by the cooling jacket 2) passes through the filter F within 3 hours before the application, is heated to the application temperature in the heat exchanger 3, and is supplied to the liquid sending tank 11 (the heat retaining tank). (Heated by the jacket 12), filtered again by the filter F and sent to the coater.

FIG. 2 is an explanatory view according to claim 5 of the present invention. Photosensitive layer coating liquid supply tank 21 (heat insulation jacket 2)
2) and the protective layer coating liquid supply tank 3
1 (heated by the heat insulation jacket 32)
The coating solution for the photosensitive layer and the coating solution for the protective layer were respectively supplied to the heat exchanger 1
It is sent to the coater via 3 and 14 and is coated simultaneously.

As a coating method, any coating method may be used. In a photothermographic material, coating is usually performed on both sides of the support. For production efficiency, it is preferable to finish the coating on both sides in one line. Subsequently, it is preferable to apply and dry the photosensitive layer. Most commonly, photothermographic materials have a photosensitive layer and a protective layer on one side, and a backcoat layer on the other side.After coating and drying the backcoat layer, the photosensitive layer and the protective layer are coated simultaneously. It is preferable to apply and dry. As a coating method capable of simultaneous multilayer coating, an extrusion coating method having a plurality of slits, a slide coating method, or the like can be adopted. In this case, the temperature of the coating solution for the photosensitive layer and the protective layer is preferably substantially the same. The method of applying the back coat layer is not particularly limited, and an extrusion coating method, a slide coating method, a roll coating method, a knife coating method, or the like is employed. The drying method for each coated surface is not particularly limited, and a known drying method such as a hot air drying method or an infrared drying method can be used.

The details of the photothermographic material are described in, for example, US Pat. Nos. 3,152,904 and 3,457,0
No. 75, D.E. Morgan's "Dry Silver Photographic Materials" and D.M. Morgan and B. Disclosed in Shelly, "Thermal Treated Silver System", Imaging Processes and Materials.

Among them, in the present invention, an image is formed by thermally developing a photosensitive material at 80 to 140 ° C.
The feature is that no fixing is performed. Therefore, the silver halide and the organic silver salt remaining in the unexposed portions are not removed and remain in the photosensitive material as they are.

In the present invention, after the heat development,
The optical transmission density of the photosensitive material including the support at 00 nm is preferably 0.2 or less, more preferably 0.02 to 0.2. If it is less than 0.02, the sensitivity may be too low to use.

The silver halide particles in the photothermographic material function as an optical sensor. In order to suppress white turbidity after image formation and obtain good image quality, the average particle size is preferably smaller, 0.1 μm or less, more preferably 0.01 to 0.1 μm, particularly 0.02 to 0.0 μm.
8 μm is preferred. The grain size referred to here means the length of the edge of the 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, the diameter refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The silver halide grains are preferably monodispersed. Here, the monodispersion means that the degree of monodispersion obtained by the following equation is 40% or less. More preferably 30%
The particle size is particularly preferably 0.1 to 20%.

Monodispersity = (standard deviation of particle size / average value of particle size) × 100 In the invention, it is more preferable that the silver halide particles have an average particle size of 0.1 μm or less and are monodisperse particles. In this range, the granularity of the image is improved.

The shape of the silver halide grains is not particularly limited, but it is preferable that the ratio occupied by the Miller index [100] plane is high, and this ratio is 50% or more, more preferably 70%.
%, Particularly preferably 80% or more. The ratio of the Miller index [100] plane is [1] in the adsorption of the sensitizing dye.
T.11] utilizing the adsorption dependence of the [100] plane.
Tani: J. et al. Imaging Sci. , 29,16
5 (1985).

Another preferred form of silver halide is tabular grains. The term “tabular grains” as used herein means that the thickness in the vertical direction is hμm, where the square root of the projected area is the particle diameter rμm.
Means that the aspect ratio (r / h) is 3 or more. Among them, the aspect ratio is preferably 3 to 50. Further, the particle size is preferably 0.1 μm or less,
Further, the thickness is preferably 0.01 to 0.08 μm. These are disclosed in U.S. Pat. Nos. 5,264,337 and 5,314,798,
No. 5,320,958, and the like, and desired tabular grains can be easily obtained. When these tabular grains are used, the sharpness of an image is further improved.

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 is P.I. By Glafkids: Chimie et
Physique Photographique (P
aul Montel, 1967); F. D
by uffin: Photographic Emuls
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
et al: Making and Coatin
g Photographic Emulsion (T
He Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, a combination thereof, and the like. Is also good.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to the reducible silver source. The silver halide may be prepared by converting part or all of the silver in the organic acid silver to silver halide by the reaction of the organic acid silver and the halogen ion, or the silver halide may be prepared in advance. This may be added and added to the solution for preparing the organic silver salt, or a combination of these methods is possible, the latter being preferred. Generally, silver halide is preferably contained in an amount of 0.75 to 30% by mass based on the organic silver salt.

Silver halides include 6-1 of the periodic table of the elements.
It preferably contains an ion or a complex ion of a metal belonging to Group 0. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0, 1-, 2-, or 3-.
Or 4-. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

The following are typical specific examples of the transition metal coordination complex. 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^4- 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) (CN) _5] ^2- 13: [Re (NO) Cl (CN) 4 ] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) (CN) _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN)] ^2- 23: [R (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^2- 27: [Ir (NS) Cl _5] ^2-these metal ions or complex ions may be one kind, the same kind of metal or different metals may be used in combination of two or more. The content of these metal ions or complex ions is generally 1 × 10 5 per mole of silver halide.
^-9 to 1 × 10 ^-2 mol is appropriate, and preferably 1 × 10 ⁻² mol.
^-8 to 1 × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation.
In the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added to the silver halide grains as described in JP-A-63-29603 and JP-A-2-3062.
No. 36, No. 3-167545, No. 4-76534,
As described in JP-A-6-110146, JP-A-5-273683, and the like, the particles can be contained in the particles with distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be prepared by using water or a suitable organic solvent (alcohols, ethers, glycols,
Ketones, esters, amides, etc.). For example, an aqueous solution of a powder of a metal compound or an aqueous solution of a metal compound and sodium chloride or potassium chloride dissolved therein may be added during the particle formation. A method of adding and placing in a water-soluble silver salt solution or a water-soluble halide solution, or, when the silver salt solution and the halide solution are simultaneously mixed, adding as a third aqueous solution, and simultaneously mixing the three solutions to form a silver halide. A method of preparing grains, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or another silver halide grain doped with metal ions or complex ions in advance during silver halide preparation. And dissolving it. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and sodium chloride and potassium chloride are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

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.
It may or may not be desalted.

The photosensitive silver halide grains are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method can be used as is well known in the art. In addition, a noble metal sensitization method or a reduction sensitization method using a gold compound, platinum, palladium, iridium compound or the like can be used.

As the compounds preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 and the like can be used. it can. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides,
Diacyltellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te
Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used.

Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, and British Patent 6
Compounds described in JP 18,061 and the like can be preferably used.

Specific compounds of the reduction sensitization method include, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like in addition to ascorbic acid and thiourea dioxide. Can be used. When the pH of the emulsion is 7 or more or p
Reduction sensitization can be achieved by ripening while keeping Ag at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

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, particularly a long chain (10 to 30 carbon atoms, preferably The aliphatic carboxylic acids and nitrogen-containing heterocycles of 15 to 25) are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful.

Examples of suitable silver salts are described in Research Disclosure (hereinafter abbreviated as RD) 17029 and 29996, and include the following: organic acid salts (gallic acid, oxalic acid, behenic acid) Arachidic acid, stearic acid, palmitic acid, lauric acid and the like); carboxyalkylthiourea salt of silver (1- (3-carboxypropyl) thiourea;
1- (3-carboxypropyl) -3,3-dimethylthiourea and the like; aldehydes and hydroxy-substituted aromatic carboxylic acids [aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (salicylic acid, benzoic acid, 3, 5-dihydroxybenzoic acid,
5,5-thiodisalicylic acid)] and a silver complex or a complex of thiones [3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thione; And 3-carboxymethyl-4-thiazoline-2-thione)]; imidazole, pyrazole,
Urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-
Complexes or salts of silver and a nitrogen acid selected from triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, silver arachidate and / or
Or 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 can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (sodium behenate, sodium arachidate, etc.) is prepared by adding an alkali metal salt (sodium hydroxide, potassium hydroxide, etc.) to an organic acid, and then controlled by a controlled double jet. A soap and silver nitrate are added to produce organic silver salt crystals. At that time, silver halide grains may be mixed.

The organic silver salt has an average particle size of 1 μm or less,
It is preferably 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 0.0
It is preferably from 1 to 0.8 μm, particularly preferably from 0.05 to 0.5 μm. The monodispersion has the same meaning as in the case of silver halide, and preferably has a monodispersity of 1 to 30. It is more preferable that the organic silver salt is monodisperse particles having an average particle size of 1 μm or less. By setting the content in this range, an image having a high density can be obtained.

Further, the organic silver salt has a tabular grain of 6% of the total organic silver.
It is preferable to have 0% or more. In the present invention, the tabular grains refer to those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between an average particle diameter and a thickness, which is represented by the following formula.

AR = average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, the organic silver crystals are dispersed and pulverized with a binder, a surfactant and the like using a ball mill or the like. can get.

In order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably 0.5 to 2.2 g / 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 50% or less by mass, preferably 25% or less, and more preferably 0.1 to 15%.

The photothermographic material preferably contains a reducing agent. Examples of suitable reducing agents are described in US Pat.
0,448, 3,773,512, 3,59
No. 3,863, and RD17029 and 29963, and include the following. Aminohydroxycycloalkenone compound (2-hydroxypiperidino-2-
Aminoreductone esters (such as piperidinohexose reductone monoacetate) as precursors of reducing agents; N-hydroxyurea derivatives (N-
hydrazones of aldehydes or ketones (anthracene aldehyde phenylhydrazone); phosphamide phenols; phosphamide anilines; polyhydroxybenzenes (hydroquinone, t-butylhydroquinone, p-methylphenyl-N-hydroxyurea);
i-propylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (benzenesulfhydroxamic acid); sulfonamidoanilines (4- (N-methanesulfonamido) aniline); 2-tetra Zolylthiohydroquinones (2-
Methyl-5- (1-phenyl-5-tetrazolylthio)
Hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-tetrahydroquinoxaline); amidooxins; azines (combinations of aliphatic carboxylic acid arylhydrazides and ascorbic acid); polyhydroxybenzenes and hydroxylamines Combinations, reductones and / or hydrazines; hydroxanoic acids; combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives; bis-β-naphthol and 1,3-
5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (2,6-dimethoxy-3,5-dicarbo) Ethoxy-1,4-dihydropyridine); bisphenols (bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol), 2,2-bis ( 4-hydroxy-3
-Methylphenyl) propane, 4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol)), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones.

Particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0049]

Embedded image

In the formula, R ₁ is a hydrogen atom or a group having 1 carbon atom.
Represents an alkyl group (butyl, 2,4,4-trimethylpentyl, etc.), wherein R ₂ and R ₃ each have 1 carbon atom
To 5 alkyl groups (methyl, ethyl, t-butyl, etc.).

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

[0052]

Embedded image

[0053]

Embedded image

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

Binders suitable for photothermographic materials are transparent or translucent and generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and poly (vinyl). Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate,
Polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylate, polyvinyl chloride, polymethacrylic acid, copoly (styrene-maleic anhydride),
Copoly (styrene-acrylonitrile), copoly (styrene-butadiene), polyvinyl acetals (polyvinyl formal, polyvinyl butyral, etc.), polyesters, polyurethanes, phenoxy resins, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters And polyamides, which may be hydrophilic or non-hydrophilic. In order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer can be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In order to increase the speed of thermal development, the photosensitive layer
The amount of binder is 1.5 to 10 g / m ^TwoPreferably
New More preferably, 1.7 to 8 g / m^TwoIt is. 1.
5g / m^TwoBelow, the density of the unexposed part increases significantly,
May not withstand use.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and a matting agent is preferably provided on the surface of the light-sensitive material in order to prevent the image after heat development from being damaged. The matting agent is preferably contained in a weight ratio of 0.5 to 30% with respect to all binders on the emulsion layer side.

The material of the matting agent used may be either an organic substance or an inorganic substance. As inorganic materials, Swiss Patent 3
Silica described in No. 30,158, French Patent 1,29
Glass powder described in US Pat.
Alkaline earth metals or carbonates such as cadmium and zinc described in 3,181 and the like can be used as a matting agent. Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent 625,451 and British Patent 981,198, etc .;
4-3643, polystyrene or polymethacrylate described in Swiss Patent 330,158, etc., polyacrylonitrile described in U.S. Pat. No. 3,079,257, U.S. Pat. No. 3,022,1
An organic matting agent such as polycarbonate described in No. 69 or the like can be used.

The shape of the matting agent may be either regular or irregular, but a regular and spherical shape is preferably used. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent preferably has an average particle size of 0.5 to 10 μm, more preferably 1.0 to 8.0 μm.
m. The variation coefficient of the particle size distribution is 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) × 10
The matting agent can be contained in any constituent layer, but is preferably a constituent layer other than the photosensitive layer in order to achieve the object of the present invention, and more preferably the outermost layer as viewed from the support. It is. The method for adding the matting agent may be a method in which the matting agent is dispersed in a coating solution in advance and a method in which the matting agent is sprayed before the drying is completed after applying the coating solution. When a plurality of types of matting agents are added, both methods may be used in combination.

The heat-developable light-sensitive material forms a photographic image by a heat-development process and suppresses the color tone of the silver source (organic silver salt) which can be reduced, the photosensitive silver halide, the reducing agent and, if necessary, the silver. It is usually preferable that the toning agent be contained in a state dispersed in an (organic) binder matrix.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (80 to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction (redox) 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. Silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas,
An image is formed. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer may be formed 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.

The dye used may be any compound as long as it has a desired absorption in a desired wavelength range. For example, JP-A-59-6481 and JP-A-59-18 can be used.
2436, U.S. Pat. Nos. 4,271,263 and 4,5
No. 94,312, European Patent Publication Nos. 533,008, 6
52,473, JP-A-2-216140, 4-3
No. 48339, No. 7-191432, No. 7-3018
Compounds described in No. 90 and the like are preferably used.

These non-photosensitive layers preferably contain the above-mentioned binder and matting agent, and may further contain a slip agent such as a polysiloxane compound, wax or liquid paraffin.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be configured as a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer in order to adjust the gradation.

It is preferable to add a toning agent to the photothermographic material for the purpose of improving the silver tone after development. Examples of suitable toning agents are disclosed in RD 17029 and include:

Imides (phthalimide and the like); cyclic imides, pyrazolin-5-ones and quinazolinones (succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-
Thiazolidinedione, etc.); naphthalimides (N-hydroxy-1,8-naphthalimide, etc.); cobalt complexes (hexamine trifluoroacetate of cobalt, etc.); mercaptans (3-mercapto-1,2,4-
N- (aminomethyl) aryldicarboximides (such as N- (dimethylaminomethyl) phthalimide); combinations of blocked pyrazoles, isothiuronium derivatives and certain photobleaches (N,
N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate, etc.), and 2- (tribromomethylsulfonyl) A) benzothiazole combination); merocyanine dye (3-ethyl-5-((3-ethyl-2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2, 4-oxazolidinedione, etc.);
Phthalazinone, phthalazinone derivatives or metal salts of these derivatives (4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazine Dione, etc.); a combination of phthalazinone and a sulfinic acid derivative (6
-Chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); a combination of phthalazine + phthalic acid; phthalazine (including an adduct of phthalazine) with maleic anhydride and phthalic acid , 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (phthalic acid,
A combination with at least one compound selected from 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinediones, benzoxazine, naltoxazine derivatives; benzoxazine-2,
4-diones (1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (2,4
-Dihydroxypyrimidine) and tetraazapentalene derivatives (3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene).

Preferred toning agents are phthalazone or phthalazine. To suppress or promote development, to control development, to improve the spectral sensitization efficiency, to improve the storage stability before and after development, and the like, mercapto compounds,
A disulfide compound and a thione compound can be contained.

When a mercapto compound is used, it may have any structure, but it may be Ar-SM, Ar-SS-
Those represented by Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably as a heteroaromatic ring, benzimidazole, naphthymidazole, benzothiazole, naphthothiazole, benzoxazole,
Naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole,
Triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine,
Purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, a halogen atom (chlorine, bromine), a hydroxyl group, an amino group, a carboxyl group, an alkyl group (having one or more carbon atoms, preferably 1 to 4 carbon atoms) and an alkoxy group. (A substituent having one or more carbon atoms, preferably 1 to 4 carbon atoms).

Specific examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2 , 4-triazole, 2-
Mercaptoquinoline, 8-mercaptopurine, 2,3
Examples include 5,6-tetrachloro-4-pyridinethiol, 4-hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole, and the like, but the invention is not limited thereto.

The photothermographic material of the present invention may contain an antifoggant. What is known as the most effective antifoggant is mercury ion. Regarding the use of mercury compounds as antifoggants in photosensitive materials,
For example, it is disclosed in U.S. Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly.

As the non-mercury type antifoggant, for example, antifoggants as disclosed in US Pat. Nos. 4,546,075, 4,452,885 and JP-A-59-57234 are preferable. Particularly preferred non-mercury antifoggants are described in U.S. Pat.
No. 6,999, the compound -C (X
₁ ) _{1 represented by} (X ₂ ) (X ₃ ) (where X ₁ and X ₂ are each a halogen atom, X ₃ is a hydrogen atom or a halogen atom)
It is a heterocyclic compound having the above substituent. Examples of suitable antifoggants include JP-A-9-288328,
The compounds described in paragraph numbers [0030] to [0036] are exemplified. Further, as another preferred example of the antifoggant, JP-A-9-90550, paragraph [00]
62] to [0063].
Further, other suitable antifoggants are disclosed in US Pat.
28,523 and European Patents 600,587, 60
Nos. 5,981 and 631,176.

The photothermographic materials include, for example, those disclosed in
140335, 63-15245, 63-15
Nos. 9841, 63-231437, 63-259
No. 651, No. 63-304242, U.S. Pat.
9,414, 4,740,455, 4,75
Sensitizing dyes described in 1,175, 4,835,096 and the like can be used.

Useful sensitizing dyes for use in the present invention are described, for example, in RD17643, page 23, section IV-A (Dec. 1978
Mon)) or in the literature cited.
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, Japanese Patent Application Laid-Open No. 60-162247 and Japanese Patent Application Laid-Open No. 2-486
No. 35, U.S. Pat. No. 2,161,331, West German Patent 93
Simple merocyanines described in JP-A-6,071 and JP-A-5-11389; for helium-neon laser light sources, JP-A-50-62425 and JP-A-54-1872.
No. 6, 59-102229, etc .; merocyanines described in JP-A-7-287338; and JP-B-48-42172 for LED light sources and infrared semiconductor laser light sources. Id. 51-960
No. 9, 55-39818, JP-A-62-28434.
No. 3, JP-A-2-105135 and the like; tricarbocyanines described in JP-A-59-19032 and JP-A-60-80841 for an infrared semiconductor laser light source; JP-A-59-19224
2, the general formulas (IIIa) and (I) of JP-A-3-67242.
The dicarbocyanines containing a 4-quinoline nucleus described in IIb) are advantageously selected.

Further, the wavelength of the infrared laser light source is 750 n
m or more, more preferably 800 nm or more.
-182639, 5-341432, Tokuhei 3-
Nos. 10931 and 6-52387, U.S. Pat.
Sensitizing dyes described in JP-A No. 1,866 and JP-A-7-13295 are preferably used. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer and other forming layers. For example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like may be used. As these additives and the other additives described above, compounds described in RD17029 (June 1978, pages 9 to 15) can be preferably used.

The support used for the photothermographic material is preferably a plastic film (polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate, polyethylene naphthalate) in order to prevent deformation of the image after the development processing. Among them, a preferred support is a plastic (SP) containing polyethylene terephthalate (PET) and a styrene polymer having a syndiotactic structure.
And the support of S). The thickness of the support is 50
It is about 300 μm, preferably 70 to 180 μm.

Further, a heat-treated plastic support may be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming the support and before the photosensitive layer is coated, the glass transition point of the support is 30 ° C. or more (preferably 35 ° C. or more, more preferably 40 ° C. or more). It is better to heat at a high temperature. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

Next, the plastic used will be described. PET is a polyester in which the components of the polyester are all composed of polyethylene terephthalate. In addition to polyethylene terephthalate, terephthalic acid, naphthalene-2,6-dicarboxylic acid, isophthalic acid, butylene dicarboxylic acid, 5-sodium sulfoisophthalic acid,
Adipic acid and the like, a modified polyester component of ethylene glycol, propylene glycol, butanediol, cyclohexane dimethanol, etc. as a glycol component,
It may be a polyester containing 10 mol% or less of the total polyester.

SPS is different from ordinary polystyrene (atactic polystyrene) and is a polystyrene having steric regularity. The regular stereoregular structure part of SPS is called a racemo chain, and it is preferable that the number of regular parts is two, three, five or more, and in the present invention, the racemo chain is 2 85% in chain
It is preferable that the ratio is 75% or more for three chains, 50% or more for five chains, and 30% or more for more chains. SPS
Can be carried out according to the method described in JP-A-3-131843.

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

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be included in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat layer, and the like. The conductive compounds described in U.S. Pat. No. 5,244,773, columns 14 to 20 are preferably used.

[0086]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. Unless otherwise specified, “%” in the examples represents “% by mass”.

<Preparation of Coating Solution for Photosensitive Layer> (Preparation of Silver Halide Emulsion A) 1.3 kg of inert gelatin and 160 ml of 1 mol / L aqueous potassium bromide solution were dissolved in 40 L of water, and the pH was adjusted to pH 3.0 at 35 ° C. After combining, 39 L of an aqueous solution containing 4.5 kg of silver nitrate and (98 /
2) An aqueous solution containing potassium bromide and potassium iodide in a molar ratio and [Ir (NO) Cl ₅ ] salt were added in an amount of 1 × 1 per mole of silver.
0 ^-6 mol and silver chloride rhodium salt per mole 1 × 1
0 ^-4 mol, it was added at a controlled double jet method while maintaining the pAg7.7. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (stabilizer) was added, the pH was adjusted to 5 with sodium hydroxide, and the average particle size was 0.06 μm and the projected diameter area was Cubic silver iodobromide grains having a variation coefficient 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, and then 4.2 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5 to obtain a silver halide emulsion.

Next, 3 × 10 3 per mol of silver was added to this emulsion.
^-2 mol of sodium thiosulfate was added and reacted at 55 ° C. for 60 minutes for chemical sensitization. Thereafter, the temperature of the emulsion was lowered to room temperature, and a photosensitive silver halide emulsion A was prepared by adding an antifoggant and the like described below, and chemically sensitized with chloroauric acid and inorganic sulfur.

(Preparation of Na Behenate Solution) In 40 L of pure water, 1.4 kg of behenic acid, 0.42 kg of arachidic acid and 0.25 kg of stearic acid were dissolved at 90 ° C. Next, 4.1 L of a 1.5 mol / L aqueous sodium hydroxide solution was added while stirring at a high speed. Next, after adding 39 L of concentrated nitric acid, the mixture was cooled to 55 ° C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion) 640 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with an aqueous sodium hydroxide solution.
6.2 L of a silver / mol / L silver nitrate solution was added, and the mixture was stirred for 20 minutes, followed by ultrafiltration to remove water-soluble salts.

The obtained silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After forming a floc of the dispersion, water was removed, and washing and removal of water were repeated six times, and then dried.

(Preparation of Photosensitive Emulsion) Polyvinyl butyral (average molecular weight: 3,000) was added to the above preform emulsion.
23 kg of methyl ethyl ketone solution (17%) and 4.5 kg of toluene were gradually added and mixed.
Dispersed with si.

(Preparation of Coating Solution for Photosensitive Layer) Using this dispersion, a coating solution for a photosensitive layer having the following composition was prepared.

Composition of coating solution for photosensitive layer Methyl ethyl ketone 70% Photosensitive emulsion dispersion 22.8% Sensitizing dye-1 (0.1% methanol solution) 0.16% Pyridinium bromide perbromide (6% methanol solution) 0.29 % Calcium bromide (0.1% methanol solution) 0.16% Antifoggant-1 (10% methanol solution) 0.11% 2- (4-chlorobenzoyl) benzoic acid (12% methanol solution) 0.87 % 2-mercaptobenzimidazole (1% methanol solution) 1.05% tribromomethylsulfoquinoline (5% methanol solution) 1.62% Developer A-4 (20% methanol solution) 2.82%

[0096]

Embedded image

(Preparation of coating solution for protective layer) A coating solution for protective layer having the following composition was prepared.

Composition of Coating Solution for Protective Layer Methyl Ethyl Ketone 82.7% Cellulose Acetate 4.61% Methanol 11.0% Phthalazine 0.50% 4-Methylphthalic acid 0.36% Tetrachlorophthalic acid 0.30% Tetrachlorophthalic anhydride Product 0.34% matting agent (monodispersity 10%, silica having an average particle size of 4 μm) 0.14% sodium p-nonylbenzenesulfonate 0.02% <Coating test 1> The viscosities of the layer coating solution and the protective layer coating solution were adjusted to 0.228 Pa · s and 0.184 Pa · s, respectively, by adjusting the amount of the solvent. Biaxially stretched heat-fixed PE with a thickness of 100 μm
The film was laminated on a T film by discharging from a slit of a film extrusion type die coater. In addition, the photosensitive layer,
The target wet film thickness of the protective layer is 100 μm and 40 μm, respectively.
m, and coating and drying were performed at a line speed of 20 m / min. Further, as the application liquid heating means, the apparatus shown in the above-mentioned "liquid preparation liquid supply apparatus" was used.

The sensitometry and coating unevenness were evaluated. <Coating Test 2> Under the photosensitive layer preparation conditions of Example 4 shown in Table 1, coating was performed in the same manner as in coating test 1 under the conditions shown in Table 2, and coating unevenness was evaluated.

<< Sensitometry >> Each coated photothermographic material is cut into 3.5 cm × 15 cm, and is exposed by a laser sensitometer equipped with a 810 nm diode.
After processing (thermal development) at 15 ° C. for 15 seconds, the fog (D _min ) and sensitivity (reciprocal of the ratio of the amount of exposure that gives a density higher than D _min 1.0) of the obtained image were measured. The sensitivity of Example 1 was set to 100
As relative sensitivity.

<< Coating Unevenness >> The coated surface of each coated photothermographic material sample was visually evaluated in three steps.

: No coating unevenness was generated at all. Δ: Scale-like unevenness was found, but practically acceptable. X: Many unevenness was generated, and the sample was not practical. The results are shown in Tables 1 and 2.

[0103]

[Table 1]

The embodiment in which the coating solution for the photosensitive layer is stagnated and stored at a low temperature, and is heated and applied within 3 hours before the application, has higher sensitivity, lower fog, and less occurrence of uneven coating than the comparative example.

[0105]

[Table 2]

In the examples in which the difference in the temperature of the coating solution between the photosensitive layer and the protective layer is within the range of the present invention, no coating unevenness occurs.

[0107]

According to the present invention, a heat-developable photographic light-sensitive material having less fog and good sensitivity can be stably produced without generation of coating unevenness.

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining claim 1 of the present invention.

FIG. 2 is a schematic diagram for explaining claim 5 of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 stagnant tank 2 cooling jacket 3, 13, 23 heat exchanger 4 coater 5 heat-developable photosensitive material support 11 liquid feed tank 12, 22, 32 heat retention jacket 21 photosensitive layer coating liquid feed tank 31 protective layer coating liquid feed Liquid tank F Filter P Pump

Claims (6)

[Claims] In a method for producing a heat-developable photographic material containing an organic silver salt, photosensitive silver halide particles and a reducing agent on a support, the photosensitive solution is stagnated at a low temperature, stored and coated before coating. A method for producing a heat-developable photographic light-sensitive material, wherein the material is heated and applied within an hour. 2. A photothermographic material according to claim 1, wherein the temperature difference ΔT (° C.) between the temperature of the photosensitive solution at the time of low temperature stagnation and the temperature of the photosensitive solution after heating is 0 to 20 ° C. Manufacturing method. 3. The temperature T _L (° C.) of the photosensitive solution after the heating is equal to T _Air −10 ≦ T _L ≦ with respect to the coating room atmosphere temperature T _Air (° C.).
2. The method for producing a photothermographic material according to claim 1, wherein T _Air +10. 4. The photosensitive solution temperature T _L (° C.) after the heating is 10 ≦.
2. The method for producing a photothermographic material according to claim 1, wherein T _L ≤30. 5. A method for producing a photothermographic material comprising an organic silver salt, photosensitive silver halide grains and a reducing agent on a support, wherein at least one photosensitive layer (image forming layer) is provided.
And at least one protective layer are simultaneously coated, the photosensitive layer coating liquid temperature _TL1 (° C) and the protective layer coating liquid temperature _TL2 (° C)
Wherein the difference in the temperature of the coating solution is -5 ≦ _TL1 − _TL2 ≦ 5. 6. A photothermographic material which is produced by the production method according to claim 1. Description: