EP1217432A2

EP1217432A2 - Silver halide photographic light-sensitive material and method for processing the same

Info

Publication number: EP1217432A2
Application number: EP01129749A
Authority: EP
Inventors: Kazuki Fuji Photo Film Co. Ltd. Yamazaki; Mitsunori Fuji Photo Film Co. Ltd. Hirano; Shoji Fuji Photo Film Co. Ltd. Yasuda
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Corp
Priority date: 2000-12-14
Filing date: 2001-12-13
Publication date: 2002-06-26
Anticipated expiration: 2021-12-13
Also published as: DE60129919T2; ATE370443T1; EP1217432A3; EP1217432B1; DE60129919D1

Abstract

A silver halide photographic light-sensitive material is disclosed, comprising a support having thereon at least one silver halide emulsion layer containing at least one light-sensitive silver halide emulsion, wherein a hydrophilic colloid layer which is the same or different from the silver halide emulsion layer contains solid grains in an amount of increasing the integrated value of spectral reflectance of the light-sensitive material in the wavelength region of 850 to 1,000 nm, by 1.5% or more, and a method for processing a silver halide photographic light-sensitive material is disclosed, comprising exposing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support using an image setter, transporting the light-sensitive material by an automatic transportation system and developing the light-sensitive material in an automatic developing machine, wherein a hydrophilic colloid layer which is the same or different from said silver halide emulsion layer contains solid grains in an amount of increasing the integrated value of spectral reflectivity of the light-sensitive material in the wavelength region of 850 to 1,000 nm by 1.5% or more.

Description

FIELD OF THE INVENTION

The present invention relates to a silver halide photographic light-sensitive material, more specifically, the present invention relates to a silver halide photographic light-sensitive material for use in the photomechanical process.

BACKGROUND OF THE INVENTION

In the field of graphic arts, in order to obtain good reproduction of a halftone image in continuous gradation or good reproduction of a line image, a system of ensuring ultrahigh contrast (particularly, γ of 10 or more) photographic properties is necessary.
An image formation system capable of obtaining ultrahigh contrast photographic properties by the development with a processing solution having good storage stability has been demanded. To meet this requirement, as described in U.S. Patents 4,166,742, 4,168,977, 4,221,857, 4,224,401, 4,243,739, 4,272,606 and 4,311,781, a system of forming an ultrahigh contrast negative image having a γ value in excess of 10 has been proposed, where a surface latent image-type silver halide photographic light-sensitive material having added thereto a specific acylhydrazine compound is processed with a developer containing 0.15 mol/λ or more of a sulfurous acid preservative and having a pH of 11.0 to 12.3. This new image formation system is characterized in that silver iodobromide or silver iodochlorobromide can be used, though only silver chlorobromide having a high silver chloride content can be used in conventional ultrahigh contrast image formation systems. Also, this new system is characterized in that a large amount of sulfurous acid preservative can be contained and therefore, relatively good storage stability is achieved, though conventional lith developers can contain only a very small amount of sulfurous acid preservative.
Furthermore, in the field of graphic arts, accompanying recent requirements for low-amount replenishment and rapid processing, reduction in the coated silver amount is demanded. To meet this requirement, studies are being aggressively made by ones skilled in the art to develop a technique for forming silver halide grains as fine grains and thereby achieving high sensitivity and high contract. By the formation of fine grains, covering power (blackened density per unit silver amount) can be elevated and the amount of silver used can be reduced.
On the other hand, an automatic transportation system from the light-sensitive supply cassette to an exposure machine and an automatic developing machine is becoming popular. According to this system, the film is detected by some optical sensors disposed inside the exposure machine and the like. The optical sensor in general uses a light source having a wavelength in the infrared region outside the wavelength region to which the light-sensitive material is sensitive and detects the film by the scattering or the like due to silver halide grains.
The optical sensor used for this purpose is roughly classified into two types, one is a "transmission type" which detects the light emitted from a light emitting device and transmitted and another is a "reflection type" which detects the reflected light. In the case of a transmission-type sensor, the detection reliability is hither than the reflection-type sensor, however, since a light emission part and a light-receiving part are independent from each other, two sensors are necessary and this disadvantageously costs highly. On the other hand, the reflection-type sensor is characterized in that since the light emission part and the light-receiving part can be integrated, the installation is easy and simple and this is advantageous in view of the cost.
The reflection-type sensor used for light-sensitive materials usually recognizes the film in such a manner that the infrared light emitted from the light emission part of the sensor is scattered mainly by the collision against silver halide grains and the light-receiving part detects the scattered light. Accordingly, when the coated silver amount is reduced or the size of silver halide grain is made smaller so as to attain low-amount replenishment or the like, the scattering on silver halide grains is reduced and the amount of light received in the sensor decreases, as a result, the light-sensitive material is not recognized. Also in the case of the transmission-type sensor, a method for coping with the reduction in the detection power of the sensor due to the enhancement of transmittance through a film accompanying the silver saving or reduction in the grain size is known, for example, in JP-A-63-131135 and JP-A-8-95198 (The term "JP-A" as used herein means an unexamined published Japanese Patent application). However, the object of these methods is to reduce the transmittance of infrared ray and the countermeasure for the reflection-type sensor is not studied. A method for enhancing the detection power of a reflection-type infrared sensor is described in JP-A-10-221809, however, this method has a problem in that the film is increased in the transparency, so-called haze.
Furthermore, when silver halide grains are formed as fine grains, the infrared scattering strength of grain decreases and therefore, the sensor may fail in the detection. Thus, improvements are being demanded.

SUMMARY OF THE INVENTION

A first object of the present invention is to provide a silver halide photographic light-sensitive material free of troubles in the sensor of an image setter, exhibiting good haze and having capability of ensuring good photographic performance even with an exhausted developer.
A second object of the present invention is to provide a processing method using the above-described silver halide light-sensitive material and reduced in the change of performance due to running.
These objects are attained by:
(1) a silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer containing at least one light-sensitive silver halide emulsion, wherein a hydrophilic colloid layer which is the same or different from the silver halide emulsion layer contains solid grains in an amount of increasing the integrated value of spectral reflectance of the light-sensitive material in the wavelength region of 850 to 1,000 nm, by 1.5% or more;
(2) the silver halide photographic light-sensitive material as described in (1) above, wherein the refractive index of the solid grain is 1.54 or more;
(3) the silver halide photographic light-sensitive material as described in (1) or (2) above, wherein the solid grain is a substantially light-insensitive silver halide grain;
(4) the silver halide photographic light-sensitive material as described in (3) above, wherein the solid grain is a substantially light-insensitive silver halide grain and the light-insensitive silver halide grain comprises a tabular grain having an average grain thickness of 0.02 to 0.20 µm;
(5) the silver halide photographic light-sensitive material as described in any one of (1) to (4) above, wherein the coated silver amount of the light-sensitive silver halide emulsion is 3.0 g/m² or less;
(6) the silver halide photographic light-sensitive material as described in any one of (1) to (5) above, wherein the solid grain is a substantially light-insensitive silver halide grain and the light-insensitive silver halide emulsion containing the light-insensitive silver halide grains in an amount of 10 to 200 mg/m² as silver is incorporated into a hydrophilic colloid layer to reduce the transmittance of the light-sensitive material at 900 to 950 nm, in terms of the absolute value, by 5% or more on average;
(7) the silver halide photographic light-sensitive material as described in any one of (1) to (6) above, wherein the silver halide emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative;
(8) a method for processing a silver halide photographic light-sensitive material, comprising exposing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support using an image setter, transporting the light-sensitive material by an automatic transportation system and developing the light-sensitive material in an automatic developing machine, wherein a hydrophilic colloid layer which is the same or different from the silver halide emulsion layer contains solid grains in an amount of increasing the integrated value of spectral reflectivity of the light-sensitive material in the wavelength region of 850 to 1,000 nm by 1.5% or more;
(9) the method for processing a silver halide photographic light-sensitive material as described in (8) above, wherein the refractive index of the solid grain is 1.54 or more;
(10) the method for processing a silver halide photographic light-sensitive as described in (8) or (9) above, wherein the solid grain is a substantially light-insensitive silver halide grain;
(11) the light-sensitive silver halide photographic light-sensitive material as described in (10) above, wherein the solid grain is a substantially light-insensitive silver halide grain and the light-insensitive silver halide grain comprises a tabular grain having an average grain thickness of 0.02 to 0.20 µm;
(12) the silver halide photographic light-sensitive material as described in any one of (8) to (11) above, wherein the coated silver amount of the light-sensitive silver halide emulsion is 3.0 g/m² or less;
(13) the method for processing a silver halide photographic light-sensitive material as described in any one of (1) to (12) above, wherein the solid grain is a substantially light-insensitive silver halide grain and the light-insensitive silver halide emulsion containing the light-insensitive silver halide grains in an amount of 10 to 200 mg/m² as silver is incorporated into a hydrophilic colloid layer to reduce the transmittance of the light-sensitive material at 900 to 950 nm, in terms of the absolute value, by 5% or more on average;
(14) the method for processing a silver halide photographic light-sensitive material as described in any one of (8) to (13) above, wherein the silver halide emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative; and
(15) the method for processing a silver halide photographic light-sensitive material as described in any one of (8) to (14) above, wherein the developer replenishing amount is 250 ml/m² or less.

BRIEF DESCRIPTION OF THE DRAWING

Fig. 1 is a view showing absorption spectra in the emulsion layer side and in the back side, respectively, in Examples of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, the average integrated value of spectral reflectance at 850 to 1,000 nm of the light-sensitive material can be simply and easily measured by a spectrophotometer. For example, using a spectrophotometer U3500 (manufactured by Hitachi, Ltd.) in which an integrating sphere is disposed in the light-receiving part, a probe ray is applied to a light-sensitive material while attaching black paper on the back surface and the reflected light from the light-sensitive material is integrated by the integrating sphere, wherefrom the value is determined.
In the present invention, a light-sensitive silver halide emulsion layer or other hydrophilic colloid layer contains solid grains which bring about increase of 1.5% or more in the average integrated value of the spectral reflectance at 850 to 1,000 nm when added as compared with the case where these solid grains are not added. The increase is preferably 2% or more and on considering worsening of haze, preferably 5% or less.
The construction material of the solid grain having a reflective property which brings about increase in the integrated value of reflectance by addition is not particularly limited and, for example, an inorganic grain or a dispersion of organic material may be used irrespective of the kind insofar as it does not affect the photographic performance, however, those having a refractive index of 1.54 or more are preferred.
The refractive index as used in the present invention means a relative refractive index to air. Although the refractive index subtly changes depending on the wavelength of light, the temperature or the like, an Na-D line (λ=589.3nm) is employed as the light source and nD20 which is a value at 20°C is used. In the case of a solid, when the refractive index is small depending on the direction due to anisotropy of the crystal, a largest value is designated as the value of the substance.
Specific examples of the compound having a refractive index of 1.54 or more include a variety of compounds such as silver halide, magnesium oxide, alumina, calcite, metal oxides represented by ZrO₂, SnO₂, ZnO, Al₂O₃ and TiO₂, barium sulfate, polystyrene and vinylidene chloride.
The refractive index is preferably from 1.6 to 3.0, more preferably from 1.7 to 3.0.
The preferred grain size of solid grains varies depending on the refractive index but is preferably from 2 nm to 20 µm, more preferably from 5 nm to 10 µm. The grain size of solid grains as used herein means a grain size determined by the light scattering method and specifically, the average grain size is determined using ELS-800 manufactured by Otsuka Denshi.
The amount of solid grains added is preferably from 10 mg/m² to 1 g/m², more preferably from 20 to 500 mg/m².
The site to which solid grains are added is not particularly limited and the solid grains may be added to an emulsion layer, between an emulsion layer and a support, to an emulsion protective layer, to a backing layer or into a support. However, the solid grains are preferably added to an uppermost layer on the surface where light emitted from an infrared sensor is directly applied. Also, a protective layer may be provided on the layer where the solid grains are added.
The solid grain must be in the grain form in the light-sensitive material and although it may vary depending on the dispersion method of fine grins, the water solubility of the solid grain is preferably lower. Also, the solid grain preferably has a property of dissolving in a processing solution.
Among those solid grains, silver halide is preferred in the present invention, and tabular and substantially light-insensitive silver halide grain is more preferred.
The light-insensitive silver halide grain for use in the present invention may have any halogen composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide, however, the AgBr content is preferably 50 mol% or more, more preferably 80 mol% or more.
The light-insensitive silver halide grain may have any shape of cubic, tetradecahedral, octahedral, amorphous and platy forms but preferably has a cubic or tetradecahedral form.
The light-insensitive silver halide grain for use in the present invention can be prepared using a method described in P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), and V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press (1964).
The substantially light-insensitive silver halide grain for use in the present invention means a silver halide grain of which sensitivity in the blue region is 1/10 or less of the sensitivity of light-sensitive silver halide grain for use in the light-sensitive material of the present invention The light-insensitive silver halide grain is preferably not spectrally sensitized. The light-insensitive silver halide grain for use in the present invention can be subjected to surface modification such as doping with metal complex or chemical sensitization which are described later in the item of light-sensitive silver halide.
The light-insensitive silver halide grain for use in the present invention is preferably monodisperse grains and the coefficient of variation represented by {(standard deviation of grain size)/(average grain size)}×100 is preferably 20% or less, more preferably 15% or less. For the sake of convenience, the grain size of silver halide grain is expressed, in the case of a cubic grain, by the length of edge and in the case of other grains (octahedral, tetradecahedral, tabular or the like), the grain size is calculated as a equivalent-circle diameter of the projected area. The average grain size of silver halide emulsion grains is preferably 0.1 µm or more, more preferably from 0.2 to 10 µm, still more preferably from 0.5 to 1.5 µm.
The light-insensitive silver halide grains for use in the present invention is used in an amount of giving a decrease of 5% or more on average in the spectral transmittance at 900 to 950 nm when the light-insensitive silver halide grains are added, though this may vary depending on the grain size. The amount in terms of silver is from 10 to 200 mg/m². The spectral transmittance at 900 to 950 nm can be measured by a general spectrophotometer. For example, the spectral transmittance can be measured using a spectrophotometer U3500 (manufactured by Hitachi, Ltd.) in which an integrating sphere is disposed in the light-receiving part, by disposing a light-sensitive material sample at the entrance port of the integrating sphere.
The majority of silver halide grains which can be used in the light-insensitive silver halide emulsion for use in the present invention must have a tabular form. The term "silver halide tabular grain" as used herein is a generic term of silver halide grains having one twin plane or two or more parallel twin planes. The twin plane means a (111) face when ions at all lattice points on both sides of the (111) face are in the mirror image relationship. The tabular grain is, when the grain is viewed from above, in the triangular, tetragonal or hexagonal form or in the circular form as a rounded triangle, tetragon or hexagon. The triangular, hexagonal or circular grain has triangular, hexagonal or circular external surfaces, respectively, which are parallel with each other.
The thickness of a grain can be easily determined by vapor-depositing a metal together with a latex for control on a grain from the oblique direction, measuring the length of the shadow thereof on a photograph taken through an electron microscope and calculating the thickness by referring to the length of the shadow of the latex. In the light-insensitive emulsion for use in the present invention, 50% or more of the entire projected area is occupied by tabular grains having an average thickness of 0.02 to 0.20 µm.
In all grains of the light-insensitive emulsion for use in the present invention, the coefficient of variation in the equivalent-circle diameter is preferably 40% or less, more preferably 25% or less, still more preferably 15% or less.
The tabular silver halide emulsion can be easily prepared by referring to a method described, for example, in JP-A-58-127927, JP-A-58-113927 and JP-A-58-113928. Also, the tabular silver halide emulsion can be obtained by a method where seed crystals of allowing the presence of tabular grains in a concentration of 40% or more by weight are formed in an atmosphere at a relatively low pBr value of 1.3 or less and while keeping the pBr value on the same level, silver and a halogen solution are simultaneously added to grow the seed crystals. In this growth process, the silver and halogen solution are preferably added not to cause the generation of a new crystal nucleus. The size of the silver halide tabular grain can be controlled by controlling the temperature, selecting the kind and amount of solvent or controlling the addition rate of silver salt and halide used at the grain growth.
The light-sensitive silver halide emulsion for use in the present invention may have any halogen composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide.
The light-sensitive silver halide grains for use in the present invention each may have any shape of cubic, tetradecahedral, octahedral, amorphous and platy forms but preferably has a cubic or platy form. In the present invention, the amount of light-sensitive silver halide added is, in terms of silver, 3.0 g/m² or less, preferably 2.0 to 3.0 g/m².
The photographic emulsion for use in the present invention can be prepared using a method described in P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), and V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press (1964).
More specifically, either an acid process or a neutral process may be used and the reaction between a soluble silver salt and a soluble halogen salt may be performed by a single jet method, a double jet method or a combination thereof.
A method of forming grains in the presence of excess silver ion (so-called reverse mixing method) may also be used. As one form of the double jet method, a method of maintaining a constant pAg in the liquid phase where silver halide is produced, namely, a so-called controlled double jet method may be used. Furthermore, the grains are preferably formed using a so-called silver halide solvent such as ammonia, thioether or tetra-substituted thiourea, more preferably a tetra-substituted thiourea compound, and this is described in JP-A-53-82408 and JP-A-55-77737. Preferred examples of the thiourea compound include tetramethyl thiourea and 1,3-dimethyl-2-imidazolidinethione. The amount of silver halide solvent added varies depending on the kind of the compound used or the objective grain size and halogen composition but is preferably from 10^-5 to 10^-2 mol per mol of silver halide. The grains may also be formed in the presence of a nitrogen-containing heterocyclic compound which forms a complex with silver, and preferred examples thereof include Compounds (N-1) to (N-59) described in JP-A-11-344788. The amount added of this compound varies over a fairly wide range depending on various conditions such as pH, temperature and size of silver halide grains but is preferably from 10^-6 to 10^-2 mol per mol of silver halide. This compound can be appropriately added at each stage before, during and after the grain formation but is preferably added during the grain formation.
According to the controlled double jet method or the grain formation method using a silver halide solvent, a silver halide emulsion having a regular crystal form and a narrow grain size distribution can be easily prepared and these methods are useful means for preparing the silver halide emulsion for use in the present invention.
In order to render the grain size uniform, the grains are preferably grown rapidly within the range of not exceeding the critical saturation degree by using a method of changing the addition rate of silver nitrate or alkali halide according to the grain growth rate described in British Patent 1,535,016, JP-B-48-36890 and JP-B-52-16364, or a method of changing the concentration of the aqueous solution described in British Patent 4,242,445 and JP-A-55-158124.
The emulsion for use in the present invention is preferably a monodisperse emulsion and the coefficient of variation represented by {(standard deviation of grain size)/(average grain size}×100 is preferably 20% or less, more preferably 15% or less.
The average grain size of silver halide grains is preferably 0.5 µm or less, more preferably from 0.1 to 0.4 µm, most preferably from 0.1 to 0.3 µm.
The light-sensitive silver halide emulsion for use in the present invention may consist of a single emulsion or two or more kinds of emulsions. In the case of two or more kinds of emulsions, these emulsions are preferably different in the grain size. The difference of the grain size is preferably 10% or more in terms of the average grain side length.
The ratio of two or more kinds of silver halide emulsions used in combination in the present invention is not particularly limited but the ratio between the emulsion having a smaller content of the nitrogen-containing heterocyclic compound capable of forming a complex with silver and the emulsion having a larger content is, in terms of a ratio in the amount of silver contained in the silver halide emulsion, preferably from 1:1 to 1:20, more preferably from 1:1 to 1:10.
The silver halide emulsion for use in the present invention is preferably a mixture of at least two emulsions different in the amount added of at least one nitrogen-containing heterocyclic compound capable of forming a complex with silver.
The amounts added of the nitrogen-containing heterocyclic compound capable of forming a complex with silver may be sufficient if the total amounts added immediately before the mixing of emulsions are different. The difference in the concentrations of the nitrogen-containing heterocyclic compound capable of forming a complex with silver is preferably 1.1 times or more, preferably 1.5 times or more, more preferably 2 times or more, based on the amount of silver contained in the emulsion.
The timing of adding the nitrogen-containing heterocyclic compound capable of forming a complex with silver is not particularly limited and the compound may be added during the grain formation, before the post-ripening, after the post-ripening or before the coating of each silver halide emulsion.
As for the method of mixing emulsions different in the amount added of the nitrogen-containing heterocyclic compound capable of forming a complex with silver, the emulsion smaller in the amount added may be added to the emulsion larger in the amount added or a method reversed thereto may be used.
Examples of the nitrogen-containing heterocyclic compound capable of forming a complex with silver, which can be used in the present invention, include a pyrazole ring, a pyrimidine ring, a 1,2,4-triazole ring, a 1,2,3-triazole ring, a 1,3,4-thiadiazole ring, a 1,2,3-thiadiazole ring, a 1,2,4-thiadiazole ring, a 1,2,5-thiadiazole ring, a 1,2,3,4-tetrazole ring, a pyridazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, a 1,3,5-triazine ring, a benzotriazole ring, a benzimidazole ring, a benzothiazole ring, a quinoline ring, a benzoxazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoimidazole ring, a rhodanine ring, a thiohydantoin ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a selenadiazole ring, a naphthoxazole ring, an oxazolidinedione ring, a triazolotriazole ring, an azaindene ring (e.g., diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring), a phthalazine ring and an indazole ring.
Among these, preferred are the compounds having an azaindene ring, more preferably azaindene compounds having a hydroxy group as a substituent, such as hydroxytriazaindene, tetrahydroxyazaindene and hydroxypentazaindene compounds. The heterocyclic ring may have a substituent other than a hydroxy group. Examples of the substituent which the heterocyclic ring may have include an alkyl group, an alkylthio group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, an arylamino group, a carboxy group, an alkoxycarbonyl group, a halogen atom, an acylamino group, a cyano group and a mercapto group.

Specific examples of the nitrogen-containing heterocyclic compound for use in the present invention are set forth below, however, the present invention is not limited thereto.

(N-1)	2,4-dihydrdoxy-6-methyl-1,3a,7-trazaindene
(N-2)	2,5-dimethyl-7-hydroxy-1,4,7a-trazaindene
(N-3)	5-amino-7-hydroxy-2-methyl-1,4,7a-trazaindene
(N-4)	4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene
(N-5)	4-hydroxy-1,3,3a,7-tetrazaindene
(N-6)	4-hydroxy-6-phenyl-1,3,3a,7-tetrazaindene
(N-7)	4-methyl-6-hydroxy-1,3,3a,7-tetrazaindene
(N-8)	2,6-dimethyl-4-hydroxy-1,3,3a,7-tetrazaindene
(N-9)	4-hydroxy-5-ethyl-6-methyl-1,3,3a,7-tetrazaindene
(N-10)	2,6-dimethyl-4-hydroxy-5-ethyl-1,3,3a,7-tetrazaindene
(N-11)	4-hydroxy-5,6-dimethyl-1,3,3a,7-tetrazaindene
(N-12)	2,5,6-trimethyl-4-hydroxy-1,3,3a,7-tetrazaindene
(N-13)	2-methyl-4-hydroxy-6-phenyl-1,3,3a,7-tetrazaindene
(N-14)	4-hydroxy-6-methyl-1,2,3a,7-tetrazaindene
(N-15)	4-hydroxy-6-ethyl-1,2,3a,7-tetrazaindene
(N-16)	4-hydroxy-6-phenyl-1,2,3a,7-tetrazaindene
(N-17)	4-hydroxy-1,2,3a,7-tetrazaindene
(N-18)	4-methyl-6-hydroxy-1,2,3a,7-tetrazaindene
(N-19)	7-hydroxy-5-methyl-1,2,3,4,6-pentazaindene
(N-20)	5-hydroxy-7-methyl-1,2,3,4,6-pentazaindene
(N-21)	5,7-dihydroxy-1,2,3,4,6-pentazaindene
(N-22)	7-hydroxy-5-methyl-2-phenyl-1,2,3,4,6-pentazaindene
(N-23)	5-dimethylamino-7-hydroxy-2-phenyl-1,2,3,4,6-pentazaindene
(N-24)	1-phenyl-5-mercapto-1,2,3,4-tetrazole
(N-25)	6-aminopurine
(N-26)	benzotriazole
(N-27)	6-nitrobenzimidazole
(N-28)	3-ethyl-2-methylbenzothiazolium p-toluenesulfonate
(N-29)	1-methylquinoline
(N-30)	benzothiazole
(N-31)	benzoxazole
(N-32)	benzoselenazole
(N-33)	benzimidazole
(N-34)	naphthothiazole
(N-35)	naphthoselenazole
(N-36)	naphthoimidazole
(N-37)	rhodanine
(N-38)	2-thiohydantoin
(N-39)	2-thio-2,4-oxazolidinedione
(N-40)	3-benzyl-2-mercaptobenzimidazole
(N-41)	2-mercapto-1-methylbenzothiazole
(N-42)	5-(m-nitrophenyl)tetrazole
(N-43)	2,4-dimethylthiazole
(N-44)	1-methyl-5-ethoxybenzothiazole
(N-45)	2-methyl-β-naphthothiazole
(N-46)	1-ethyl-5-mercaptotetrazole
(N-47)	5-methylbenzotriazole
(N-48)	5-phenyltetrazole
(N-49)	1-methyl-2-mercapto-5-benzoylamino-1,3,5-triazole
(N-50)	1-benzoyl-2-mercapto-5-acetylamino-1,3,5-triazole
(N-51)	2-mercapto-3-aryl-4-methyl-6-hydroxypyrimidine
(N-52)	2,4-dimethyloxazole
(N-53)	1-methyl-5-phenoxybenzoxazole
(N-54)	2-ethyl-β-naphthoxazole
(N-55)	2-mercapto-5-aminothiadiazole
(N-56)	2-mercapto-5-aminooxadiazole
(N-57)	2-mercapto-5-aminoselenadiazole
(N-58)	sodium 3-(5-mercaptotetrazole)benzenesulfonate
(N-59)	sodium 3-(5-mercaptotetrazole)benzenecarboxylate

The amount of the nitrogen-containing heterocyclic compound added varies over a wide range depending on the size, composition and ripening conditions of silver halide grain but is preferably from 10 to 1,000 mg, more preferably from 50 to 200 mg per mol of silver halide. The nitrogen-containing heterocyclic compound is preferably added in an amount sufficiently large to form from a single molecule layer to 10 molecule layers on the surface of a silver halide grain. This amount added may be adjusted by controlling the adsorption equilibrated state which fluctuates due to change of pH and/or temperature during the ripening. As for the method of adding the nitrogen-containing heterocyclic compound for use in the present invention to the emulsion, a method of dissolving the compound in an appropriate solvent (for example, water or aqueous alkali solution) which does not adversely affect the emulsion, and adding as a solution may be used.
The silver halide emulsion for use in the present invention may contain a metal belonging to Group VIII. In order to achieve high contrast and low fogging, the silver halide emulsion preferably contains a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound or the like. These heavy metals are preferably in the form of a metal coordination complex, and the hexa-coordinated complex represented by the following formula is preferred: [M(NY)mL6-m]n- wherein M is a heavy metal selected from Ir, Ru, Rh, Re, Cr and Fe, L is a crosslinking ligand, Y is oxygen or sulfur, m is 0, 1 or 2, and n is 0, 1, 2 or 3.
Specific preferred examples of L include a halide ligand (e.g., fluoride, chloride, bromide, iodide), a cyanide ligand, a cyanate ligand, a thiocyanate ligand, a selenocyanate ligand, a tellurocyanate ligand, an acid ligand and an aquo ligand. When an aquo ligand is present, it preferably occupies one or more of the ligands.
In order to achieve high sensitivity, the silver halide emulsion for use in the present invention preferably contains an iron compound, more preferably a metal coordination complex having a cyan ligand as a ligand.
These compounds each is used by dissolving it in water or an appropriate solvent and a method commonly used for stabilizing a solution of the compound, namely, a method of adding an aqueous solution of hydrogen halogenide (e.g., hydrochloric acid, bromic acid, hydrofluoric acid) or an alkali halide (e.g., KCl, NaCl, KBr, NaBr) may be used. It is also possible to add and dissolve separately prepared silver halide grains which are previously doped with such a compound.
Specific examples of the metal coordination complex are set forth below.
1. [Rh(H₂O)Cl₅]^2-
2. [RuCl₆]^3-
3. [Ru(NO)Cl₅]^2-
4. [RhCl₆]^3-
5. [Ru(H₂O)Cl₅]^2-
6. [Ru(NO)(H₂O)Cl₄]^-
7. [Ru₂Cl₁₀O]^6-
8. [Re(NO)Cl₅]^2-
9. [Ir(NO)Cl₅]^2-
10. [Ir(H₂O)Cl₅]^2-
11. [Re(H₂O)Cl₅]^2-
12. [RhBr₆]^3-
13. [ReCl₆]^3-
14. [IrCl₆]^3-
15. [Re(NS)Cl₄(SeCN)]^2-
16. [Cr(CN)₆]^3-
17. [Fe(CN)₆]^3-
Other than these, the compounds described in Japanese Patent Application No. 2000-95144, paragraphs 0027 to 0056 may also be preferably used.
The amount of such a compound added is from 1×10^-8 to 5×10^-6, preferably from 5×10^-8 to 1×10^-6 mol, per mol of silver in the silver halide emulsion.
The above-described heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grain is not particularly limited and the grain may have uniform distribution, may be a core-shell type grain different in the distribution between the surface and the interior or may be continuously changed in the distribution. This compound may be appropriately added at the preparation of silver halide emulsion grains or at each stage before coating the emulsion but is preferably added at the time of emulsion formation and introduced into the silver halide grain.
The silver halide emulsion for use in the present invention is preferably subjected to chemical sensitization. The chemical sensitization may be performed using a well-known method such as sulfur sensitization, selenium sensitization, tellurium sensitization or noble metal sensitization, and these sensitization methods may be used individually or in combination. In the case of using these sensitization methods in combination, for example, a combination of sulfur sensitization and gold sensitization, a combination of sulfur sensitization, selenium sensitization and gold sensitization, and a combination of sulfur sensitization, tellurium sensitization and gold sensitization are preferred.
The sulfur sensitization for use in the present invention is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40°C or more, for a predetermined time. The sulfur sensitizer may be a well-known compound and examples thereof include, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfate, thioureas, thiazoles and rhodanines. In addition, sulfur sensitizers described in U.S. Patents 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313 and 3,656,955, German Patent 1,422,869, JP-B-56-24937 and JP-A-55-45016 can also be used. Among these sulfur compounds, preferred are thiosulfate and thiourea compounds.
The amount of the sulfur sensitizer added varies depending upon various conditions such as pH and temperature at the chemical ripening and size of silver halide grains, however, the amount added is preferably from 10^-7 to 10^-2 mol, more preferably from 10^-5 to 10^-3 mol, per mol of silver halide.
The selenium sensitizer for use in the present invention may be a well-known selenium compound. The selenium sensitization is usually performed by adding a labile selenium compound and/or a non-labile selenium compound and stirring the emulsion at a high temperature, preferably 40°C or more, for a predetermined time. Examples of the labile selenium compound which is preferably used include the compounds described in JP-B-44-15748, JP-B-43-13489, JP-A-4-25832, JP-A-4-109240 and JP-A-4-324855. Specific examples of the labile selenium sensitizer include isocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (e.g., 2-selenopropiones, 2-selenobutyric acid), selenoesters, diacylselenides (e.g., bis(3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides and colloidal metal selenium. Preferred examples of the labile selenium compound are described above but not limited to these. Generally, the labile selenium compound as a sensitizer for photographic emulsions is understood by one skilled in the art that the structure of the compound is not so important as far as the selenium is labile and that the organic moiety of the selenium sensitizer molecule carries selenium and has no other role than to allow the selenium to be present in a labile state in the emulsion. In the present invention, labile selenium compounds in such a broad concept are advantageously used. As for the non-labile selenium compound for use in the present invention, the compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 are used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary salt of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione, and derivatives thereof. In particular, the compounds represented by formulae (VIII) and (IX) of JP-A-4-324855 are preferred.
A low decomposition activity selenium compound can also be preferably used. The low decomposition activity selenium compound is a selenium compound such that when a water/1,4-dioxane (1/1 by volume) mixed solution (pH: 6.3) containing 10 mmol of AgNO₃, 0.5 mmol of the selenium compound and 40 mmol of 2-(N-morpholino)ethanesulfonic acid buffer was reacted at 40°C, the half life of the selenium compound is 6 hours or more. In the determination of half life, the detection of selenium compound can be analyzed by HPLC and the like. Preferred examples of the low decomposition activity selenium compound include Compounds SE-1 to SE-8 of JP-A-9-166841.
The tellurium sensitizer for use in the present invention is a compound of forming silver telluride presumed to become a sensitization nucleus, on the surface or in the inside of a silver halide grain. The formation rate of silver telluride in a silver halide emulsion can be tested by the method described in JP-A-5-313284.
Specific examples of the tellurium sensitizer include the compounds described in U.S. Patents 1,623,499, 3,320,069 and 3,772,031, British Patents 235,211, 1,121,496, 1,295,462 and 1,396,696, Canadian Patent 800,958, JP-A-4-204640, JP-A-4-271341, JP-A-4-333043, JP-A-5-303157, J. Chem. Soc. Chem. Commun., 635 (1980), ibid., 1102 (1979), ibid., 645 (1979), J. Chem. Soc. Perkin. Trans., 1, 2191 (1980), S. Patai (compiler), The Chemistry of Organic Selenium and Tellurium Compounds, Vol. 1 (1986), and ibid., Vol. 2 (1987). The compounds represented by formulae (II), (III) and (IV) of JP-A-5-313284 are particularly preferred.
The amount used of the selenium or tellurium sensitizer for use in the present invention varies depending upon silver halide grains used or chemical ripening conditions but the amount used is usually from 10^-8 to 10^-2 mol, preferably on the order of 10^-7 to 10^-3 mol, per mol of silver halide. In the present invention, the conditions for chemical sensitization are not particularly limited, however, the pH is from 5 to 8, the pAg is from 6 to 11, preferably from 7 to 10, and the temperature is from 40 to 95°C, preferably from 45 to 85°C.
Examples of the noble metal sensitizer for use in the present invention include gold, platinum, palladium and iridium, and gold sensitization is particularly preferred. The gold sensitizer may have a gold oxidation number of either +1 valence or +3 valence and gold compounds usually used as the gold sensitizer can be used. Representative examples thereof include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold and gold sulfide. The gold sensitizer can be used in an amount of approximately from 10^-7 to 10^-2 mol per mol of silver halide.
In the silver halide emulsion for use in the present invention, a cadmium salt, a sulfite, a lead salt or a thallium salt may be present together during formation or physical ripening of silver halide grains.
In the present invention, reduction sensitization may be used. Examples of the reduction sensitizer which can be used include stannous salt, amines, formamidinesulfinic acid and silane compounds.
To the silver halide emulsion for use in the present invention, a thiosulfonic acid compound may be added according to the method described in EP-A-293917.
In the light-sensitive material of the present invention, two or more kinds of silver halide emulsions different in the kind, distribution or content of metal complex, different in the crystal habit or shape, different in the kind or amount added of chemical sensitizer or chemical sensitization conditions, or different in the kind or amount added of spectral sensitizing dye or spectral sensitization conditions, may be used in combination. Furthermore, a multilayer structure may be formed by these emulsion layers.
The light-sensitive silver halide emulsion for use in the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength, by a sensitizing dye according to the use of the light-sensitive material. Examples of the sensitizing dye which can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes and hemioxonol dyes.
Useful sensitizing dyes for use in the present invention are described, for example, in Research Disclosure, Item 17643IV-A, page 23 (December, 1978), ibid., Item 1841X, page 437 (August, 1979), and publications cited therein.
In particular, sensitizing dyes having spectral sensitivity suitable for spectral characteristics of various light sources in a scanner, an image setter or a photomechanical camera can be advantageously selected.
For example, A) for an argon laser light source, Compounds (1)-1 to (1)-8 described in JP-A-60-162247, Compounds I-1 to I-28 described in JP-A-2-48653, Compounds I-1 to I-13 described in JP-A-4-330434, Compound Examples 1 to 14 described in U.S. Patent 2,161,331, and Compounds 1 to 7 described in West German Patent 936,071, B) for a helium-neon laser light source and a red laser diode light source, Compounds I-1 to I-38 described in JP-A-54-18726, Compounds I-1 to I-35 described in JP-A-6-75322, Compounds I-1 to I-34 described in JP-A-7-287338, and Compounds 2-1 to 2-14, 3-(1) to 3-(14) and 4-1 to 4-6 described in Japanese Patent 2,822,138, C) for an LED light source, Dyes 1 to 20 described in JP-B-55-39818 (The term "JP-B" as used herein means an examined Japanese Patent publication), Compounds I-1 to I-37 described in JP-A-62-284343, Compounds I-1 to I-34 described in JP-A-7-287338, and Compounds 2-1 to 2-14, 3-(1) to 3-(14) and 4-1 to 4-6 described in Japanese Patent 2,822,138, D) for a semiconductor laser light source, Compounds I-1 to I-12 described in JP-A-59-191032, Compounds I-1 to I-22 described in JP-A-60-80841, Compounds I-1 to I-29 described in JP-A-4-335342, and Compounds I-1 to I-18 described in JP-A-59-192242, and E) for a tungsten or xenon light source for photomechanical cameras, Compounds (1) to (19) represented by formula [I] of JP-A-55-45015, Compounds 4-A to 4-S, Compounds 5-A to 5-Q and Compounds 6-A to 6-T described in JP-A-6-242547 and Compounds I-1 to I-97 described in JP-A-9-160185 are advantageously selected, however, the present invention is not limited thereto.
These sensitizing dyes may be used individually or in combination, and a combination of sensitizing dyes is often used for the purpose of supersensitization. In combination with a sensitizing dye, a dye which itself has no spectral sensitization activity or a material which absorbs substantially no visible light, but which exhibits supersensitization may be incorporated into the emulsion.
Useful sensitizing dyes, the combination of dyes which exhibits supersensitization, and materials which show supersensitization are described in Research Disclosure, Vol. 176, 17643, page 23, Item IV-J (December, 1978), JP-B-49-25500, JP-B-43-4933, JP-A-59-19032 and JP-A-59-192242.
The sensitizing dyes for use in the present invention may be used in combination of two or more thereof. The sensitizing dye may be added to a silver halide emulsion by dispersing it directly in the emulsion or by dissolving it in a sole or mixed solvent of water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol or N,N-dimethylformamide and then adding the solution to the emulsion.
Also, the sensitizing dye may be added to the emulsion by the method described in U.S. Patent 3,469,978 where a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid and the dispersion is added to the emulsion, the method described in JP-B-44-23389, JP-B-44-27555 and JP-B-57-22091 where a dye is dissolved in an acid and the solution is added to the emulsion or formed into an aqueous solution in the presence of an acid or a base together and then added to the emulsion, the method described in U.S. Patents 3,822,135 and 4,006,025 where a dye is formed into an aqueous solution or a colloid dispersion in the presence of a surfactant together and the aqueous solution or dispersion is added to the emulsion, the method described in JP-A-53-102733 and JP-A-58-105141 where a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to the emulsion, or the method described in JP-A-51-74624 where a dye is dissolved using a compound capable of red shifting and the solution is added to the emulsion. Ultrasonic waves may also be used in the solution.
The sensitizing dye for use in the present invention may be added to a silver halide emulsion of the present invention at any step heretofore recognized as useful during the preparation of emulsion. For example, the dye may be added during the formation of silver halide grains and/or in the period before the desalting, or during the desilvering and/or in the period after the desalting until the initiation of chemical ripening as disclosed in U.S. Patents 2,735,766, 3,628,960, 4,183,756 and 4,225,666, JP-A-58-184142 and JP-A-60-196749, or may be added in any period or step before the coating of emulsion such as immediately before or during the chemical ripening or in the period after the chemical ripening until the coating as described in JP-A-58-113920. Also, a sole kind of compound alone or compounds different in the structure in combination may be added in parts, for example, during the grain formation and during or after completion of the chemical ripening, or before or during the chemical ripening and after completion of the chemical ripening as disclosed in U.S. Patent 4,225,666 and JP-A-58-7629. Also, different kinds of compounds may be added in parts or the compounds in different combinations may be added in parts.
The amount added of the sensitizing dye for use in the present invention varies depending upon the shape, size, halogen composition of silver halide grains, the method and degree of chemical sensitization and the kind of antifoggant, however, the sensitizing dye can be added in an amount of 4×10^-6 to 8×10^-3 mol per mol of silver halide. For example, in the case where the silver halide grain size is from 0.2 to 1.3 µm, the amount added is preferably from 2×10^-7 to 3.5×10^-6, more preferably from 6.5×10^-7 to 2.0×10^-6 mol, per m² of the surface area of a silver halide grain.
The term "other hydrophilic colloid layer " as used in the present invention means a hydrophilic colloid layer having a water-permeable or water-impermeable relationship with the silver halide emulsion layer. Examples of the former include protective layer and interlayer and examples of the latter include back layer.
Examples of the support for use in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyester film such as polyethylene terephthalate, supports comprising a styrene-based polymer having a syndiotactic structure described in JP-A-7-234478 and U.S. Patent 5,558,979, and supports obtained by coating a polyester film with a vinylidene chloride copolymer described in JP-A-64-538 and U.S. Patents 4,645,731, 4,933,267 and 4,954,430. The support is appropriately selected from these supports according to the use end of each silver halide photographic light sensitive material.
For the binder in the silver halide emulsion layer and other hydrophilic colloid layers, gelatin is preferably used, however, polymers described in JP-A-10-268464 may also be used. As for the amount of the binder coated, the amount of binder in all hydrophilic colloid layers in the side having a silver halide emulsion layer is 3 g/m² or less (preferably from 1.0 to 3.0 g/m²) and the total amount of the binder in all hydrophilic colloid layers in the side having a silver halide emulsion layer and the binder in all hydrophilic colloid layer in the opposite side thereto is 7.0 g/m² or less, preferably from 2.0 to 7.0 g/m².
In the present invention, for the purpose of controlling the surface roughness on the surface of an outermost layer of a silver halide light-sensitive material, fine powder particles of an inorganic polymer and/or an organic polymer (hereinafter referred to as a matting agent) is used in a hydrophilic colloid layer. The surface roughness on the surface of an outermost layer in the side having a silver halide emulsion layer of a light-sensitive material and the surface roughness on the surface of an outermost layer in the opposite side can be controlled by variously changing the average particle size and the amount added of the matting agent. The layer in which the matting agent is contained may be any layer of the light-sensitive material constituent layers but in the side having a silver halide emulsion layer, the matting agent is preferably contained in the layer farther from the support so as to prevent pinholes and more preferably in an outermost layer.
The matting agent for use in the present invention may be any material insofar as it is a solid particle not adversely affecting the photographic various properties. Specific examples thereof include those describe in JP-A-10-268464, paragraphs 0009 to 0013.
In the present invention, the average particle size of the matting agent is preferably 20 µm or less, more preferably from 1 to 10 µm. The amount added of the matting agent for use in the present invention is from 5 to 400 mg/m², preferably from 10 to 200 mg/m².
As for the surface roughness of the light-sensitive material of the present invention, the Bekk's smoothness on at least one, preferably both of the outermost surfaces in the side having an emulsion layer and in the opposite side thereof is 4,000 seconds or less, more preferably from 10 to 4,000 seconds. The Beck smoothness can be easily determined by Japanese Industrial Standard (JIS) P8119 and TAPPI Standard Method T479.
In the present invention, colloidal inorganic particles may be used in a silver halide emulsion, an interlayer, a protective layer, a back layer, a back protective layer and the like for the purpose of preventing the matting agent from sinking at the time of coating and drying a silver halide light-sensitive material or in the handling at the automatic transportation, exposure, development and the like, for improving the pressure sensitization/desensitization, curling balance, scratch resistance, adhesive resistance and the like. Preferred examples of the colloidal inorganic particle include long and thin silica particle described in JP-A-10-268464, paragraphs 0008 to 0014, colloidal silica, pearls-like (pearl necklace-like) colloidal silica "Snowtex-PS" produced by Nissan Chemicals Industries, Ltd.
The amount used of colloidal inorganic particles for use in the present invention is, in terms of the dry weight ratio, from 0.01 to 2.0, preferably from 0.1 to 0.6, to the binder (for example, gelatin) in the layer where the colloidal inorganic particles are added.
In the present invention, for the purpose of improving the pressure sensitization/desensitization, polyhydroxybenzene compounds described in JP-A-3-39948, from page 10, right lower column, line 11 to page 12, left lower column, line 5 are preferably used. Specific examples thereof include Compounds (III)-1 to (III)-25 described in the same patent publication.
In the present invention, for the purpose of improving the fragility, dimensional stability, pressure sensitization/desensitization and the like, a polymer latex may be used. Examples of the polymer latex include polymer latex comprising various monomers such as alkyl acrylate and alkyl methacrylate described in U.S. Patents 2,763,652 and 2,852,382, JP-A-64-538, JP-A-62-115152, JP-A-5-66512, JP-A-5-80449, JP-B-60-15935, JP-B-6-64058 and JP-B-5-45014, and polymer latex obtained by the copolymerization of a monomer having an active methylene group and a monomer such as alkyl acrylate described in JP-B-45-5819, JP-B-46-22507, JP-A-50-73625, JP-A-7-152112 and JP-A-8-137060. In particular, polymer latex having a core/shell structure containing a repeating unit comprising an ethylenically unsaturated monomer having an active methylene group in the shell part, described in JP-A-8-248548, JP-A-8-208767 and JP-A-220669. By using this polymer latex having a core/shell structure containing an active methylene group in the shell part, the properties such as fragility, dimensional stability and difficulty in adhesion of light-sensitive material with each other, can be improved without causing reduction in the wet film strength of the photographic light-sensitive material and also, the shearing stability of the latex itself can be improved.
The amount of the polymer latex used is, in terms of the dry weight ratio, from 0.01 to 4.0, preferably from 0.1 to 2.0, to the binder (for example, gelatin) in the layer where the polymer latex is added.
In the present invention, for lowering the pH of the coating and thereby improving the storability, pressure sensitization/desensitization or the like of a silver halide light-sensitive material, acidic polymer latex described in JP-A-7-104413, page 14, from left first line to right 30th line, is preferably used. Specific examples thereof include Compounds II-1) to II-9) described in the same patent publication, page 15, and the compound having an acid radical described in JP-A-2-103536, from page 18, right lower column, line 6 to page 19, left upper column, line 1.
The pH of the coating in the side having a silver halide emulsion layer is preferably from 4 to 6.
In the present invention, at least one constituent layer of the silver halide light-sensitive material may contain an electrically conducting layer having a surface resistivity of 10¹² Ω or less in an atmosphere at 25°C and 25% RH.
Examples of the electrically conducting material for use in the present invention include electrically conducting substances described in JP-A-2-18542, from page 2, left lower column, line 13 to page 3, right upper column, line 7. Specific examples thereof include metal oxides described at page 2, right lower column, lines 2 to 10 of the same patent publication, Compounds P-1 to P-7 as an electrically conducting polymer compound described in the same patent publication, and acicular metal oxides described in U.S. Patent 5,575,957, JP-A-10-142738, paragraphs 0034 to 0043, and JP-A-11-223901, paragraphs 0013 to 0019.
In the present invention, in addition to the above-described electrically conducting material, a fluorine-containing surfactant described in JP-A-2-18542, page 4, from right upper column, line 2 to right lower column, line 3 from the bottom, and JP-A-3-39948, from page 12, left lower column, line 6 to page 13, right lower column, line 5 may be used in combination, whereby higher antistatic property can be obtained.
In the present invention, the silver halide emulsion layer or other hydrophilic colloid layer may contain various surfactants as a coating aid or a dispersant/solubilizing agent for additives or for the purpose of enhancing the lubricity, preventing the adhesion, improving photographic properties (for example, acceleration of development, high contrast, sensitization, storability) and the like. Examples of the surfactant include surfactants described in JP-A-2-12236, page 9, from right upper column, line 7 to right lower column, line 3, and PEG-based surfactants described in JP-A-2-103536, page 18, left lower column, lines 4 to 7. Specific examples thereof include Compounds VI-1 to VI-15 described in JP-A-2-103536, and fluorine-containing surfactants described in JP-A-2-18542, page 4, from right upper column, line 2 to right lower column, line 3 from the bottom, and JP-A-3-39948, from page 12, left lower column, line 6 to page 13, right lower column, line 5.
In the present invention, various lubricants can be used for the purpose of improving transportation property, scratch resistance, pressure sensitization/desensitization property and the like of the silver halide light-sensitive material in an automatic transporting machine. Examples thereof include the lubricants described in JP-A-2-103536, page 19, from left upper column, line 5 to right upper column, line 15, and JP-A-4-214551, paragraphs 0006 to 0031.
In the present invention, a plasticizer for the coating of the silver halide light-sensitive material may be contained and examples thereof include the plasticizers described in JP-A-2-103536, page 19, from left upper column, line 12 to right upper column, line 15.
In the present invention, a crosslinking agent for the hydrophilic binder may be used and examples thereof include the compounds described in JP-A-2-103536), page 18, right upper column, lines 5 to 17, and JP-A-5-297508, paragraphs 0008 to 0011.
In the silver halide photographic light-sensitive material of the present invention, the swelling rate of hydrophilic colloid layers including emulsion layer and protective layer is preferably from 50 to 200%, more preferably from 70 to 180%. The swelling rate of hydrophilic colloid layers is determined by measuring the thickness (d0) of hydrophilic colloid layers including emulsion layer and protective layer of the silver halide photographic light-sensitive material, dipping the silver halide photographic light-sensitive material in distilled water at 25°C for 1 minute, measuring the swelled thickness (Δd) and applying these measured valued to the formula: swelling rate (%) = Δd÷d0×100.
In the present invention, the drying at the time of drying the silver halide light-sensitive material after the coating, and the environment, working, heat-treatment at the time of taking up the light-sensitive material into a roll after the drying are preferably performed by the methods described in JP-A-10-268464, paragraphs 0026 to 0032.
In the present invention, the silver halide light-sensitive material after the coating is preferably heat-treated at an arbitrary time from the coating until the development processing. The heat treatment may be performed in subsequence immediately after the coating or may be performed after the passing of a certain period of time but is preferably performed within a short period of time, for example, within one day. The heat treatment is performed mainly for promoting the hardening reaction to obtain a film strength highly enough to endure the heat development. The heat-treatment conditions must be appropriately selected according to the kind and the amount added of the hardening agent, the film pH, the required film strength and the like, but the temperature is preferably from 30 to 60°C, more preferably from 35 to 50°C. The heat-treatment time is preferably from 30 minutes to 10 days.
In the present invention, at least one hydrazine derivative represented by formula (D) is preferably contained as a nucleating agent.
wherein R₂₀ represents an aliphatic group, an aromatic group or a heterocyclic group, R₁₀ represents a hydrogen atom or a block group, G₁₀ represents -CO-, -COCO-, -C(=S)-, -SO₂-, -SO-, -PO(R₃₀)- (wherein R₃₀ is selected from the same range as the groups defined for R₁₀ and may be different from R₁₀) or an iminomethylene group, A₁₀ and A₂₀ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group.
In formula (D), the aliphatic group represented by R₂₀ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl group having from 1 to 30 carbon atoms, an alkenyl group or an alkynyl group.
In formula (D), the aromatic group represented by R₂₀ is a monocyclic or condensed ring aryl group and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic group represented by R₂₀ is a monocyclic or condensed ring, saturated or unsaturated, aromatic or nonaromatic heterocyclic group and examples thereof include a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a piperidine ring and a triazine ring.
R₂₀ is preferably an aryl group, more preferably a phenyl group.
The group represented by R₂₀ may be substituted and representative examples of the substituent include a halogen atom (e.g., fluorine, chlorine, bromine, iodine), an alkyl group (including an aralkyl group, a cycloalkyl group and an active methine group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (e.g., pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxyl group and salts thereof, a sulfonylcarbamoyl group, an acylcarbamoyl group, a sulfamoylcarbamoyl group, a carbazoyl group, an oxalyl group, an oxamoyl group, a cyano group, a thiocarbamoyl group, a hydroxy group, an alkoxy group (including a group containing an ethyleneoxy group or a propyleneoxy group as a repeating unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, N-substituted nitrogen-containing heterocyclic group, an acylamino group, a sulfonamido group, a ureido group, a thioureido group, an isothioureido group, an imido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, a semicarbazide group, a thiosemicarbazide group, a hydrazino group, a quaternary ammonio group, an oxamoylamino group, an alkylsulfonylureido group, an arylsulfonylureido group, an acylureido group, an N-acylsulfamoylamino group, a nitro group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfo group and salts thereof, a sulfamoyl group, an N-acylsulfamoyl group, a sulfonylsulfamoyl group and salts thereof, and a group containing a phosphoric acid amide structure or a phosphoric acid ester structure.
These substituents each may further be substituted by these substituents.
The substituent which R₂₀ may have is preferably an alkyl group having from 1 to 30 atoms (including active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acrylamino group, a sulfonamido group, a ureido group, a sulfamoylamino group, an imido group, a thioureido group, a phosphoric acid amide group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group (including a salt thereof), an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfo group (including a salt thereof), a sulfamoyl group, a halogen atom, a cyano group or a nitro group.
In formula (D), R₁₀ represents a hydrogen atom or a block group and the block group specifically represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group.
The alkyl group represented by R₁₀ is preferably an alkyl group having from 1 to 10 carbon atoms and examples thereof include a methyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl group, a pyridiniomethyl group, a difluoromethoxymethyl group, a difluorocarboxymethyl group, a 3-hydroxypropyl group, a methanesulfonamidomethyl group, a benzenesulfonamidomethyl group, a hydroxymethyl group, a methoxymethyl group, a methylthiomethyl group, a phenylsulfonylmethyl group and an o-hydroxybenzyl group. The alkenyl group is preferably an alkenyl group having from 1 to 10 carbon atoms and examples thereof include a vinyl group, 2,2-dicyanovinyl group, a 2-ethoxycarbonylvinyl group and a 2-trifluoro-2-methoxycarbonylvinyl group. The alkynyl group is preferably an alkynyl group having from 1 to 10 carbon atoms and examples thereof include an ethynyl group and 2-methoxycarbonylethynyl group. The aryl group is preferably a monocyclic or condensed ring aryl group, more preferably an aryl group containing a benzene ring, and examples thereof include a phenyl group, a 3,5-dichlorophenyl group, a 2-methanesulfonamidophenyl group, a 2-carbamoylphenyl group, a 4-cyanophenyl group and a 2-hydroxymethylphenyl group.
The heterocyclic group is preferably a 5- or 6-membered, saturated or unsaturated, monocyclic or condensed ring heterocyclic group containing at least one of nitrogen, oxygen and sulfur atoms and may be a heterocyclic group containing quaternized nitrogen atom. Examples thereof include a morpholino group, a piperidino group (N-substituted), a piperazino group, an imidazolyl group, an indazolyl group (e.g., 4-nitroindazolyl), a pyrazolyl group, a triazolyl group, a benzimidazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group (e.g., N-methyl-3-pyridinio group), a quinolinio group and a quinolyl group. Among these, a morpholino group, a piperidino group, a pyridyl group and a pyridinio group are preferred.
The alkoxy group is preferably an alkoxy group having from 1 to 8 carbon atoms and examples thereof include a methoxy group, a 2-hydroxyethoxy group and a benzyloxy group. The aryloxy group is preferably a phenoxy group and the amino group is preferably an unsubstituted amino group or an alkylamino, arylamino group or saturated or unsaturated heterocyclic amino group (including a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom) having from 1 to 10 carbon atoms. Examples of the amino group include 2,2,6,6-tetramethylpiperidin-4-ylamino group, a propylamino group, a 2-hydroxyethylamino group, an anilino group, an o-hydroxyanilino group, a 5-benzotriazolylamino group and an N-benzyl-3-pyridinioamino group. The hydrazino group is preferably a substituted or unsubstituted hydrazino group, or a substituted or unsubstituted phenylhydrazino group (e.g., 4-benzenesulfonamidophenylhydrazino).
The group represented by R₁₀ may be substituted and preferred examples of the substituent are the same as those described above for the substituent of R₂₀.
In formula (D), R₁₀ may be a group which occurs a cyclization reaction of cleaving the G₁₀-R₁₀ moiety from the remaining molecule to produce a cyclic structure containing the atoms in the -G₁₀-R₁₀ moiety, and examples thereof include those described, for example, in JP-A-63-29751.
The hydrazine derivative represented by formula (D) may be introduced with an adsorptive group capable of adsorbing to silver halide. Examples of the adsorptive group include the groups described in U.S. Patents 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-201046, JP-A-59-201047, JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, JP-A-63-234245 and JP-A-63-234246, such as an alkylthio group, an arylthio group, a thiourea group, a thioamido group, a mercaptoheterocyclic group and a triazole group. The adsorptive group to silver halide may be formed into a precursor and examples of the precursor include the groups described in JP-A-2-285344.
R₁₀ or R₂₀ in formula (D) may be a group in which a ballast group or polymer commonly used in the immobile photographic additives such as a coupler is introduced. In the present invention, the ballast group means a group having 6 or more carbon atoms and having a linear or branched alkyl or alkylene group, a linear or branched alkoxy or alkyleneoxy group, a linear or branched alkylamino or alkylene amino group, a linear or branched alkylthio group, or a group having such a group as a partial structure, preferably a group having from 7 to 24 carbon atoms and having a linear or branched alkyl or alkylene group, a linear or branched alkoxy or alkyleneoxy group, a linear or branched alkylamino or alkyleneamino group, an alkylthio group, or a group having such a group as a partial structure. Examples thereof include those described in JP-A-1-100530.
In formula (D), R₁₀ or R₂₀ may contain a plurality of hydrazino groups as substituents and at this time, the compound represented by formula (D) is a polymer (i.e., a multimer) with respect to a hydrazino group and specific examples thereof include the compounds described in JP-A-64-86134, JP-A-4-16938, JP-A-5-197091, WO95-32452, WO95-32453, JP-A-9-179229, JP-A-9-235264, JP-A-9-235265, JP-A-9-235266 and JP-A-9-235267.
R₁₀ or R₂₀ in formula (D) may contain a cationic group (specifically, a group containing a quaternary ammonio group, a group containing a quaternized phosphorus atom, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, etc.), a group containing an ethyleneoxy group or a propyleneoxy group as a repeating unit, an alkylthio group, an arylthio group, a heterocyclic thio group or a dissociative group (a group, a partial structure or a salt thereof, containing a proton having acidity low enough to dissociate in an alkaline developer; specific examples thereof include a carboxy group/-COOH, a sulfo group/-SO₃H, a phosphonic acid group/-PO₃H, a phosphorus acid group/-OPO₃H, a hydroxy group/-OH group, a mercapto group/-SH, a -SO₂NH₂ group, an N-substituted sulfonamido group/-SO₂NH-, a -CONHSO₂- group, a -CONHSO₂NH-group, a -NHCONHSO₂- group, a -SO₂NHSO₂- group, a -CONHCO- group, an active methylene group, a -NH- group and salts thereof). Examples of the case containing such a group include the compounds described in JP-A-7-234471, JP-A-5-333466, JP-A-6-19032, JP-A-6-19031, JP-A-5-45761, U.S. Patents 4,994,365 and 4,988,604, JP-A-7-259240, JP-A-7-5610, JP-A-7-244348, German Patent 4,006,032 and JP-A-11-7093.
In formula (D), A₁₀ and A₂₀ each is a hydrogen atom, an alkyl- or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted such that the sum of Hammett's substituent constants is -0.5 or more) or an acyl group having 20 or less carbon atoms (preferably a benzoyl group, a benzoyl group substituted such that the sum of Hammett's substituent constants is -0.5 or more, or a branched or linear substituted or unsubstituted aliphatic acyl group (examples of the substituent include a halogen atom, an ether group, a sulfonamido group, a carbonamido group, a hydroxy group, a carboxy group and a sulfo group). A₁₀ and A₂₀ each is most preferably a hydrogen atom.
The hydrazine derivative particularly preferred in the present invention is described below.
R₂₀ is preferably a substituted phenyl group and the substituent is preferably a sulfonamido group, an acylamino group, a ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group or an N-acylsulfamoylamino group, more preferably a sulfonamido group or a ureido group, and most preferably a sulfonamido group.
In the hydrazine derivative represented by formula (D), R₂₀ or R₁₀ preferably contains, as a substituent, a ballast group, an adsorbent to silver halide, a quaternary ammonio group-containing group, a nitrogen-containing heterocyclic group containing quaternized nitrogen atom, a group containing an ethyleneoxy group as a repeating unit, an alkylthio group, an arylthio group, a heterocyclic thio group, a dissociative group capable of dissociating in an alkaline developing solution, or a hydrazino group (a group represented by -NHNH-G₁₀-R₁₀) capable of forming a polymer (i.e., a multimer). More preferably, R₂₀ directly or indirectly contains any one of those groups described above, and most preferably, R₂₀ represents a phenyl group substituted by a benzenesulfonamido group and as a substituent on the benzenesulfonamido group, directly or indirectly contains any one of those groups described above.
Among the groups represented by R₁₀, when G₁₀ is a -CO- group, preferred are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, more preferred are a hydrogen atom, an alkyl group, a substituted aryl group (the substituent is preferably an electron attractive group or an o-hydroxymethyl group), most preferred are a hydrogen atom and an alkyl group.
When G₁₀ is a -COCO- group, preferred are an alkoxy group, an aryloxy group and an amino group, more preferred are a substituted amino group. Specifically, an alkylamino group, an arylamino group and a saturated or unsaturated heterocyclic amino group are preferred.
When G₁₀ is an -SO₂- group, R₁₀ is preferably an alkyl group, an aryl group or a substituted amino group.
In formula (D), G₁₀ is preferably a -CO- group or a -COCO- group, more preferably a -CO- group.
Specific examples of the compound represented by formula (D) are set forth below, however, the present invention is not limited to the following compounds (In the following description, for example, the item "1a" means the Compound 1a wherein X is 3-NHCOC₉H₁₉(n) and R is -H in D-1).
In addition to the above-described compounds, the following hydrazine derivatives may be preferably used as the hydrazine derivative for use in the present invention. The hydrazine derivative for use in the present invention may also be synthesized by various methods described in the patent publications described blow.
The compounds represented by (Chem. 1) of JP-B-6-77138, specifically, the compounds described at pages 3 and 4; the compounds represented by formula (I) of JP-B-6-93082, specifically, Compounds 1 to 38 described at pages 8 to 18; the compounds represented by formulae (4), (5) and (6) of JP-A-6-230497, specifically, Compounds 4-1 to 4-10 described at pages 25 and 26, Compounds 5-1 to 5-42 described at pages 28 to 36 and Compounds 6-1 to 6-7 described at pages 39 and 40; the compounds represented by formulae (1) and (2) of JP-A-6-289520, specifically, Compounds 1-1) to 1-17) and 2-1) described at pages 5 to 7; the compounds represented by (Chem. 2) and (Chem. 3) of JP-A-6-313936, specifically the compounds described at pages 6 to 19; the compounds represented by (Chem. 1) of JP-A-6-313951, specifically, the compounds described at pages 3 to 5; the compounds represented by formula (I) of JP-A-7-5610, specifically, Compounds I-1 to I-38 described at pages 5 to 10; the compounds represented by formula (II) of JP-A-7-77783, specifically, Compounds II-1 to II-102 described at pages 10 to 27; the compounds represented by formulae (H) and (Ha) of JP-A-7-104426, specifically, Compounds H-1 to H-44 described at pages 8 to 15; compounds having in the vicinity of the hydrazine group an anionic group or a nonionic group capable of forming an intramolecular hydrogen bond with a hydrogen atom of the hydrazine described in JP-A-9-22082, particularly, the compounds represented by formulae (A), (B), (C), (D), (E) and (F), specifically, Compounds N-1 to N-30; and the compounds represented by formula (1) of JP-A-9-22082, specifically, Compounds D-1 to D-55. Other examples include the hydrazine derivatives described in WO95-32452, WO95-32453, JP-A-9-179229, JP-A-9-235264, JP-A-9-235265, JP-A-9-235266, JP-A-9-235267, JP-A-9-319019, JP-A-9-319020, JP-A-10-130275, JP-A-11-7093, JP-A-6-332096, JP-A-7-209789, JP-A-8-6193, JP-A-8-248549, JP-A-8-248550, JP-A-8-262609, JP-A-8-314044, JP-A-8-328184, JP-A-9-80667, JP-A-9-127632, JP-A-9-146208, JP-A-9-160156, JP-A-10-161260, JP-A-10-221800, JP-A-10-213871, JP-A-10-254082, JP-A-10-254088, JP-A-7-120864, JP-A-7-244348, JP-A-7-333773, JP-A-8-36232, JP-A-8-36233, JP-A-8-36234, JP-A-8-36235, JP-A-8-272022, JP-A-9-22083, JP-A-9-22084, JP-A-9-54381 and JP-A-10-175946.
In the present invention, the hydrazine-based nucleating agent may be used by dissolving it in an appropriate water-miscible organic solvent such as alcohols (e.g., methanol, ethanol, propanol, fluorinated alcohol), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide and methyl cellosolve.
Also, the nucleating agent may be used in the form of an emulsified dispersion obtained by a well-known emulsified dispersion method of dissolving the nucleating agent using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate and diethyl phthalate, or an auxiliary solvent such as ethyl acetate and cyclohexanone, and mechanically forming the solution into an emulsified dispersion. Furthermore, the nucleating agent may be used by dispersing a hydrazine derivative powder in water using a ball mill, a colloid mill or an ultrasonic wave according to a method known as a solid dispersion method.
In the present invention, the hydrazine-based nucleating agent may be added to any of silver halide emulsion layers and other hydrophilic colloid layers in the silver halide emulsion layer side with respect to the support but is preferably added to a silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto. Also, two or more hydrazine-based nucleating agents may be used in combination.
In the present invention, the amount of the nucleating agent added is preferably from 1×10^-5 to 1×10^-2 mol, more preferably from 1×10^-5 to 5×10^-3 mol, most preferably from 2×10^-5 to 5×10^-3 mol, per mol of silver halide.
In the present invention, the light-sensitive material preferably contains an amine derivative, an onium salt, a disulfide derivative or a hydroxymethyl derivative as a nucleation accelerator. Examples of the nucleating accelerator include the compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, Compounds A-1) to A-73) described at pages 49 to 58; the compounds represented by (Chem. 21), (Chem. 22) and (Chem. 23) of JP-A-7-84331, specifically, the compounds described at pages 6 to 8; the compounds represented by formulae [Na] and [Nb] of JP-A-7-104426, specifically, Compounds Na-1 to Na-22 and Compounds Nb-1 to Nb-12 described at pages 16 to 20; the compounds represented by formulae (1), (2), (3), (4), (5), (6) and (7) of JP-A-8-272023, specifically, Compounds 1-1 to 1-19, Compounds 2-1 to 2-22, Compounds 3-1 to 3-36, Compounds 4-1 to 4-5, Compounds 5-1 to 5-41, Compounds 6-1 to 6-58 and Compounds 7-1 to 7-38; and the nucleating accelerators described in JP-A-9-297377, page 55, from column 108, line 8 to column 136, line 44.
Specific examples of the nucleation accelerator for use in the present invention are set forth below, however, the present invention is not limited to the following compounds.
The nucleation accelerator for use in the present invention may be used by dissolving it in an appropriate water-miscible organic solvent such as alcohols (e.g., methanol, ethanol, propanol, fluorinated alcohol), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide and methyl cellosolve.
The nucleation accelerator may also be used in the form of an emulsified dispersion obtained by a well-known emulsified dispersion method of dissolving the nucleation accelerator using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate and diethyl phthalate, or an auxiliary solvent such as ethyl acetate and cyclohexanone, and mechanically forming it into an emulsified dispersion. Furthermore, the nucleation accelerator may be used by dispersing a nucleation accelerator powder in water using a ball mill, a colloid mill or an ultrasonic wave according to a method known as a solid dispersion method.
The nucleation accelerator for use in the present invention may be added to any of silver halide emulsion layers and other hydrophilic colloid layers in the silver halide emulsion layer side with respect to the support but is preferably added to a silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto.
The amount used of the nucleation accelerator for use in the present invention is preferably from 1×10^-6 to 2×10^-2 mol, more preferably from 1×10^-5 to 2×10^-2 mol, most preferably from 2×10^-5 to 1×10^-2 mol, per mol of silver halide. Two or more nucleation accelerators may also be used in combination.
Various additives for use in the light-sensitive material of the present invention are not particularly limited and, for example, those described in the portion shown below can be preferably used:
the polyhydroxybenzene compounds described in JP-A-3-39948, from page 10, right lower column, line 11 to page 12, left lower column, line 5, specifically, Compounds (III)-1 to (III)-25;
the compounds having substantially no absorption maximum in the visible region represented by formula (I) of JP-A-118832, specifically, Compounds I-1 to I-26;
the antifoggants described in JP-A-2-103536, from page 17, right lower column, line 19 to page 18, right upper column, line 4;
the polymer latexes described in JP-A-2-103536, page 18, left lower column, lines 12 to 20; the polymer latexes having an active methylene group represented by formula (I) of JP-A-9-179228, specifically Compounds I-1 to I-16; polymer latexes having a core/shell structure described in JP-A-9-179228, specifically, Compounds P-1 to P-55; the acidic polymer latexes described in JP-A-7-104413, page 14, left column, line 1 to right column, line 30, specifically Compounds II-1) to II-9) described at page 15;
the matting agents, lubricants and plasticizers described in JP-A-2-103536, page 19, from left upper column, line 15 to right upper column, line 15;
the hardening agents described in JP-A-2-103536, page 18, right upper column, lines 5 to 17;
the compounds having an acid radical described in JP-A-2-103536, from page 18, right lower column, line 6 to page 19, left upper column, line 1;
the electrically conducting substances described in JP-A-2-18542, from page 2, left lower column, line 13 to page 3, right upper column, line 7, specifically metal oxides described at page 2, right lower column, lines 2 to 10 and Compounds P-1 to P-7 as an electrically conducting polymer compound;
the water-soluble dyes described in JP-A-2-103536, page 17, right lower column, line 1 to right upper column, line 18;
the solid disperse dyes represented by formulae (FA), (FA1), (FA2) and (FA3) of JP-A-9-179243, specifically, Compounds F1 to F-34; Compounds (II-2) to (II-24), Compounds (III-5) to (III-18) and Compounds (IV-2) to (IV-7) described in JP-A-7-152112; and the solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382;
the surfactants described in JP-A-2-12236, page 9, from right upper column, line 7 to right lower column, line 3; the PEG-based surfactants described in JP-A-2-103536, page 18, left lower column, lines 4 to 7; the fluorine-containing surfactants described in JP-A-3-39948, from page 12, left lower column, line 6 to page 13, right lower column, line 5, specifically, Compounds VI-1 to VI-15;
the following nucleation accelerators such as amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives: the compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, Compounds A-1) to A-73) described at pages 49 to 58; the compounds represented by (Chem. 21), (Chem. 22) and (Chem. 23) of JP-A-7-84331, specifically, the compounds described at pages 6 to 8; the compounds represented by formulae [Na] and [Nb] of JP-A-7-104426, specifically, Compounds Na-1 to Na-22 and Compounds Nb-1 to Nb-12 described at pages 16 to 20; the compounds represented by formulae (1), (2), (3), (4), (5), (6) and (7) of JP-A-8-272023, specifically, Compounds 1-1 to 1-19, Compounds 2-1 to 2-22, Compounds 3-1 to 3-36, Compounds 4-1 to 4-5, Compounds 5-1 to 5-41, Compounds 6-1 to 6-58 and Compounds 7-1 to 7-38;
the following hydrazine derivatives: the compounds represented by formula (I) of JP-A-7-287335, specifically, Compounds I-1 to I-53; the compounds represented by (Chem. 1) of JP-B-6-77138, specifically, the compounds described at pages 3 and 4; the compounds represented by formula (I) of JP-B-6-93082, specifically, Compounds 1 to 38 described at pages 8 to 18; the compounds represented by formulae (4), (5) and (6) of JP-A-6-230497, specifically, Compounds 4-1 to 4-10 described at pages 25 and 26, Compounds 5-1 to 5-42 described at pages 28 to 36, and Compounds 6-1 to 6-7 described at pages 39 and 40; the compounds represented by formulae (1) and (2) of JP-A-6-289520, specifically, Compounds 1-1) to 1-17) and 2-1) described at pages 5 to 7; the compounds represented by (Chem. 2) and (Chem. 3) of JP-A-6-313936, specifically, the compounds described at pages 6 to 19; the compounds represented by (Chem. 1) of JP-A-6-313951, specifically, the compounds described at pages 3 to 5; the compounds represented by formula (1) of JP-A-7-5610, specifically, Compounds I-1 to I-38 described at pages 5 to 10; the compounds represented by formula (II) of JP-A-7-77783, specifically, Compounds II-1 to II-102 described at pages 10 to 27; the compounds represented by formulae (H) and (Ha) of JP-A-7-104426, specifically, Compounds H-1 to H-44 described at pages 8 to 15; the compounds characterized by having, in the vicinity of the hydrazine group, an anionic group or a nonionic group of forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine described in JP-A-9-22082, particularly, the compounds represented by formulae (A), (B), (C), (D), (E) and (F), specifically, Compounds N-1 to N-30; the compounds represented by formula (1) of JP-A-9-22082, specifically, Compounds D-1 to D-55;
the redox compounds capable of releasing a development inhibitor upon oxidation described in JP-A-5-274816, preferably, the redox compounds represented by formulae (R-1), (R-2) and (R-3), specifically, Compounds R-1 to R-68; and
the binders described in JP-A-2-18542, page 3, right lower column, lines 1 to 20.
The processing agents such as developer and fixing solution and the processing method for use in the present invention are described below, however, of course, the present invention is by no means limited to the following description and specific examples.
In the development for use in the present invention, any well-known method may be used and a well-known development processing solution may be used.
The developing agent used in the developer (hereinafter, the development initiating solution and the development replenisher are collectively called a developer) for use in the present invention is not particularly limited but preferably contains dihydroxybenzenes, ascorbic acid derivatives and hydroquinone monosulfonates individually or in combination. In particular, the developing agent preferably contains a dihydroxybenzene-based developing agent and an auxiliary developing agent of showing superadditivity therewith and preferred examples of this combination include a combination of a dihydroxybenzene or an ascorbic acid derivative with a 1-phenyl-3-pyrazolidone, and a combination of a dihydroxybenzene or an ascorbic acid derivative with a p-aminophenol.
In the developing agents for use in the present invention, examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropylhydroquinone and methylhydroquinone, with hydroquinone being particularly preferred. Examples of the ascorbic acid derivative developing agent include ascorbic acid, isoascorbic acid and salts thereof, with sodium erythorbate being particularly preferred in view of the cost for materials.
Examples of the 1-phenyl-3-pyrazolidone and derivatives thereof as the developing agent for use in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.
Examples of the p-aminophenol-based developing agent for use in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, o-methoxyp-(N,N-dimethylamino)phenol, o-methoxy-p-(N-methylamino)phenol, with N-methyl-p-aminophenol and aminophenols described in JP-A-9-297377 and JP-A-9-297378 being particularly preferred.
The dihydroxybenzene-based developing agent is usually used in an amount of preferably from 0.05 to 0.8 mol/liter. In the case where a dihydroxybenzene and a 1-phenyl-3-pyrazolidone or a p-aminophenol are used in combination, the former is preferably used in an amount of 0.05 to 0.6 mol/liter, more preferably from 0.10 to 0.5 mol/liter, and the latter is preferably used in an amount of 0.06 mol/liter or less, more preferably from 0.003 to 0.03 mol/liter.
The ascorbic acid derivative developing agent is usually used in an amount of preferably from 0.01 to 0.5 mol/liter, more preferably from 0.05 to 0.3 mol/liter. In the case of using an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or a p-aminophenol in combination, the ascorbic acid derivative is preferably used in an amount of 0.01 to 0.5 mol/liter, and the 1-phenyl-3-pyrazolidone or p-aminophenol is preferably used in an amount of 0.005 to 0.2 mol/liter.
The developer used in processing the light-sensitive material of the present invention may contain additives (e.g., developing agent, alkali agent, pH buffer, preservative, chelating agent) which are commonly used. Specific examples thereof are described below, however, the present invention is by no means limited thereto.
Examples of the buffer for use in the developer used in development-processing the light-sensitive material of the present invention include carbonates, boric acids described in JP-A-62-186259, saccharides (e.g., saccharose) described in JP-A-60-93433, oximes (e.g., acetoxime), phenols (e.g., 5-sulfosalicylic acid) and tertiary phosphates (e.g., sodium salt, potassium salt), with carbonates and boric acids being preferred. The amount used of the buffer, particularly carbonate, is preferably from 0.05 mol/liter or more, more preferably from 0.08 to 1.0 mol/liter.
In the present invention, the development initiating solution and the development replenisher bot preferably have a property such that "when 0.1 mol of sodium hydroxide is added to 1 liter of the development initiating solution or development replenisher, the increment in pH is from 0.2 to 1.5". Whether the development initiating solution or development replenisher used has this property can be confirmed by the following method. The development initiating solution or development replenisher tested is adjusted to a pH of 10.5, 0.1 mol of sodium hydroxide is added to 1 liter of the development initiating solution or development replenisher, the pH of the solution at this time is measured, and when the increment in the pH value is from 0.2 to 1.5, the development initiating solution or development replenisher is judged to have the property specified above. In the present invention, the development initiating solution or development replenisher preferably has a property such that the increment of the pH value in the above-described test is from 0.3 to 1.0 (preferably from 0.3 to 0.4).
Examples of the preservative for use in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, sodium metabisulfite and formaldehyde-sodium bisulfite. The sulfite is preferably used in an amount of 0.2 mol/liter or more, more preferably 0.3 mol/liter or more, but if the sulfite is added in an excessively large amount, silver staining is caused in the developer. Accordingly, the upper limit is preferably 1.2 mol/liter. The amount used is more preferably from 0.35 to 0.7 mol/liter.
In combination with the sulfite, a small amount of an ascorbic acid derivative which is described above, may be added as a preservative for the dihydroxybenzene-based developing agent. In particular, sodium erythorbate is preferred in view of the cost for materials. The amount added thereof is preferably from 0.03 to 0.12, more preferably from 0.05 to 0.10, in terms of the molar ratio to the dihydroxybenzene-based developing agent. In the case of using an ascorbic derivative as a preservative, the developer preferably contains no boron compound.
Examples of the additives other than those described above include a development inhibitor such as sodium bromide and potassium bromide, an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide, a development accelerator such as alkanolamine (e.g., diethanolamine, triethanolamine), imidazole and derivatives thereof, and a physical development unevenness inhibitor such as heterocyclic mercapto compounds (e.g., sodium 3-(5-mercaptotetrazol-1-yl)benzenesulfonate, 1-phenyl-5-mercaptotetrazole) and the compounds described in JP-A-62-212651.
Furthermore, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound or a benzimidazole-based compound may be added as an antifoggant or a black spot (black pepper) inhibitor. Specific examples thereof include 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio)butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole and 2-mercaptobenzotriazole. The amount added thereof is usually from 0.01 to 10 mmol, preferably from 0.1 to 2 mmol, per liter of the developer.
In the developer for use in the present invention, various organic or inorganic chelating agents may also be used individually or in combination.
Examples of the inorganic chelating agent which can be used include sodium tetrapolyphosphate and sodium hexametaphosphate.
Examples of the organic chelating agent which can be mainly used include organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid.
Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, itaconic acid, malic acid, citric acid and tartaric acid.
Examples of the aminopolycarboxylic acid include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid and the compounds described in JP-A-52-25632, JP-A-55-67747, JP-A-57-102624 and JP-B-53-40900.
Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in U.S. Patents 3,214,454 and 3,794,591 and German Patent Publication (OLS) No. 2,227,639, and the compounds described in Research Disclosure, Vol. 181, Item 18170 (May, 1979).
Examples of the aminophosphonic acid include aminotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid and the compounds described in Research Disclosure, No. 18170 supra, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883 and JP-A-56-97347.
Examples of the organic phosphonocarboxylic acid include the compounds described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127, JP-A-55-4024, JP-A-55-4025, JP-A-55-126241, JP-A-55-65955, JP-A-55-56956 and Research Disclosure, No. 18170 supra.
The organic and/or inorganic chelating agents are not limited to those described above. The organic and/or inorganic chelating agent may also be used in the form of an alkali metal salt or an ammonium salt. The amount of the chelating agent added is preferably from 1×10^-4 to 1×10^-1 mol, more preferably from 1×10^-3 to 1×10^-2 mol, per liter of the developer.
The developer may also contain a silver staining inhibitor and examples thereof include the compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, JP-A-4-362942 and JP-A-8-6215, triazine having one or more mercapto group (for example, the compounds described in JP-B-6-23830, JP-A-3-282457 and JP-A-7-175178), pyrimidine having one or more mercapto group (for example, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine and the compounds described in JP-A-9-274289), pyridine having one or more mercapto group (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine and the compounds described in JP-A-7-248587), pyrazine having one or more mercapto group (for example, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine and 2,3,5-trimercaptopyrazine), pyridazine having one or more mercapto group (for example, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine and 3,4,6-trimercaptopyridazine), the compounds described in JP-A-7-175177 and polyoxyalkylphosphonic acid esters described in U.S. Patent 5,457,011. These silver staining inhibitors may be used individually or in combination of a plurality of the compounds. The amount added thereof is preferably from 0.05 to 10 mmol, more preferably from 0.1 to 5 mmol, per liter of the developer.
The developer may also contain a dissolution aid and examples thereof include the compounds described in JP-A-61-267759.
If desired, the developer may further contain a color toner, a surfactant, a defoaming agent and a hardening agent.
The pH of the developer is preferably from 9.0 to 12.0, more preferably from 9.0 to 11.0, still more preferably from 9.5 to 11.0. The alkali agent used for adjusting the pH may be a normal water-soluble inorganic alkali metal salt (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate).
If the specific gravity of the developer used is excessively high, the exposed light sensitivity is liable to have low density in the blackened area. Therefore, the specific gravity of the developer used is preferably from 1.100 or less, more preferably from 1.020 to 1.100, still more preferably from 1.040 to 1.100.
As for the cation of the developer, potassium ion is preferred because it does not inhibit the development and causes less indentation called fringe in the periphery of the blackened portion as compared with sodium ion. When the developer is stored as a concentrated solution, potassium ion is generally preferred because of its higher solubility. However, potassium ion inhibits the fixing in the fixing solution on the same level as the silver ion and if the developer has a high potassium ion concentration, the developer is carried over by the light-sensitive material and disadvantageously elevates the potassium ion concentration in the fixing solution. From these reasons, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of potassium ion to sodium ion can be freely controlled within the above-described range by the counter cation such as pH buffer, pH adjusting agent, preservative or chelating agent.
The replenishing amount of the developer is 390 ml or less, preferably from 30 to 325 ml, most preferably from 120 to 250 ml, per m² of the light-sensitive material. The developer replenisher may have the same composition and/or concentration as the development initiating solution or may have a different composition and/or concentration from the initiating solution.
Examples of the fixing agent which can be used in the fixing processing agent for use in the present invention include ammonium thiosulfate, sodium thiosulfate and ammonium sodium thiosulfate. The amount of the fixing agent used may be varied appropriately but is generally from about 0.7 to about 3.0 mol/liter.
The fixing solution for use in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt, which acts as a hardening agent. Of these, a water-soluble aluminum salt is preferred. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, ammonium aluminum sulfate, aluminum nitrate and aluminum lactate. The hardening agent is preferably contained, in terms of the aluminum ion concentration in the solution on use, in an amount of 0.01 to 0.15 mol/liter.
In the case of storing the fixing solution in the form of a concentrated solution or a solid agent, the fixing agent may be constructed by a plurality of parts where a hardening agent or the like is prepared as a separate part, or may be constructed as a one-part agent containing all components.
The fixing processing agent may contain, if desired, a preservative (for example, sulfite, bisulfite or metabisulfite in an amount of 0.015 mol/liter or more, preferably from 0.02 to 0.3 mol/liter), a pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid or adipic acid in an amount of 0.1 to 1 mol/liter, preferably from 0.2 to 0.7 mol/liter) or a compound having aluminum-stabilizing ability or hard water-softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid; citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, Tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, a derivative or a salt thereof, or a sugar in an amount of 0.001 to 0.5 mol/liter, preferably from 0.005 to 0.3 mol/liter). In view of recent environmental protection, boron-based compounds are preferably not contained.
In addition, the fixing processing agent may contain the compounds described in JP-A-62-78551, a pH adjusting agent (e.g., sodium hydroxide, ammonia, sulfuric acid), a surfactant, a wetting agent, a fixing accelerator and the like. Examples of the surfactant include anionic surfactants such as sulfated product and sulfonated product, polyethylene-based surfactants, and the amphoteric surfactants described in JP-A-57-6840. A well-known defoaming agent may also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include the alkyl- or aryl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, the thiourea derivatives described in JP-B-45-35754, JP-B-58-122535 and JP-B-58-122536, alcohols having a triple bond within the molecule, the thioether compounds described in U.S. Patent 4,126,459, mercapto compounds described in JP-A-64-4739, JP-A-1-4739, JP-A-1-159645 and JP-A-3-101728, the meso-ionic compounds described in JP-A-4-170539 and thiocyanates.
The pH of the fixing solution for use in the present invention is preferably 4.0 or more, more preferably from 4.5 to 6.0. The pH of the fixing solution elevates due to mingling of the developer on processing and in this case, the pH is, in the case of hardening fixing solution, 6.0 or less, preferably 5.7 or less, and in the case of non-hardening fixing solution, 7.0 or less, preferably 6.7 or less.
The replenishing amount of the fixing solution is 500 ml or less, preferably 390 ml or less, more preferably from 80 to 320 ml, per 1 m² of the light-sensitive material. The replenisher may have the same composition and/or concentration as the initiating solution or may have a different composition and/or concentration from the initiating solution.
The fixing solution may be regenerated and reused using a well-known fixing solution regenerating method such as electrolytic silver recovery. Examples of the regenerating apparatus include FS-2000 manufactured by Fuji Photo Film Co., Ltd..
It is also preferred to remove dyes or the like using an adsorption filter such as activated carbon.
In the case where the development processing solution and the fixing processing solution for use in the present invention are a liquid agent, these are each preferably stored in a packaging material having a low oxygen permeability described, for example, in JP-A-61-73147. In the case where these solutions are a concentrated solution, each solution on use is diluted with water at a ratio such that the water is from 0.2 to 3 parts per 1 part of the concentrated solution, to have a predetermined concentration.
Even when the development processing agent or the fixing processing agent for use in the present invention is formed as a solid, the same effects as provided by the liquid agent can be obtained. The solid processing agent is described below.
The solid processing agent for use in the present invention may have a well-known shape (e.g., powder, grain, granule, lump, tablet, compactor, briquette, plate, bar, paste). The solid agent may be prepared by coating respective components with a water-soluble coating agent or film so as to separate the components which react with each other on contacting, or may be prepared to have a multilayer structure so as to separate the components reactive with each other. These techniques may also be used in combination.
The coating agent or the granulating aid used may be a well-known compound, however, preferred examples thereof include polyvinyl pyrrolidone, polyethylene glycol, sulfonated polystyrene and vinyl-based compounds. In addition, JP-A-5-45805, from column 2, line 48 to column 3, line 13, may be referred to.
In the case where the solid agent is prepared to have a multilayer structure, a component which does not react on contacting may be interposed between components which react with each other and the obtained laminate may be formed into a tablet or a briquette. Also, the components each in a well-known shape may be formed into the same layer structure as above and then packaged. These methods are described, for example, in JP-A-61-259921, JP-A-4-16841, JP-A-4-78848 and JP-A-5-93991.
The bulk density of the solid processing agent is preferably from 0.5 to 6.0 g/cm³, more preferably from 1.0 to 5.0 g/cm³ in the case of a tablet and from 0.5 to 1.5 g/cm³ in the case of a granule.
The solid processing agent for use in the present invention can be prepared by any well-known method described, for example, in JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, JP-A-4-78848, JP-A-5-93991, JP-A-4-85533, JP-A-4-85534, JP-A-4-85535, JP-A-5-134362, JP-A-5-197070, JP-A-5-204098, JP-A-5-224361, JP-A-6-138604, JP-A-6-138605 and JP-A-8-286329 may be used.
More specifically, a rolling granulation method, an extrusion granulation method, a compressive granulation method, a cracking granulation method, an agitating granulation method, a spray dry method, a dissolving coagulation method, a briquetting method or a roller compacting method may be used.
The solubility of the solid agent for use in the present invention may be controlled by changing the surface state (e.g., smooth, porous) or partially changing the thickness or by preparing the solid agent in a hollow doughnut form. Furthermore, the solid agent may be prepared as a plurality of granulated products having different solubilities or may be prepared to have a plurality of shapes so that a plurality of stock materials different in the solubility can coincide in the solubility. Also, the solid agent may be prepared as a granulated product having a multilayer structure different in the composition between the surface and the inside.
The packaging material for the solid agent is preferably a material having low permeability to oxygen and water. The shape of the packaging material may be a well-known form such as bag, cylinder and box. Furthermore, the packaging material may have a foldable shape disclosed in JP-A-6-242585 to JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, JP-A-6-301189, JP-A-7-5664 and JP-A-7-5666 to JP-A-7-5669 and this is preferred because the space for storing waste packaging materials can be saved. The port for taking out the processing agent of the packaging material may be secured with a screw cap, a pull-top or an aluminum seal or may be heat sealed, however, this is not particularly limited and other well-known means may be used. The waste packaging material is preferably recycled or reused in view of the environmental conservation.
The method for dissolving or replenishing the solid processing agent for use in the present invention is not particularly limited and well-known methods may be used. Examples of the method include a method of dissolving a constant amount of the solid processing agent by a dissolving apparatus having a stirring function and replenishing the solution, a method of dissolving the solid processing agent by a dissolving apparatus having a dissolving portion and a portion for stocking the finished solution and replenishing the solution from the stock portion described in JP-A-9-80718, a method of charging the processing agent into a circulation system of an automatic developing machine, dissolving it and replenishing the solution described in JP-A-5-119454, JP-A-6-19102 and JP-A-7-261357, and a method of charging and dissolving the processing agent according to the light-sensitive material processed in an automatic developing machine self-containing a dissolution tank. Other than these, any well-known method may be used. The processing agent may be charged manually or may be automatically unsealed and automatically charged using a dissolving apparatus or automatic developing machine having an unsealing mechanism described in JP-A-9-138495. In view of the working environment, the latter is preferred. More specifically, the methods of bursting, peeling off, cutting out or pushing away the takeout port and the methods described in JP-A-6-19102 and JP-A-6-95331 may be used.
The light-sensitive material processed through development and fixing is then subjected to water washing or stabilization (hereinafter, unless otherwise specified, water washing includes stabilization processing and the solution used therefor is called water or washing water). The water for use in water washing may be tap water, ion exchanged water, distilled water or stabilizing solution. The replenishing amount of the washing water is generally from about 8 to about 17 liter per m² of the light-sensitive material, however, a replenishing amount lower than the above-described range may also be used. In particular, when the replenishing amount is 3 liter or less (including 0, namely, standing (i.e., pooled) water washing), not only the processing can achieve water saving but also the piping for installing an automatic developing machine can be dispensed with. When water washing is performed with a low replenishing amount, a rinsing tank with a squeeze roller or a cross-over roller described in JP-A-63-18350 and JP-A-62-287252 is preferably provided. Also, for the purpose of reducing the pollution load problem encountered in the case of small-amount water washing or preventing water scale, the addition of various oxidizing agents (e.g., ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide salt) and the filter filtration may be combined.
A multi-stage countercurrent system (for example, two stages or three stages) has been long known as a method for reducing the replenishing amount of washing water and the replenishing amount of washing water is preferably from 50 to 200 ml per m² of the light-sensitive material. This effect can be obtained similarly in the case of an independent multi-stage system (a method of not using a countercurrent system but supplying a new solution individually to the multi-stage water washing tanks).
In the method for use in the present invention, means for preventing water scale may be provided in the water washing step. The water scale preventing means is not particularly restricted and well-known means may be used. Examples thereof include a method of adding a fungicide (so-called water scale inhibitor), a method of passing electricity, a method of irradiating ultraviolet rays, infrared rays or far infrared rays, a method of applying a magnetic field, a method of performing an ultrasonic wave treatment, a method of applying heat and a method of evacuating the tank on standing. The water scale preventing means may be applied according to the processing of the light-sensitive material, may be applied at predetermined intervals irrespective of the use state or may be applied only in the period of non-processing time such as night time. Furthermore, the washing water may be previously treated with a water scale preventing means and then replenished. In view of preventing generation of resistance microbes, it is preferred to apply different water scale preventing means at predetermined intervals.
As for the water saving and water scale preventing apparatus, AC-1000 manufactured by Fuji Photo Film Co., Ltd. may be used, and as for the water scale preventing agent, AB-5 produced by Fuji Photo Film Co., Ltd. and the method of JP-A-11-231485 may be used.
The fungicide is not particularly restricted and a well-known fungicide may be used. Examples thereof include, in addition to the above-described oxidizing agents, a chelating agent such as glutaraldehyde and aminopolycarboxylic acid, a cationic surfactant, and a mercaptopyridine oxide (e.g., 2-mercaptopyridine-N-oxide). These fungicide may be used either individually or in plurality in combination.
For passing the electricity, the methods described in JP-A-3-224685, JP-A-3-224687, JP-A-4-16280 and JP-A-4-18980 may be used.
In addition, a well-known water-soluble surfactant or defoaming agent may be added so as to prevent uneven processing due to bubbling or to prevent transfer of stains. Furthermore, a dye adsorbent described in JP-A-63-163456 may be provided in the water washing system so as to prevent stains due to a dye eluted out from the light-sensitive material.
The overflow solution from the water washing step may be partially or wholly used by mixing it with the processing solution having fixing ability as described in JP-A-60-235133. In view of the conservation of natural environment, the solution is preferably discharged after passing through a microorganism treatment (for example, treatment by sulfur oxidation bacteria or activated sludge, or treatment through a filter in which microorganisms are supported on a porous support such as activated carbon or ceramic) or an oxidation treatment using electrification or an oxidizing agent so as to reduce the biochemical oxygen demand (BOD), chemical oxygen demand (COD) or iodine consumption before discharge. Also, for reducing the silver concentration in waste water, the solution is preferably passed through a filter using a polymer having affinity for silver or filtered after adding a compound of forming a sparingly soluble silver complex, such as trimercaptotriazine, to precipitate silver.
In some cases, a stabilization processing is performed subsequent to the water washing and as one example thereof, a bath containing the compound described in JP-A-2-201357, JP-A-2-132435, JP-A-1-102553 and JP-A-46-44446 may be used as a final bath of the light-sensitive material. This stabilization bath may also contain, if desired, an ammonium compound, a metal compound such as Bi and Al, a fluorescent brightening agent, various chelating agents, a film pH adjusting agent, a hardening agent, a bactericide, a fungicide, an alkanolamine and a surfactant.
The additives such as fungicide and the stabilizing agent added to the water washing or stabilization bath may be prepared in the solid agent form similarly to the above-described development and fixing processing agents.
The waste water of developer, fixing solution, washing water or stabilizing solution for use in the present invention is preferably burned for disposal. Also, the waste water may be disposed after forming it into a concentrated solution or a solid using a concentrating apparatus described, for example, in JP-B-7-83867 and U.S. Patent 5,439,560.
In the case of reducing the replenishing amount of the processing agent, the contact area of the processing tank with air is preferably made small to prevent evaporation or air oxidation of the solution. A roller transportation-type automatic developing machine is described in U.S. Patents 3,025,779 and 3,545,971, and in the present invention, this is simply referred to as a roller transportation-type automatic processor. This automatic processor consists of four steps of development, fixing, water washing and drying, and the method for use in the present invention most preferably follows this four-step processing, though other steps (e.g., stopping step) are not rejected. Also, a rinsing bath may be further provided between the development and the fixing and/or between the fixing and the water washing.
In the development processing for use in the present invention, the dry-to-dry time (from the initiation of processing until the completion of drying) is preferably from 25 to 160 seconds, the development time and the fixing time each is 40 seconds or less, preferably from 6 to 35 seconds, and the temperature of each solution is preferably from 25 to 50°C, more preferably from 30 to 40°C. The temperature and the processing time of water washing are preferably from 0 to 50°C and 40 seconds or less, respectively. According to the method for use in the present invention, the light-sensitive material after development, fixing and water washing may be dried after passing through squeeze rollers for squeezing out the washing water. The drying is performed at a temperature of about 40°C to about 100°C. The drying time may be appropriately varied depending upon the ambient state. The drying method is not particularly restricted and any well-known method may be used, however, hot air drying, drying by a heat roller disclosed in JP-A-4-15534, JP-A-5-2256 and JP-A-5-289294, and drying by far infrared rays may be used, and a plurality of these drying methods may also be used in combination.
The present invention is described in greater detail below, however, the present invention should not be construed as being limited thereto.

EXAMPLE I-1

Preparation of Emulsion A:

Solution 1:
Water	750 ml
Gelatin	20 g
Sodium chloride	3 g
1,3-Dimethylimidazolidine-2-thione	20 mg
Sodium benzenethiosulfonate	10 mg
Citric acid	0.7 g

Solution 2:
Water	300 ml
Silver nitrate	150 g

Solution 3:
Water	300 ml
Sodium chloride	38 g
Potassium bromide	32 g
Potassium hexachloroiridate(III) (20% by weight aqueous solution containing 0.005% by weight of KCl)	5 ml
Ammonium hexachlororhodate (20% by weight aqueous solution containing 0.001% by weight of NaCl)	7 ml

The potassium hexachloroiridate(III) (20% by weight aqueous solution containing 0.005% by weight of KCl) and ammonium hexachlororhodate (20% by weight aqueous solution containing 0.001% by weight of NaCl) used in Solution 3 were prepared by dissolving each powder in a 20% by weight aqueous solution of KCl or a 20% by weight aqueous solution of NaCl and heating the solution at 40°C for 120 minutes.
Solution 2 and Solution 3 each in an amount corresponding to 90% were simultaneously added to Solution 1 kept at 38°C and a pH of 4.5 while stirring over 20 minutes to form core grains (i.e., nucleus grains) of 0.16 µm. Subsequently, Solution 4 and Solution 5 shown below were added over 8 minutes and then, the remaining Solution 2 and Solution 3 each corresponding to 10% were added over 2 minutes to grow the grains up to 0.21 µm. Furthermore, 0.15 g of potassium iodide was added and the grains were ripened for 5 minutes, thereby completing the grain formation.

Solution 4:

Water 100 ml

Silver nitrate 50 g

Solution 5:

Water 100 ml

Sodium chloride 13 g

Potassium bromide 11 g

Yellow prussiate of potash 5 mg
The obtained emulsion was water-washed by a flocculation method in a usual manner. More specifically, the temperature was lowered to 35°C, 3 g of Anionic Precipitant 1 shown below was added and the pH was lowered using sulfuric acid until silver halide was precipitated (pH: 3.2±0.2). Thereafter, about 3 liter of the supernatant was removed (first water washing). After 3 liter of distilled water was added, sulfuric acid was added until silver halide was precipitated and 3 liter of the supernatant was again removed (second water washing). The same operation as in the second water washing was once more repeated (third water washing), whereby the water washing/desalting step was completed. To the water-washed and desalted emulsion, 45 g of gelatin was added, the pH and the pAg were adjusted to 5.6 and 7.5, respectively, and then the emulsion was chemically sensitized to obtain an optimal sensitivity at 55°C by adding 10 mg of sodium benzenethiosulfate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid. Thereto, 100 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer and 100 mg of Proxel (trade name, produced by ICI Co., Ltd.) as an antiseptic were added.
At last, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.22 µm and a coefficient of variation of 9% was obtained (finally, as an emulsion, the pH was 5.7, the pAg was 7.5, the electric conductivity was 40 µS/m, the density was from 1.2 to 1.25×10³ kg/m³ and the viscosity was 50 mPa·s).

Preparation of Emulsion B:

Solution 1:
Water	750 ml
Gelatin	20 g
Sodium chloride	1 g
1,3-Dimethylimidazolidine-2-thione	20 mg
Sodium benzenethiosulfonate	10 mg
Citric acid	0.7 g

Solution 2:
Water	300 ml
Silver nitrate	150 g

Solution 3:
Water	300 ml
Sodium chloride	38 g
Potassium bromide	32 g
Potassium hexachloroiridate(III) (20% by weight aqueous solution containing 0.005% by weight of KCl)	5 ml
Ammonium hexachlororhodate (20% by weight aqueous solution containing 0.001% by weight of NaCl)	15 ml

The potassium hexachloroiridate(III) (20% by weight aqueous solution containing 0.005% by weight of KCl) and ammonium hexachlororhodate (20% by weight aqueous solution containing 0.001% by weight of NaCl) used in Solution 3 were prepared by dissolving each powder in a 20% by weight aqueous solution of KCl or a 20% by weight aqueous solution of NaCl and heating the solution at 40°C for 120 minutes.
Solution 2 and Solution 3 each in an amount corresponding to 90% were simultaneously added to Solution 1 kept at 38°C and a pH of 4.5 while stirring over 20 minutes to form core grains of 0.16 µm. Subsequently, 500 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added, then Solution 4 and Solution 5 shown below were added over 8 minutes and further, the remaining Solution 2 and Solution 3 each corresponding to 10% were added over 2 minutes to grow the grains up to a size of 0.18 µm. Furthermore, 0.15 g of potassium iodide was added and the grains were ripened for 5 minutes, thereby completing the grain formation.

Solution 4:

Water 100 ml

Silver nitrate 50 g

Solution 5:

Water 100 ml

Sodium chloride 13 g

Potassium bromide 11 g

Yellow prussiate of potash 2 mg
The obtained emulsion was water-washed by a flocculation method in a usual manner. More specifically, the temperature was lowered to 35°C, 3 g of Anionic Precipitant 1 shown below was added and the pH was lowered using sulfuric acid until silver halide was precipitated (pH: 3.2±0.2). Thereafter, about 3 liter of the supernatant was removed (first water washing) . After 3 liter of distilled water was added, sulfuric acid was added until silver halide was precipitated and 3 liter of the supernatant was again removed (second water washing). The same operation as in the second water washing was once more repeated (third water washing), whereby the water washing/desalting step was completed. To the water-washed and desalted emulsion, 45 g of gelatin was added, the pH and the pAg were adjusted to 5.6 and 7.5, respectively, and then the emulsion was chemically sensitized to obtain an optimal sensitivity at 55°C by adding 10 mg of sodium benzenethiosulfate, 3 mg of sodium benzenethiosulfinate, 2 mg of triphenylphosphine selenide and 1 mg of chloroauric acid. Thereto, 100 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer and 100 mg of Proxel as an antiseptic were added.
At last, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.18 µm and a coefficient of variation of 10% was obtained (finally, as an emulsion, the pH was 5.7, the pAg was 7.5, the electric conductivity was 40 µS/m, the density was 1.2×10³ kg/m³ and the viscosity was 50 mPa·s).

Preparation of Light-Insensitive Silver Halide Grain I:

Solution 1:
Water	1 liter
Gelatin	20 g
Potassium bromide	0.9 g
Citric acid	0.2 g
NH₄NO₃	20 g
Hydrogen peroxide	3.5 g
Sodium benzenethiosulfonate	15 mg

Solution 2:
Water	400 ml
Silver nitrate	200 g

Solution 3:
Water	400 ml
Potassium bromide	140.0 g
Potassium hexachlororhodate(III) (0.001% by weight aqueous solution)	4,000 ml

While stirring Solution 1 kept at 60°C, 40 ml of NaOH (1N) was added and further, 0.7 g of an aqueous silver nitrate solution was added. Thereafter, Solution 2 and Solution 3 each in a half (1/2) portion were added by a controlled double jet method while keeping the silver potential at +24 mV over 20 minutes. After physical ripening for 2 minutes, Solution 2 and Solution 3 each in the remaining half (1/2) were added by the same controlled double jet method over 20 minutes, thereby performing the grain formation.
The obtained emulsion was water-washed by a flocculation method in a usual manner. More specifically, the temperature was lowered to 35°C, 3 g of Anionic Precipitant 1 shown below was added and the pH was lowered using sulfuric acid until silver halide was precipitated (pH: 3.1±0.2). Thereafter, about 3 liter of the supernatant was removed (first water washing) . After 3 liter of distilled water was added, sulfuric acid was added until silver halide was precipitated and 3 liter of the supernatant was again removed (second water washing). The same operation as in the second water washing was once more repeated (third water washing), whereby the water washing/desalting step was completed. To the water-washed and desalted emulsion, 45 g of gelatin was added, the pH and the pAg were adjusted to 5.7 and 7.5, respectively, and thereto, phenoxyethanol as an antiseptic was added. At last, a dispersion of primitive silver bromide tetradecahedral emulsion grains containing 30 mol% on average of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.8 µm and a coefficient of variation of 10%, was obtained (finally, as an emulsion, the pH was 5.7, the pAg was 7.5, the electric conductivity was 40 µS/m, the density was 1.3×10³ kg/m³ and the viscosity was 30 mPa·s).

Preparation of Light-Insensitive Silver Halide Grain II:

A dispersion of primitive silver bromide tetradecahedral emulsion grains having an average grain size of 0.5 µm and a coefficient of variation of 10% was obtained by appropriately changing the conditions at the grain formation of Light-Insensitive Silver Halide Grain I.

Preparation of Light-Insensitive Silver Halide Grain (1):

The grain formation was performed by adding potassium hexachlororhodate(III) in an amount corresponding to 1×10^-5 mol per mol of KBr to the following Aqueous Solutions X-1 to X-4.

(Preparation of 1st Solution)

1,300 mL of an aqueous solution containing 0.6 g of KBr and 1.1 g of gelatin having an average molecular weight of 15,000 was stirred while keeping at 35°C.

(Addition 1)

24 mL of Aqueous Solution Ag-1 (containing 4.9 g of AgNO₃ in 100 mL), 24 mL of Aqueous Solution X-1 (containing 4.1 g of KBr in 100 mL) and 24 mL of Aqueous Solution G-1 (containing 1.8 g of gelatin having an average molecular weight of 15,000 in 100 mL) were added by a triple jet method at a constant flow rate over 30 seconds.
Thereafter, 1.3 g of KBr was added and the temperature was elevated to 75°C. Through ripening for 12 minutes after the elevation of temperature, 300 mL of Aqueous Solution G-2 (containing 12.7 g of gelatin obtained by reacting an aqueous solution of alkali-treated ossein gelatin with the addition of trimellitic anhydride under the conditions of 50°C and pH 9.0 and removing the residual trimellitic acid, in 100 mL) was added and then, 2.1 g of disodium 4,5-dihydroxy-1,3-disulfonate monohydrate and 0.002 g of thiourea dioxide were sequentially added at an interval of 1 minute.

(Addition 2)

Thereafter, 157 mL of Aqueous Solution Ag-2 (containing 22.1 g of AgNO₃ in 100 mL) and Aqueous Solution X-2 (containing 15.5 g of KBr in 100 mL) were added by a double jet method over 14 minutes. At this time, the addition of Aqueous Solution Ag-2 was performed by accelerating the flow rate such that the final flow rate became 3.4 times the initial flow rate, and the addition of Aqueous Solution X-2 was performed while keeping the bulk emulsion solution within the reactor at a pAg of 8.3.

(Addition 3)

Thereafter, 329 mL of Aqueous Solution Ag-3 (containing 32.0 g of AgNO₃ in 100 mL) and Aqueous Solution X-3 (containing 21.5 g of KBr and 1.6 g of KI in 100 mL) were added by a double jet method over 27 minutes. At this time, the addition of Aqueous Solution Ag-3 was performed by accelerating the flow rate such that the final flow rate became 1.6 times the initial flow rate, and the addition of Aqueous Solution X-3 was performed while keeping the bulk emulsion solution within the reactor at a pAg of 8.3.

(Addition 4)

Thereafter, 156 mL of Aqueous Solution Ag-4 (containing 32.0 g of AgNO₃ in 100 mL) and Aqueous Solution X-4 (containing 22.4 g of KBr in 100 mL) were added by a double jet method over 17 minutes. At this time, the addition of Aqueous Solution Ag-4 was performed at a constant flow rate and the addition of Aqueous Solution X-3 was performed while keeping the bulk emulsion solution within the reactor at a pAg of 8.3.
Subsequently, 0.0025 g of sodium benzenethiosulfonate and 125 mL of Aqueous Solution G-3 (containing 12.0 g of alkali-treated ossein gelatin in 100 mL) were sequentially added at an interval of 1 minute.
Furthermore, 43.7 g of KBr was added and after adjusting the pAg of the bulk emulsion solution within the reactor to 9.0, 73.9 g of AgI fine grains (containing 13.0 g of AgI fine grains having an average grain size of 0.047 µm, in 100 g) was added.

(Addition 5)

2 Minutes after that, 249 mL of Aqueous Solution Ag-4 and Aqueous Solution X-4 were added by a double jet method. At this time, Aqueous Solution Ag-4 was added at a constant flow rate over 16 minutes and Aqueous Solution X-4 was added while keeping at a pAg of 9.10.

(Addition 6)

Over subsequent 10 minutes, addition was performed while keeping the bulk emulsion within the reactor at a pAg of 7.5.
Thereafter, the emulsion was desalted by a normal flocculation method and while stirring, water, NaOH and alkali-treated ossein gelatin were added to adjust the pH and the pAg to 5.8 and 8.9, respectively, at 56°C.
The obtained grains were composed of tabular silver halide grains having an equivalent-circle diameter of 1.2 µm, a grain thickness of 0.20 µm, an average AgI content of 3.94 mol% and parallel (111) main planes. The coefficient of variation in the equivalent-circle diameter of all grains was 24%.

Preparation of Light-Insensitive Silver Halide Grains (2) and (3):

Tabular emulsions different in the equivalent-circle diameter/grain thickness as shown in the Table were prepared by appropriately changing the conditions for the grain growth or the like of Light-Insensitive Silver Halide Grain (1).

Preparation of Coated Sample:

On a polyethylene terephthalate film support having on both surfaces thereof a moisture-proof undercoat layer containing vinylidene chloride, layers were coated to have a structure of UL layer/emulsion layer/protective lower layer/protective upper layer.
The preparation method, coated amount and coating method of each layer are described below.

Emulsion A and Emulsion B were mixed at a ratio of 1:2 in terms of the Ag amount and then subjected to spectral sensitization by adding 5.7×10^-4 mol/mol-Ag of Sensitizing Dye (SD-1). Furthermore, 3.4×10^-4 mol/mol-Ag of KBr, 2.0×10^-4 mol/mol-Ag of Compound (Cpd-1), 2.0×10^-4 mol/mol-Ag of Compound (Cpd-2) and 8.0×10^-4 mol/mol-Ag of Compound (Cpd-3) were added and thoroughly mixed. Subsequently, 1.2×10^-4 mol/mol-Ag of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 1.2×10^-2 mol/mol-Ag of hydroquinone, 3.0×10^-4 mol/mol-Ag of citric acid, Hydrazine-based Nucleating Agents D-2g, D-11g and D-68 each in an amount of 1.5×10^-4 mol/mol-Ag, 6.0×10^-4 mol/mol-Ag of Nucleation Accelerator (Cpd-4), 90 mg/m² of 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt, colloidal silica having a particle size of 10 µm in an amount of 15% by weight based on gelatin, 100 mg/m² of Aqueous Latex (Cpd-5), 150 mg/m² of polyethyl acrylate latex, 150 mg/m² of a latex copolymer of methyl acrylate, sodium 2-acrylamide-s-methylpropanesulfonate and 2-acetoxyethyl methacrylate (88:5:7 by weight), 150 mg/m² of core/shell-type latex (core: styrene/butadiene copolymer (37/63 by weight), shell: styrene/2-acetoxyethyl acrylate (84/16 by weight), core/shell ratio=50/50) and Compound (Cpd-6) in an amount of 4% by weight based on gelatin were added. Then, the pH of the obtained coating solution was adjusted to 5.6 using citric acid. The thus-prepared coating solution for emulsion layer was coated on a support shown below to theoretically have an Ag coverage of 2.9 g/m² and a gelatin coverage of 1.3 g/m².

<Protective Upper Layer>
Gelatin	0.3 g/m²
Solid grains of the present invention	in an amount shown in Table
Amorphous silica matting agent having an average particle size of 3.5 µm	25 mg/m²
Compound (Cpd-7) (gelatin dispersion)	20 mg/m²
Colloidal silica having a particle size of 10 to 20 µm (Snowtex C, produced by Nissan Chemical)	30 mg/m²
Compound (Cpd-8)	50 mg/m²
Sodium dodecylbenzenesulfonate	20 mg/m²
Compound (Cpd-9)	20 mg/m²
Compound (Cpd-10)	20 mg/m²
Antiseptic (Proxel, trade name, produced by ICI Co., Ltd.)	1 mg/m²

<Protective Lower Layer>
Gelatin	0.5 g/m²
Compound (Cpd-11)	15 mg/m²
1,5-Dihydroxy-2-benzaldoxime	10 mg/m²
Polyethyl acrylate latex	150 mg/m²
Compound (Cpd-12)	3 mg/m²
Antiseptic (Proxel)	1.5 mg/m²

<UL Layer>
Gelatin	0.5 g/m²
Solid grains of the present invention	in an amount shown in Table
Polyethyl acrylate latex	150 mg/m²
5-Methyl-benzotriazole	40 mg/m²
Compound (Cpd-6)	40 mg/m²
Compound (Cpd-13)	10 mg/m²
Antiseptic (Proxel)	1.5 mg/m²

The viscosity of each coating solution was adjusted by adding the thickener represented by the following structure (Z):

The samples used in the present invention had a back layer and an electrically conducting layer each having the following composition.

<Back Layer>
Gelatin	3.3 g/m²
Solid grains of the present invention	in an amount shown in Table
Compound (Cpd-14)	40 mg/m²
Compound (Cpd-15)	20 mg/m²
Compound (Cpd-16)	90 mg/m²
Compound (Cpd-17)	40 mg/m²
Compound (Cpd-18)	26 mg/m²
Compound (Cpd-19)	5 mg/m ²
1,3-Divinylsulfonyl-2-propanol	60 mg/m²
Polymethyl methacrylate fine particles (average particle size: 6.5 µm)	30 mg/m²
Liquid paraffin	78 mg/m²
Compound (Cpd-6)	120 mg/m²
Calcium nitrate	20 mg/m²
Antiseptic (Proxel)	12 mg/m²

<Electrically Conducting Layer>
Gelatin	0.1 g/m²
Sodium dodecylbenzenesulfonate	20 mg/m²
SnO₂/Sb (9/1 by weight, average particle size: 0.25 µm)	200 mg/m²
Antiseptic (Proxel)	0.3 mg/m²

Cpd-17
CH₃(CH₂)₁₁-CH=CHSO₃Na Cpd-18
CH₃(CH₂)₁₁-CH₂-CH₂SO₃Na

On both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 µm), undercoat first and second layers each having the following composition were coated.

<Undercoat First Layer>
Core-Shell Type Vinylidene Chloride Copolymer (1)	15 g
2,4-Dichloro-6-hydroxy-s-triazine	0.25 g
Polystyrene fine particles (average particle size: 3 µm)	0.05 g
Compound (Cpd-20)	0.20 g
Colloidal silica (Snowtex ZL, produced by Nissan Chemical, particle size: from 70 to 100 µm)	0.12 g
Water to make	100 g

This coating solution was adjusted to a pH of 6 by adding 10% by weight of KOH and then coated to have a dry thickness of 0.9 µm after drying at a temperature of 180°C for 2 minutes.

<Undercoat Second Layer>

Gelatin 1 g

Methyl cellulose 0.05 g

Compound (Cpd-21) 0.02 g

C₁₂H₂₅O (CH₂CH₂O)₁₀H 0.03 g

Proxel 3.5×10^-3 g

Acetic acid 0.2 g

Water to make 100 g
This coating solution was coated to have a dry thickness of 0.1 µm after drying at a temperature of 170°C for 2 minutes.

On the support with undercoat layers prepared above, four layers were simultaneously multilayer-coated one on another in the emulsion side in the order of UL layer, emulsion layer, protective lower layer and protective upper layer from the support side by a slide bead coater method while keeping at 35°C. After passing the coated sample through a cold air set zone (5°C), electrically conducting layer and back layer in this order were simultaneously multilayer-coated one on another from the support side on the surface opposite the emulsion surface by a curtain coater method while adding a hardening agent solution. Thereafter, the coated sample was passed through a cold air set zone (5°C). At the time when the coated sample was passed through each set zone, the coating solutions exhibited satisfactory setting property. Subsequently, both surfaces were simultaneously dried in a dry zone under the following drying conditions. Incidentally, the coated sample was transported by a roller after the coating in the back surface side until the taking up and thereafter, transported in an absolutely non-contact state. At this time, the coating speed was 200 m/min.

After the setting, the coated sample was dried with a dry air at 30°C until the weight ratio of water/gelatin reached 800% and with a dry air at 35°C and 30% RH between 800% and 200%. Thereafter, the air blowing was continued and 30 seconds after the surface temperature reached 34°C (regarded as the completion of drying), the coated sample was dried with an air at 48°C and 2% RH for 1 minute. At this time, the drying time was 50 seconds from the initiation of drying until the water/gelatin ratio reached 800%, 35 seconds between 800% and 200%, and 5 seconds from 200% until the completion of drying.
The obtained light-sensitive material was taken up at 25°C and 55% RH, heat-treated at 35°C and 30% RH for 72 hours and cut at 25°C and 55% RH. After conditioning the humidity at 25°C and 50% RH for 8 hours, the light-sensitive material was sealed together with carton also subjected to humidity conditioning at 25°C and 50% RH for 2 hours, in a barrier bag of which humidity was conditioned for 6 hours. Thus, samples shown in Table 1 were prepared. For the purpose of comparison, samples not subjected to the heat treatment after the taking up were also prepared.
The humidity within the barrier bag was measured and found to be 45% RH. The pH on the surface in the emulsion layer side of the obtained samples was from 5.5 to 5.8 and the surface pH in the back layer side was 6.0 to 6.5. Fig. 1 shows the absorption spectra in the emulsion layer side and in the back layer side. The absorption spectra were measured using a spectrophotometer Model U-3500 manufactured by Hitachi Ltd. by placing a sample after stripping the coatings on the surface opposite the measuring surface side, in a 200 integrating sphere disposed in a sample chamber.
The evaluations were performed by the following methods.

[Evaluation of Spectral Reflectance]

In the evaluation of spectral reflectance, a spectrophotometer Model U-3500 manufactured by Hitachi Ltd. was used and a sample after attaching black paper to the surface opposite the measuring surface side was placed in a 200 integrating sphere disposed in a sample chamber. On the sample, probe light was applied and the light reflected from the measuring surface was integrated by the integrating sphere.

[Evaluation of Sensor Aptitude]

Each sample was loaded in the following image setters and the image setters were operated to actually perform an exposure processing. Thereafter, the presence or absence of sensor detection failures was evaluated.
Dolev 450 manufactured by Nippon Scitex
F9000 manufactured by Fuji Photo Film Co., Ltd.
Lux Setter RC5600V manufactured by Fuji Photo Film Co., Ltd.
At the occurrence of sensor detection failure, an error mark such as "NO FILM" was displayed.
Through ND filter with a density of 0.3 on the sensor surface, the sensor aptitude was evaluated by the appearance frequency of error mark. The appearance frequency of error mark "NO FILM" in 10 tests is shown.

[Evaluation of Haze]

Each sample was developed without passing through exposure and by superposing five sheets one on another, the haze was evaluated with an eye. The practically allowable lower limit was ranked as 3 and the level of not causing a problem at all in practice was ranked as 5.

[Evaluation of Photographic Properties]

Each sample obtained was exposed through an interference filter having a peak at 633 nm and a step wedge with xenon flash light having an emission time of 10^-6 second.
Thereafter, the sample was developed with Developer (A) or Fixing Solution (B) according to the following formulation under the development conditions of 35°C and 30 seconds using an automatic developing machine AP-560 (manufactured by Fuji Photo Film Co., Ltd.).

Developer (A):

A composition per 1 liter of concentrated solution is shown.

Water	600 ml
Potassium hydroxide	105.0 g
Diethylenetriaminepentaacetic acid	6.0 g
Potassium carbonate	120.0 g
Sodium metabisulfite	120.0 g
Potassium bromide	9.0 g
Hydroquinone	75.0 g
5-Methylbenzotriazole	0.24 g
Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone	1.35 g
Sodium 2-mercaptobenzimidazole-5-sulfonate	0.432 g
4-(N-Carboxymethyl-N-methylamino-2,6-dimercaptopyrimidine)	0.18 g
2-(N-Carboxymethyl-N-methylamino-4,6-dimercaptopyrimidine)	0.06 g
Sodium erythorbate	9.0 g
Diethylene glycol	60.0 g

Potassium hydroxide was added, water was added to make 1 liter and the pH was adjusted to 10.7. In the case of starting solution (mother solution), water was added to the solution above at a ratio of 3:1 (water:solution) (pH: 10.4) and in the case of replenisher, water was added to the solution above at a ratio of 2:1 (water:solution) (pH: 10.45).

Formulation of Fixing Solution (B):

A formulation per 1 liter of concentrated solution is shown.

Ammonium thiosulfate	360 g
Disodium ethylenediaminetetraacetate dihydrate	0.09 g
Sodium thiosulfate pentahydrate	33.0 g
Sodium metasulfite	57.0 g
Sodium hydroxide	37.2 g
Acetic acid (100%)	90.0 g
Tartaric acid	8.7 g
Sodium gluconate	5.1 g
Aluminum sulfate	25.2 g
PH	4.85

On use, 1 part of this concentrated solution was diluted with 2 parts of water. The pH of the use solution was 4.8.

[Evaluation of Photographic Properties]

A reciprocal of exposure amount necessary for giving a density of 1.5 was designated as sensitivity and the sensitivity was shown as a relative sensitivity. The γ was a value represented by ((1.5-0.3)/log(exposure amount necessary for giving a density of 1.5) - log(exposure amount necessary for giving a density of 0.3)).

[Evaluation of Practical Density]

Using an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd. and an automatic developing machine AP-560 connected to the image setter, a test step was output while changing the amount of light at 175 lines/inch and then developed under the above-described development conditions. The D_max part when exposed at an LV value of giving a halftone dot of 50% was measured and defined as the practical density. Incidentally, the dot % and the practical density were measured suing Macbeth TD904.

[Evaluation of Photographic Properties with Exhausted Developer]

Film samples each having a blackening percentage of 80% per day were treated with Developer (A), more specifically, 300 sheets in full size (50.8 cm × 61 cm) were processed while replenishing 50 ml of use solution per the full size sheet. This processing was continued for 4 days and thus, by processing a large amount of film, a developer decreased to a pH of 10.2 and increased in the bromide ion concentration was obtained.
Using this exhausted developer, the changes in sensitivity and practical density were evaluated.
It is seen from Table I-1 that in samples of the present invention, the sensor aptitude is improved, the performance is scarcely changed by the processing with an exhausted developer and kept good, and when tabular silver halide is used, the haze is advantageously not worsened.

EXAMPLE I-2

Samples were prepared and evaluated thoroughly in the same manner as in Example I-1 except for using Emulsion C shown below in place of Emulsions A and B in the coating solution for emulsion layer in Example I-1 and applying the coating solution to have Ag and gelatin concentrations of 2.5 g/m² and 1.1 g/m², respectively. Similarly to Example I-1, the samples having the construction of the present invention exhibited good performance.

Preparation of Emulsion C:

Solution 1:
Water	1 liter
Gelatin	20 g
Sodium chloride	3.0 g
1,3-Dimethylimidazolidine-2-thione	20 mg
Sodium benzenethiosulfonate	8 mg

Solution 2:
Water	400 ml
Silver nitrate	100 g

Solution 3:
Water	400 ml
Sodium chloride	19.0 g
Potassium bromide	31.5 g
Potassium hexachloroiridate(III) (20% by weight aqueous solution containing 0.005% by weight of KCl)	5 ml
Ammonium hexachlororhodate (20% by weight aqueous solution containing 0.001% by weight of NaCl)	7 ml

The potassium hexachloroiridate(III) (20% by weight aqueous solution containing 0.005% by weight of KCl) and ammonium hexachlororhodate (20% by weight aqueous solution containing 0.001% by weight of NaCl) used in Solution 3 were prepared by dissolving each powder in a 20% by weight aqueous solution of KCl or a 20% by weight aqueous solution of NaCl and heating the solution at 40°C for 120 minutes.
Solution 2 and Solution 3 were simultaneously added to Solution 1 kept at 42°C and a pH of 4.5 while stirring over 15 minutes to form core grains. Subsequently, Solution 4 and Solution 5 shown below were added over 15 minutes. Furthermore, 0.15 g of potassium iodide was added, thereby completing the grain formation.

Solution 4:

Water 400 ml

Silver nitrate 100 g

Solution 5:

Water 400 ml

Sodium chloride 19.0 g

Potassium bromide 31.5 g

Potassium hexacyanoferrate(II) (0.1% by weight aqueous solution) 10 ml
The obtained emulsion was water-washed by a flocculation method in a usual manner and then, 40 g of gelatin was added.
The emulsion was adjusted to a pH of 5.7 and a pAg of 7.5 and then chemically sensitized to obtain an optimal sensitivity at 55°C by adding 10 mg of sodium thiosulfate, 4.0 mg of chloroauric acid, 1.5 mg of triphenylphosphine selenide, and 8 mg of sodium benzenethiosulfate and 2 mg of sodium benzenethiosulfinate.
Thereto, 100 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer and phenoxyethanol as an antiseptic were added. At last, Silver Chloroiodobromide Cubic Emulsion A containing 55 mol% of silver chloride and having an average grain size of 0.19 µm was obtained.

EXAMPLE I-3

Using the samples of Examples I-1 and I-2, the same test as in Example I-1 was performed with Solid Developer (C) and Solid Fixing Agent (D) shown below, as a result, similarly to Examples I-1 and I-2, the samples having the construction of the present invention exhibited good performance.

Formulation of Solid Developer (C):

Sodium hydroxide (beads) 99.5%	11.5 g
Potassium sulfite (stock powder)	63.0 g
Sodium sulfite (stock powder)	46.0 g
Potassium carbonate	62.0 g
Hydroquinone (briquette)	40.0 g

The followings were collectively briquetted.

Diethylenetriaminepentaacetic acid	2.0 g
5-Methylbenzotriazole	0.35 g
4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone	1.5 g
4-(N-Carboxymethyl-N-methylamino)-2,6-dimercaptopyrimidine	0.2 g
Sodium 3-(5-mercaptotetrazol-1-yl)benzenesulfonate	0.1 g
Sodium erythorbate	6.0 g
Potassium bromide	6.6 g

These were dissolved in water to make 1 liter.

PH 10.65
The stock powders in the raw material form each was a general industrial product as it was and the alkali metal salt bead was a commercially available product.
In the case where the raw material form was a briquette, the briquette was compressed into a plate form under pressure using a briquetting machine and then cracked. As for trace components, respective components were blended and then briquetted.
The thus-prepared processing agent in a 10 liter portion was filled in a high-density polyethylene-made foldable container and the take-out port was sealed with an aluminum seal. For dissolving and replenishing this processing agent, a dissolving and replenishing apparatus having an automatic unsealing mechanism disclosed in JP-A-9-80718 and JP-A-9-138495 was used.

Formulation of Solid Fixing Agent (D):

Agent A (solid)
Ammonium thiosulfate (compact)	125.0 g
Anhydrous sodium thiosulfate (stock powder)	19.0 g
Sodium metabisulfite (stock powder)	18.0 g
Anhydrous sodium acetate (stock powder)	42.0 g

Agent B (liquid)
Disodium ethylenediaminetetraacetate dihydrate	0.03 g
Tartaric acid	2.9 g
Sodium gluconate	1.7 g
Aluminum sulfate	8.4 g
Sulfuric acid	2.1 g

These were dissolved in water to make 50 ml.
Agent A and Agent B were dissolved in water to make 1 liter and this was designated as Fixing Solution (D). The pH was 4.8.
The ammonium thiosulfate (compact), which was obtained by compressing a flake product prepared according to a spray dry method using a roller compactor, was cracked into amorphous chips of approximately from 4 to 6 mm and then blended with anhydrous sodium thiosulfate. Other stock powders each was a general industrial product .
Agent A and Agent B each in a 10 liter portion were separately filled in a high-density polyethylene-made foldable container. The take-out port of the Agent A container was sealed with an aluminum seal and the opening of the Agent B container was tightly closed with a screw cap. For dissolving and replenishing respective processing agents, a dissolving and replenishing apparatus having an automatic unsealing mechanism disclosed in JP-A-9-80718 and JP-A-9-138495 was used.

EXAMPLE I-4

Using Developer (E) or (F) shown below in place of Developer (A) in Example I-1 and using the samples of Examples I-1 and I-2, the same tests as in Examples I-1 and Example I-2 were performed, as a result, similarly to Examples I-1 and I-2, the samples having the construction of the present invention exhibited good performance.

Formulation of Solid Developer (E):

A composition per 1 liter of concentrated solution of Developer (E) is shown below.

Potassium hydroxide	105.0 g
Diethylenetriaminepentaacetic acid	6.0 g
Potassium carbonate	120.0 g
Sodium metabisulfite	120.0 g
Potassium bromide	9.0 g
Hydroquinone	75.0 g
5-Methylbenzotriazole	0.25 g
4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone	1.35 g
4-(N-Carboxymethyl-N-methylamino)-2,6-dimercaptopyrimidine	0.3 g
Sodium 2-mercaptobenzimidazole-5-sulfonate	0.45 g
Sodium erythorbate	9.0 g
Diethylene glycol	60.0 g
PH	10.7

On use, the starting solution (mother solution) was prepared by adding water to the solution above at a ratio of 3:1 (water:solution) (pH: 10.4) and the replenisher was prepared by adding water to the solution above at a ratio of 2:1 (water:solution) (pH: 10.45).

A composition per 1 liter of concentrated solution of Developer (F) is shown below.

Water	600 ml
Potassium hydroxide	96.0 g
Diethylenetriaminepentaacetic acid	6.0 g
Potassium carbonate	48.0 g
Sodium metabisulfite	120.0 g
Potassium bromide	9.0 g
Hydroquinone	70.0 g
5-Methylbenzotriazole	0.24 g
1-Phenyl-3-pyrazolidone	1.7 g
2-Mercaptobenzothiazole	0.18 g
1-Phenyl-5-mercaptotetrazole	0.06 g
Sodium erythorbate	9.0 g
Diethylene glycol	40.0 g

To these, potassium hydroxide was added, water was then added to make 1 liter and the pH was adjusted to 10.8. On use, water was added to the concentrated solution above at a ratio of 2:1 (water:concentrated solution) (pH: 10.45)

EXAMPLE I-5

In Examples I-1 to I-4, the processing was performed by setting the development temperature to 38°C, the fixing temperature to 37°C and the development time to 20 seconds, as a result, the same results as in Examples I-1 to I-4 were obtained, revealing that the effect of the present invention was not lost.

EXAMPLE I-6

In Examples I-1 to I-5, the same processing was performed using an automatic developing machine FG-680AS manufactured by the same company while setting the transportation speed to a linear velocity of 1,500 mm/min, as a result, the same results were also obtained.

EXAMPLE I-7

The same evaluations as in Examples I-1 to I-6 were performed using any one of Image Setter FT-R5055 manufactured by Dainippon Screen Co., Ltd., Select Set 5000, Avantra 25 and Accuset 1000 manufactured by AGFA-Gevaert, Dolev 450 and Dolev 800 manufactured by Scitex, Lino 630, Quasar, Herkules Elite, Signa-Setter and Luxel F-9000 manufactured by Heidel, and Panther-Pro 62 manufactured by Prepress, in place of Lux Setter RC-5600V manufactured by Fuji Photo Film Co., Ltd., as a result, the same results were obtained in the samples of the present invention.

EXAMPLE II-1

Preparation of Emulsion A:

Solution 2:
Water	300 ml
Silver nitrate	150 g

Solution 3:
Water	300 ml
Sodium chloride	38 g
Potassium bromide	32 g
Potassium hexachloroiridate(III) (20% aqueous solution containing 0.005% of KCl)	5 ml
Ammonium hexachlororhodate (20% aqueous solution containing 0.001% of NaCl)	7 ml

The potassium hexachloroiridate(III) (20% aqueous solution containing 0.005% of KCl) and ammonium hexachlororhodate (20% aqueous solution containing 0.001% of NaCl) used in Solution 3 were prepared by dissolving each powder in a 20% aqueous solution of KCl or a 20% aqueous solution of NaCl and heating the solution at 40°C for 120 minutes.
Solution 2 and Solution 3 each in an amount corresponding to 90% were simultaneously added to Solution 1 kept at 38°C and a pH of 4.5 while stirring over 20 minutes to form core grains (i.e., nucleus grains) of 0.16 µm. Subsequently, Solution 4 and Solution 5 shown below were added over 8 minutes and then, the remaining Solution 2 and Solution 3 each corresponding to 10% were added over 2 minutes to grow the grains up to 0.21 µm. Furthermore, 0.15 g of potassium iodide was added and the grains were ripened for 5 minutes, thereby completing the grain formation.

Solution 4:

Water 100 ml

Silver nitrate 50 g

Solution 5:

Water 100 ml

Sodium chloride 13 g

Potassium bromide 11 g

Yellow prussiate of potash 5 mg
The obtained emulsion was water-washed by a flocculation method in a usual manner. More specifically, the temperature was lowered to 35°C, 3 g of Anionic Precipitant 1 shown below was added and the pH was lowered using sulfuric acid until silver halide was precipitated (pH: 3.2±0.2). Thereafter, about 3 liter of the supernatant was removed (first water washing) . After 3 liter of distilled water was added, sulfuric acid was added until silver halide was precipitated and 3 liter of the supernatant was again removed (second water washing). The same operation as in the second water washing was once more repeated (third water washing), whereby the water washing/desalting step was completed. To the water-washed and desalted emulsion, 45 g of gelatin was added, the pH and the pAg were adjusted to 5.6 and 7.5, respectively, and then the emulsion was chemically sensitized to obtain an optimal sensitivity at 55°C by adding 10 mg of sodium benzenethiosulfate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid. Thereto, 100 mg of 1,3,3a,7-tetrazaindene as a stabilizer and 100 mg of Proxel (trade name, produced by ICI Co., Ltd.) as an antiseptic were added.
At last, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.22 µm and a coefficient of variation of 9% was obtained (finally, as an emulsion, the pH was 5.7, the pAg was 7.5, the electric conductivity was 40 µS/m, the density was 1.2×10^-3 kg/m3 and the viscosity was 50 mPa·s).

Preparation of Emulsion B:

Solution 2:
Water	300 ml
Silver nitrate	150 g

Solution 3:
Water	300 ml
Sodium chloride	38 g
Potassium bromide	32 g
Potassium hexachloroiridate(III) (20% aqueous solution containing 0.005% of KCl)	5 ml
Ammonium hexachlororhodate (20% aqueous solution containing 0.001% of NaCl)	15 ml

The potassium hexachloroiridate(III) (20% aqueous solution containing 0.005% of KCl) and ammonium hexachlororhodate (20% aqueous solution containing 0.001% of NaCl) used in Solution 3 were prepared by dissolving each powder in a 20% aqueous solution of KCl or a 20% aqueous solution of NaCl and heating the solution at 40°C for 120 minutes.
Solution 2 and Solution 3 each in an amount corresponding to 90% were simultaneously added to Solution 1 kept at 38°C and a pH of 4.5 while stirring over 20 minutes to form core grains of 0.16 µm. Subsequently, 500 mg of 1,3,3a,7-tetrazaindene was added, then Solution 4 and Solution 5 shown below were added over 8 minutes and further, the remaining Solution 2 and Solution 3 each corresponding to 10% were added over 2 minutes to grow the grains up to a size of 0.18 µm. Furthermore, 0.15 g of potassium iodide was added and the grains were ripened for 5 minutes, thereby completing the grain formation.

Solution 4:

Water 100 ml

Silver nitrate 50 g

Solution 5:

Water 100 ml

Sodium chloride 13 g

Potassium bromide 11 g

Yellow prussiate of potash 2 mg
The obtained emulsion was water-washed by a flocculation method in a usual manner. More specifically, the temperature was lowered to 35°C, 3 g of Anionic Precipitant 1 shown below was added and the pH was lowered using sulfuric acid until silver halide was precipitated (pH: 3.2±0.2). Thereafter, about 3 liter of the supernatant was removed (first water washing). After 3 liter of distilled water was added, sulfuric acid was added until silver halide was precipitated and 3 liter of the supernatant was again removed (second water washing). The same operation as in the second water washing was once more repeated (third water washing), whereby the water washing/desalting step was completed. To the water-washed and desalted emulsion, 45 g of gelatin was added, the pH and the pAg were adjusted to 5.6 and 7.5, respectively, and then the emulsion was chemically sensitized to obtain an optimal sensitivity at 55°C by adding 10 mg of sodium benzenethiosulfate, 3 mg of sodium benzenethiosulfinate, 2 mg of triphenylphosphine selenide and 1 mg of chloroauric acid. Thereto, 100 mg of 1,3,3a,7-tetrazaindene as a stabilizer and 100 mg of Proxel as an antiseptic were added.
At last, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.18 µm and a coefficient of variation of 10% was obtained (finally, as an emulsion, the pH was 5.7, the pAg was 7.5, the electric conductivity was 40 µS/m, the density was 1.2×10^-3 kg/m³ and the viscosity was 50 mPa·s).

Preparation of Light-Insensitive Silver Halide Grain (1):

Solution 2:
Water	400 ml
Silver nitrate	100 g

Solution 3:
Water	400 ml
Sodium chloride	13.5 g
Potassium bromide	45.0 g
Potassium hexachlororhodate(III) (0.001% aqueous solution)	860 ml

Solution 1, Solution 2 and Solution 3 each kept at 70°C and a pH of 4.5 were added while stirring to form core grains. Subsequently Solution 4 and Solution 5 shown below were added over 15 minutes. Furthermore, 0.15 g of potassium iodide was added, thereby completing the grain formation.
The obtained emulsion was water-washed by a flocculation method in a usual manner. More specifically, the temperature was lowered to 35°C, 3 g of Anionic Precipitant 1 shown below was added and the pH was lowered using sulfuric acid until silver halide was precipitated (pH: 3.2±0.2). Thereafter, about 3 liter of the supernatant was removed (first water washing). After 3 liter of distilled water was added, sulfuric acid was added until silver halide was precipitated and 3 liter of the supernatant was again removed (second water washing). The same operation as in the second water washing was once more repeated (third water washing), whereby the water washing/desalting step was completed. To the water-washed and desalted emulsion, 45 g of gelatin was added, the pH and the pAg were adjusted to 5.7 and 7.5, respectively, and thereto, phenoxyethanol as an antiseptic was added. At last, Dispersion (1) of primitive silver iodochlorobromide cubic emulsion grains containing 30 mol% on average of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.45 µm and a coefficient of variation of 10%, was obtained (finally, as an emulsion, the pH was 5.7, the pAg was 7.5, the electric conductivity was 40 µS/m, the density was 1.3×10^-3 kg/m³ and the viscosity was 50 mPa·s).

Preparation of Light-Insensitive Silver Halide Grain (2):

Light-Insensitive Silver Halide Grain (2) (primitive silver iodochlorobromide cubic emulsion grains having an average grain size of 0.8 µm and a coefficient of variation of 10%) was obtained by changing the temperature and the pH at the grain formation of Light-Insensitive Silver Halide Grain (1).

Preparation of Light-Insensitive Silver Halide Grain (3):

Solution 2:
Water	400 ml
Silver nitrate	200 g

Solution 3:
Water	400 ml
Potassium bromide	140.0 g
Potassium hexachlororhodate(III) (0.001% aqueous solution)	4,000 ml

While stirring Solution 1 kept at 60°C, 40 ml of NaOH (1N) was added and further, 0.7 g of an aqueous silver nitrate solution was added. Thereafter, Solution 2 and Solution 3 each in a half (1/2) portion were added by a controlled double jet method while keeping the silver potential at +24 mV over 20 minutes. After physical ripening for 2 minutes, Solution 2 and Solution 3 each in the remaining half (1/2) were added by the same controlled double jet method over 20 minutes, thereby performing the grain formation.
The obtained emulsion was water-washed by a flocculation method in a usual manner. More specifically, the temperature was lowered to 35°C, 3 g of Anionic Precipitant 1 shown below was added and the pH was lowered using sulfuric acid until silver halide was precipitated (pH: 3.1±0.2). Thereafter, about 3 liter of the supernatant was removed (first water washing). After 3 liter of distilled water was added, sulfuric acid was added until silver halide was precipitated and 3 liter of the supernatant was again removed (second water washing). The same operation as in the second water washing was once more repeated (third water washing), whereby the water washing/desalting step was completed. To the water-washed and desalted emulsion, 45 g of gelatin was added, the pH and the pAg were adjusted to 5.7 and 7.5, respectively, and thereto, phenoxyethanol as an antiseptic was added. At last, Dispersion (3) of primitive silver bromide tetradecahedral emulsion grains containing 30 mol% on average of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.8 µm and a coefficient of variation of 10%, was obtained (finally, as an emulsion, the pH was 5.7, the pAg was 7.5, the electric conductivity was 40 µS/m, the density was 1.3×10^-3 kg/m³ and the viscosity was 50 mPa·s).

Preparation of Liaht-Insensitive Silver Halide Grain (4):

Light-Insensitive Silver Halide Grain (4) (primitive silver bromide tetradecahedral emulsion grains having an average grain size of 0.45 µm and a coefficient of variation of 10%) was obtained by changing the temperature and the pH at the grain formation of Light-Insensitive Silver Halide Grain (2).

Preparation of Coated Sample:

Emulsion A and Emulsion B were mixed at a ratio shown in the table and then subjected to spectral sensitization by adding 5.7×10^-4 mol/mol-Ag of Sensitizing Dye (sd-1). Furthermore, 3.4×10^-4 mol/mol-Ag of KBr, 2.0×10^-4 mol/mol-Ag of Compound (cpd-1), 2.0×10^-4 mol/mol-Ag of Compound (cpd-2) and 8.0×10^-4 mol/mol-Ag of Compound (cpd-3) were added and thoroughly mixed. Subsequently, 1.2×10^-4 mol/mol-Ag of 1,3,3a,7-tetrazaindene, 1.2×10^-2 mol/mol-Ag of hydroquinone, 3.0×10^-4 mol/mol-Ag of citric acid, 1.5×10^-4 mol/mol-Ag of Hydrazine-based Nucleating Agent (cpd-4), 6.0×10^-4 mol/mol-Ag of Nucleation Accelerator (cpd-5), 90 mg/m² of 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt, colloidal silica having a particle size of 10 µm in an amount of 15% by weight based on gelatin, 100 mg/m² of Aqueous Latex (aqL-6), 150 mg/m² of polyethyl acrylate latex, 150 mg/m² of a latex copolymer of methyl acrylate, sodium 2-acrylamide-2-methylpropanesulfonate and 2-acetoxyethyl methacrylate (88:5:7 by weight), 150 mg/m² of core/shell-type latex (core: styrene/butadiene copolymer (37/63 by weight), shell: styrene/2-acetoxyethyl acrylate (84/16 by weight), core/shell ratio=50/50) and Compound (cpd-7) in an amount of 4% by weight based on gelatin were added. Then, the pH of the obtained coating solution was adjusted to 5.6 using citric acid. The thus-prepared coating solution for emulsion layer was coated on a support shown below to have an Ag coverage of 3.4 g/m² and a gelatin coverage of 1.5 g/m².

<Protective Upper Layer>
Gelatin	0.3 g/m²
Amorphous silica matting agent having an average particle size of 3.5 µm	25 mg/m²
Compound (cpd-8) (gelatin dispersion)	20 mg/m²
Colloidal silica having a particle size of 10 to 20 µm (Snowtex C, produced by Nissan Chemical)	30 mg/m²
Compound (cpd-9)	50 mg/m²
Sodium dodecylbenzenesulfonate	20 mg/m²
Compound (cpd-10)	20 mg/m²
Compound (cpd-11)	20 mg/m²
Antiseptic (Proxel, trade name, produced by ICI Co., Ltd.)	1 mg/m²

<Protective Lower Layer>
Gelatin	0.5 g/m²
Light-insensitive silver halide grain	in an amount shown in Table
Compound (cpd-12)	15 mg/m ²
1,5-Dihydroxy-2-benzaldoxime	10 mg/m²
Polyethyl acrylate latex	150 mg/m²
Compound (cpd-13)	3 mg/m²
Antiseptic (Proxel)	1.5 mg/m²

<UL Layer>
Gelatin	0.5 g/m²
Polyethyl acrylate latex	150 mg/m²
Compound (cpd-7)	40 mg/m²
Compound (cpd-15)	10 mg/m²
Antiseptic (Proxel)	1.5 mg/m²

The viscosity of the coating solution for each layer was adjusted by adding the thickener represented by the following structure (Z):

<Back Layer>
Gelatin	3.3 g/m²
Compound (Cpd-15)	40 mg/m²
Compound (Cpd-16)	20 mg/m²
Compound (Cpd-17)	90 mg/m²
Compound (Cpd-18)	40 mg/m²
Compound (Cpd-19)	26 mg/m ²
1,3-Divinylsulfonyl-2-propanol	60 mg/m²
Polymethyl methacrylate fine particles (average particle size: 6.5 µm)	30 mg/m²
Liquid paraffin	78 mg/m²
Compound (cpd-7)	120 mg/m²
Calcium nitrate	20 mg/m²
Antiseptic (Proxel)	12 mg/m²

Cpd-18
CH₃(CH₂)₁₁-CH=CHSO₃Na Cpd-19
CH₃(CH₂)₁₁-CH₂-CHSO₃Na

This coating solution was adjusted to a pH of 6 by adding 10% by weight of KOH and then coated to have a dry thickness of 0.9 µm after drying at a temperature of 180°C for 2 minutes.

<Undercoat Second Layer>

Gelatin 1 g

Methyl cellulose 0.05 g

Compound (Cpd-21) 0.02 g

C₁₂H₂₅O(CH₂CH₂O)₁₀H 0.03 g

Proxel 3.5×10^-3 g

Acetic acid 0.2 g

Water to make 100 g
This coating solution was coated to have a dry thickness of 0.1 µm after drying at a temperature of 170°C for 2 minutes.

After the setting, the coated sample was dried with a dry air at 30°C until the weight ratio of water/gelatin reached 800% and with a dry air at 35°C and 30% RH between 800% and 200%. Thereafter, the air blowing was continued and 30 seconds after the surface temperature reached 34°C (regarded as the completion of drying), the coated sample was dried with an air at 48°C and 2% RH for 1 minute. At this time, the drying time was 50 seconds from the initiation of drying until the water/gelatin ratio reached 800%, 35 seconds between 800% and 200%, and 5 seconds from 200% until the completion of drying.
The obtained light-sensitive material was taken up at 25°C and 55% RH, heat-treated at 35°C and 30% RH for 72 hours and cut at 25°C and 55% RH. After conditioning the humidity at 25°C and 50% RH for 8 hours, the light-sensitive material was sealed together with carton subjected to humidity conditioning at 25°C and 50% RH for 2 hours, in a barrier bag of which humidity was conditioned for 6 hours. Thus, samples shown in Table 1 were prepared. For the purpose of comparison, samples not subjected to the heat treatment after the taking up were also prepared.
The humidity within the barrier bag was measured and found to be 45%. The pH on the surface in the emulsion layer side of the obtained samples was from 5.5 to 5.8 and the surface pH in the back layer side was 6.0 to 6.5. Fig. 1 shows the absorption spectra in the emulsion layer side and in the back layer side. The absorption spectra were measured using a spectrophotometer Model U-3500 manufactured by Hitachi Ltd. by placing a sample after stripping the coatings on the surface opposite the measuring surface side, in a 200 integrating sphere disposed in a sample chamber.
The evaluations were performed by the following methods.

[Evaluation of Optical Property]

The transmittance of the obtained sample at a wavelength of 900 to 950 nm was measured using a spectrophotometer Model U-3500 manufactured by Hitachi Ltd. In the measurement, an integrating sphere was disposed in the light-receiving part of the spectrophotometer so that the transmitted light of the film can be integrated by the integrating sphere. The data in Evaluation of Spectral Reflectance obtained in Example 1 are shown together. Because of back scattering, transverse scattering or the like from the film sample, the increment in the reflectance is slightly smaller than the decrement in the spectral transmittance.

[Evaluation of Sensor Aptitude]

Each sample was loaded in the following image setters and the image setters were operated to actually perform an exposure processing. Thereafter, the presence or absence of sensor detection failures was evaluated.
Dolev 450 manufactured by Nippon Scitex
F9000 manufactured by Fuji Photo Film Co., Ltd.
Lux Setter RC5600V manufactured by Fuji Photo Film Co., Ltd.
At the occurrence of sensor detection failure, an error mark such as "NO FILM" was displayed.

[Evaluation of Photographic Properties]

Each sample obtained was exposed through an interference filter having a peak at 667 nm and a step wedge with xenon flash light having an emission time of 10^-6 second.
Thereafter, the sample was developed with Developer (A) or Fixing Solution (B) according to the following formulation under the development conditions of 35°C and 30 seconds using an automatic developing machine FG-680AG (manufactured by Fuji Photo Film Co., Ltd.).

Developer (A):

A composition per 1 liter of concentrated solution is shown.

Potassium hydroxide	60.0 g
Diethylenetriaminepentaacetic acid	3.0 g
Potassium carbonate	90.0 g
Sodium metabisulfite	105.0 g
Potassium bromide	10.5 g
Hydroquinone	60.0 g
5-Methylbenzotriazole	0.53 g
4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone	2.3 g
Sodium 3-(5-mercaptotetrazol-1-yl)benzenesulfonate	0.15 g
Sodium 2-mercaptobenzimidazole-5-sulfonate	0.45 g
Sodium erythorbate	9.0 g
Diethylene glycol	7.5 g
PH	10.79

On use, the developer was diluted with water at a ratio, in the case of mother solution, of 1 part of water to 2 parts of concentrated solution prepared above. The pH of the mother solution was 10.65. In the case of replenisher, the developer was diluted at a ratio of 3 parts of water to 4 parts of concentrated solution. The pH of the replenisher was 10.62.

Formulation of Fixing Solution (B):

A formulation per 1 liter of concentrated solution is shown.

[Evaluation of Photographic Properties]

[Evaluation of Practical Density]

Using an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd., a test step was output while changing the amount of light at 175 lines/inch and then developed under the above-described development conditions. The D_max part when exposed at an LV value of giving a halftone dot of 50% was measured and defined as the practical density. Incidentally, the dot % and the practical density were measured suing Macbeth TD904.

[Evaluation of Photographic Properties with Exhausted Developer]

Film samples each having a blackening percentage of 80% per day were treated with Developer (A), more specifically, 300 sheets in full size (50.8 cm × 61 cm) were processed while replenishing 50 ml of use solution per the full size sheet. This processing was continued for 4 days and thus, by processing a large amount of film, a developer decreased to a pH of 10.2 and increased in the bromide ion concentration was obtained.
Using this exhausted developer, the changes in sensitivity and practical density were evaluated.
As seen from Table II-1 that samples where light-insensitive silver halide is added and the transmittance is lowered by 5% or more exhibit good sensor aptitude. As the amount added increases, the practical density in the exhausted developer processing is more decreased and there arises a problem in the practical use. In the samples of the present invention, it is understood that both the sensor aptitude and the practical density (>4.5) with exhausted developer can be attained. Furthermore, it is revealed that light-insensitive silver halide grain having a high silver bromide content is advantageous for decreasing the transmittance.

EXAMPLE II-2

The same test as in Example II-1 was performed using Solid Developer (C) and Solid Fixing Agent (D) shown below, as a result, similarly to Example II-1, samples having the construction of the present invention exhibited good performance.

Formulation of Solid Developer (C):

The followings were collectively briquetted.

Formulation of Solid Fixing Agent (D):

EXAMPLE II-3

Using Developer (E) shown below in place of Developer (A) in Example II-1, the same test as in Example II-1 was performed, as a result, similarly to Example II-1, the light-sensitive materials having the construction of the present invention exhibited good performance.

On use, the developer was diluted with water at a ratio of 1 part of this concentrated solution to 2 parts of water. The pH of use solution was 10.5.

EXAMPLE II-4

In Examples II-1 to II-3, the processing was performed by setting the development temperature to 38°C, the fixing temperature to 37°C and the development time to 20 seconds, as a result, the same results as in Examples II-1 to II-3 were obtained, revealing that the effect of the present invention was not lost.

EXAMPLE II-5

In Examples II-1 to II-4, the same processing was performed using an automatic developing machine FG-680AS manufactured by the same company while setting the transportation speed to a linear velocity of 1,500 mm/min, as a result, the same results were also obtained.

EXAMPLE II-6

The same evaluations as in Examples II-1 to II-5 were performed using any one of Image Setter FT-R5055 manufactured by Dainippon Screen Co., Ltd., Select Set 5000, Avantra 25 and Accuset 1000 manufactured by AGFA-Gevaert, Dolev 450 and Dolev 800 manufactured by Scitex, Lino 630, Quasar, Herkules Elite, Signa-Setter and Luxel F-9000 manufactured by Heidel, and Panther-Pro 62 manufactured by Prepress, in place of Lux Setter RC-5600V manufactured by Fuji Photo Film Co., Ltd., as a result, the same results were obtained in the samples of the present invention.
The entitle disclosure of each and every foreign patent application from which the benefit of foreign priority has been claimed in the present application is incorporated herein by reference, as if fully set forth herein.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

A silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer containing at least one light-sensitive silver halide emulsion, wherein a hydrophilic colloid layer which is the same or different from said silver halide emulsion layer contains solid grains in an amount of increasing the integrated value of spectral reflectance of the light-sensitive material in the wavelength region of 850 to 1,000 nm, by 1.5% or more.
The silver halide photographic light-sensitive material as claimed in claim 1, wherein the refractive index of the solid grain is 1.54 or more.
The silver halide photographic light-sensitive material as claimed in claim 1 or 2, wherein the solid grain is a substantially light-insensitive silver halide grain.
The silver halide photographic light-sensitive material as claimed in claim 3, wherein the solid grain is a substantially light-insensitive silver halide grain and said light-insensitive silver halide grain comprises a tabular grain having an average grain thickness of 0.02 to 0.20 µm.
The silver halide photographic light-sensitive material as claimed in any one of claims 1 to 4, wherein the coated silver amount of the light-sensitive silver halide emulsion is 3.0 g/m² or less.
The silver halide photographic light-sensitive material as claimed in any one of claims 1 to 5, wherein the solid grain is a substantially light-insensitive silver halide grain and said light-insensitive silver halide emulsion containing said light-insensitive silver halide grains in an amount of 10 to 200 mg/m² as silver is incorporated into a hydrophilic colloid layer to reduce the transmittance of said light-sensitive material at 900 to 950 nm, in terms of the absolute value, by 5% or more on average.
The silver halide photographic light-sensitive material as claimed in any one of claims 1 to 6, wherein the silver halide emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative.
A method for processing a silver halide photographic light-sensitive material, comprising exposing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support using an image setter, transporting the light-sensitive material by an automatic transportation system and developing the light-sensitive material in an automatic developing machine, wherein a hydrophilic colloid layer which is the same or different from said silver halide emulsion layer contains solid grains in an amount of increasing the integrated value of spectral reflectivity of the light-sensitive material in the wavelength region of 850 to 1,000 nm by 1.5% or more.
The method for processing a silver halide photographic light-sensitive material as claimed in claim 8, wherein the refractive index of the solid grain is 1.54 or more.
The method for processing a silver halide photographic light-sensitive as claimed in claims 8 or 9, wherein the solid grain is a substantially light-insensitive silver halide grain.
The light-sensitive silver halide photographic light-sensitive material as claimed in claim 10, wherein the solid grain is a substantially light-insensitive silver halide grain and said light-insensitive silver halide grain comprises a tabular grain having an average grain thickness of 0.02 to 0.20 µm.
The silver halide photographic light-sensitive material as claimed in any one of claim 8 to 11, wherein the coated silver amount of the light-sensitive silver halide emulsion is 3.0 g/m² or less.
The method for processing a silver halide photographic light-sensitive material as claimed in any one of claims 1 to 12, wherein the solid grain is a substantially light-insensitive silver halide grain and said light-insensitive silver halide emulsion containing said light-insensitive silver halide grains in an amount of 10 to 200 mg/m² as silver is incorporated into a hydrophilic colloid layer to reduce the transmittance of said light-sensitive material at 900 to 950 nm, in terms of the absolute value, by 5% or more on average.
The method for processing a silver halide photographic light-sensitive material as claimed in any one of claims 8 to 13, wherein the silver halide emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative.
The method for processing a silver halide photographic light-sensitive material as claimed in any one of claims 8 to 14, wherein the developer replenishing amount is 250 ml/m² or less.