JP2002351011A - Silver halide photographic sensitive material and processing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material free of trouble of a sensor in an image setter and having good haze, and to provide a processing method for the material in which a change in performance due to running is small. SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer containing at least one photosensitive silver halide emulsion on a substrate, solid particles are contained in the silver halide emulsion layer or another hydrophilic colloidal layer in such an amount as to increase the average integrated value of spectral reflectance of a photosensitive material in the wavelength range of 850-1,000 nm by >=1.5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material used especially for photolithography.

[0002]

2. Description of the Related Art In the field of graphic arts,
With the recent demand for low replenishment and rapid processing, it has been desired to reduce the amount of coated silver, and technical development of finer silver halide grains and higher sensitivity has been enthusiastic among those skilled in the art. It has been done. By making the particles fine, covering power (blackening density per unit silver amount) can be increased, and the amount of silver used can be reduced.

On the other hand, a system in which a photosensitive material supply cassette is automatically conveyed from an exposure machine to an automatic developing machine is becoming common. In this method, a film is detected by several optical sensors installed inside an exposure machine or the like. The optical sensor generally uses a light source in the infrared region that is outside the photosensitive wavelength of the photosensitive material, and is a method of detecting a film by scattering of silver halide particles or the like.

Optical sensors used for such purposes are roughly classified into two types, a "transmission type" for detecting transmitted light of light emitted from the light emitting element and a "reflection type" for detecting reflected light. There are types. In the case of the transmission type sensor, the detection power is higher than that of the reflection type, but since the light emitting unit and the light receiving unit are separate, two sensors are required, and there is a disadvantage that the cost is high. On the other hand, the reflection-type sensor has a feature that the light-emitting unit and the light-receiving unit can be integrated, so that the installation is simple and the cost is advantageous.

[0005] Generally, a reflection type sensor used for a photosensitive material recognizes infrared light emitted from a light emitting portion of the sensor mainly by scattering of silver halide particles, and detecting the scattered light by a light receiving portion. ing. Therefore, when the coated silver amount is reduced for low replenishment or the like, or when the particle size of the silver halide particles is reduced, scattering at the silver halide particles is reduced, and the light reception amount of the sensor is reduced. There was a problem that the photosensitive material was difficult to recognize. Japanese Patent Application Laid-Open Nos. 63-131135 and 8-95198 also disclose a method for dealing with a reduction in sensor detection power due to an increase in film transmittance due to silver saving and small particle size in transmission type sensors. However, these methods are aimed at reducing the transmittance of infrared rays, and no study has been made on countermeasures for the reflective sensor. Japanese Patent Laid-Open No. 10-22180 discloses a method corresponding to the detection power of a reflective infrared sensor.
However, this method has a disadvantage that the transparency of the film, that is, the so-called haze is increased, and is not sufficient.

[0006]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having a good haze without a sensor trouble in an image setter. . A second object of the present invention is to provide a processing method using the silver halide photographic light-sensitive material as described above and having a small change in performance due to running.

[0007]

This problem has been solved by the following. (1) In a silver halide photographic material having at least one silver halide emulsion layer having at least one photosensitive silver halide emulsion on a support, the same layer as the silver halide emulsion layer or another hydrophilic layer is used. 85 in the aqueous colloid layer
A silver halide photographic light-sensitive material containing an amount of solid particles that increases the average value of the integrated value of the spectral reflectance of the light-sensitive material in the wavelength range of 0 to 1,000 nm by 1.5% or more. (2) The photosensitive silver halide photographic material as described in (1), wherein the refractive index of the solid particles is 1.54 or more. (3) The light-sensitive silver halide photographic material as described in (1) or (2), wherein the solid particles are substantially light-insensitive silver halide particles. (4) The solid particles are substantially light-insensitive silver halide grains, and the light-insensitive silver halide grains are tabular grains having an average grain thickness of 0.02 to 0.20 μm. The photosensitive silver halide photographic light-sensitive material as described in the above. (5) The coated silver amount of the photosensitive silver halide emulsion is 3.0 g /
The photosensitive silver halide photographic material according to any one of (1) to (4), wherein m is ² or less. (6) A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support is exposed using an imagesetter, then conveyed by an automatic conveyance system, and subjected to development processing by an automatic developing machine. In a method for automatically processing a silver halide photographic light-sensitive material, 85% of the silver halide emulsion layer may be contained in the same layer as the silver halide emulsion layer or in another hydrophilic colloid layer.
A method for processing a silver halide photographic light-sensitive material, comprising adding solid particles which increase the average value of the integrated value of the spectral reflectance of the light-sensitive material in the wavelength range of 0 to 1,000 nm by 1.5% or more. (7) The method for processing a photosensitive silver halide photographic material as described in (6), wherein the refractive index of the solid particles is 1.54 or more. (8) The method for processing a light-sensitive silver halide photographic material according to (6) or (7), wherein the solid particles are substantially light-insensitive silver halide particles. (9) The solid particles are substantially light-insensitive silver halide particles, and the light-insensitive silver halide particles are tabular grains having an average grain thickness of 0.02 to 0.20 μm. A method for processing the light-sensitive silver halide photographic material as described in the above. (10) The coated silver amount of the photosensitive silver halide emulsion is 3.0 g.
/ M ² or less processing method of the light-sensitive silver halide photographic material according to any one of (6) (9).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The average value of the integrated value of the spectral reflectance at 850 to 1000 nm of the light-sensitive material of the present invention can be easily measured using a spectrometer. For example, a spectrometer U350 manufactured by Hitachi, Ltd.
By using a light-receiving part with an integrating sphere installed on the light-receiving part, irradiating probe light on a black paper placed on the back of the photosensitive material, and integrating and measuring the reflected light from the photosensitive material with the integrating sphere. Can be measured.

In the present invention, the addition of 850
The solid silver halide emulsion layer or other hydrophilic colloid layer contains solid grains whose average value of the integrated value of the spectral reflectance of １０００1000 nm is increased by 1.5% or more as compared with the case where no additive is added. It is preferably at least 2%, but is preferably at most 5% from the viewpoint of haze deterioration.

The solid particles used in the present invention, which increase the integrated value of the reflectance by adding, have no particular limitation on the material as long as they have the above-mentioned reflection characteristics, and do not affect the photographic performance. Any kind of inorganic particles, organic dispersion, etc. may be used as long as it has a refractive index of 1.54 or more. The refractive index in the present invention indicates a relative refractive index to air. The refractive index slightly changes depending on the wavelength, temperature, etc. of the light.
9.3 nm) and nD20 having a value of 20 ° C. was used.
In the case of a solid, when the refractive index is small depending on the direction due to the anisotropy of the crystal, the largest value is taken as the value of the substance.

Specific examples of the compound having a refractive index of 1.54 or more include silver halide, magnesium oxide, alumina, calcite, ZrO ₂ , SnO ₂ , ZnO, and Al ₂ O _3.
And various compounds such as metal oxides represented by TiO _{2 and the} like, barium sulfate, polystyrene, and vinylidene chloride resin.

The preferred range of the refractive index is 1.6 to
3.0, particularly preferably 1.7 to 3.0.

Although the preferred range of the particle size of the solid particles varies depending on the refractive index, it is preferably 2 nm to 20 μm,
nm-10 μm is more preferred. Here, the particle diameter of the solid particles represents the particle diameter determined by the light scattering method, and specifically, the average particle diameter was determined using ELS-800 manufactured by Otsuka Electronics Co., Ltd. Note that, in the present invention, the symbol “to (or)” indicates a range including numerical values described before and after it as a minimum value and a maximum value, respectively.

Preferably, the solid particles are added in an amount of 1
0 mg to 1 g / m ² , particularly preferably 20 to 500 m
g / m ² .

The position at which the solid particles are added is not particularly limited, and they can be used in the emulsion layer, between the emulsion layer and the support, in the emulsion protective layer, the backing layer, and in the support. A protective layer may be provided on the uppermost layer on the surface directly exposed to the emitted light or on the layer to which the solid particles are added.

These solid particles need to be in the form of particles in the light-sensitive material, and depending on the method of dispersing the fine particles,
Lower water solubility is preferred. Further, the property of dissolving in the processing solution is preferably used.

Further, in the present invention, it is preferable to use silver halide among the solid grains. Further, it is preferable to use tabular substantially light-insensitive silver halide grains.

The non-photosensitive silver halide grains used in the present invention may have a halogen composition of silver chloride, silver bromide,
Any of silver chlorobromide, silver iodobromide, silver iodochloride, and silver iodochlorobromide can be used, but the AgBr content is 5%.
0 mol% or more is preferable.

The non-photosensitive silver halide grains used in the present invention are described in Chimieet Physique Photogr by P. Glafkides.
aphique (Paul Montel, 1967), by GF Dufin
Photographic Emulsion Chemistry (The Focal Pre
ss, 1966), VLZelikman et al, Making and
Coating Photographic Emulsion (Published by The FocalPress,
1964) and the like.

The substantially light-insensitive silver halide grains in the present invention are silver halides having a blue region sensitivity of 1/10 or less of the photosensitive silver halide grains used in the light-sensitive material of the present invention. Refers to particles. Further, the non-photosensitive silver halide grains are preferably not spectrally sensitized. The non-photosensitive silver halide grains of the present invention can be subjected to surface modification such as metal complex dopant and chemical sensitization described in the section of photosensitive silver halide below.

The morphology of the silver halide grains which can be used in the non-light-sensitive silver halide emulsion of the present invention requires that most of them be tabular. Here, the tabular silver halide grains are a general term for silver halide having one twin plane or two or more parallel twin planes. The twin plane is (1
11) When the ions at all lattice points on both sides of the plane are in a mirror image relationship, this means the (111) plane. When the tabular grains are viewed from above, they have a triangular, square, hexagonal or rounded circular shape.The triangular grains are triangular, and the hexagonal grains are hexagonal. Square, circular ones have circular parallel outer surfaces.

A metal is vapor-deposited from the oblique direction of the particles together with the latex for reference, the length of the shadow is measured on an electron micrograph, and it is easily obtained by calculating with reference to the length of the latex shadow. . In the non-light-sensitive emulsion of the present invention, 50% or more of the total projected area is 0.02 to 0.2.
Occupied by 20 μm tabular grains.

The coefficient of variation of the equivalent circle diameter in all grains of the non-photosensitive emulsion of the present invention is preferably 40% or less, more preferably 25% or less, and further preferably 15% or less.

Tabular silver halide emulsions are disclosed in
It can be easily prepared by referring to the methods described in JP-A-127927, JP-A-58-113927 and JP-A-58-11328. Further, in an atmosphere having a relatively low pBr value of pBr 1.3 or less, a seed crystal in which tabular grains are present at 40% or more by weight is formed, and silver and a halogen solution are added simultaneously while maintaining the same pBr value. Obtained by growing a seed crystal. In this growth process, it is desirable to add a silver and halogen solution so that no new crystal nuclei are generated. The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.

The halogen composition of the photosensitive silver halide emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide. May be.

The shape of each photosensitive silver halide grain used in the present invention may be any one of a cube, a tetradecahedron, an octahedron, an irregular shape, and a plate shape, but is preferably a cube or plate shape. In the present invention, the amount of the photosensitive silver halide to be added is 3.0 g / m ² or less, preferably 2.0 g / m ² or less.
Ｇ3.0 g / m ² .

The photographic emulsion used in the present invention is P. Glaf
kides Chimie et PhysiquePhotographique (Pau
l Montel, 1967), Photographi by GF Dufin
cEmulsion Chemistry (The Focal Press, 1966), V.
Making and Coating Photograph by L. Zelikman et al
ic Emulsion (The Focal Press, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and the method of reacting the soluble silver salt with the soluble halide salt may be any of a one-side mixing method, a double-mixing method, and a combination thereof. Is also good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. Particle size to the type and purpose of the addition amount is used a compound of silver halide solvent varies depending halogen composition, 10 ^-5 to 10 ^-2 mol per mol of silver halide is preferred. Further, the particles may be formed in the presence of a nitrogen-containing heterocyclic compound which forms a complex with silver. preferable. The addition amount of these compounds varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but is preferably from 10 ⁻⁶ to 10 ⁻² mol per mol of silver halide. Is preferred. The addition of these compounds can be appropriately performed at each stage before, during, or after the formation of the particles, and is particularly preferably performed at the time of the formation of the particles.

In the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or an alkali halide in accordance with the grain growth rate, a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above paragraph to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodispersed emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
It is 1 μm to 0.4 μm.

The photosensitive silver halide emulsion used in the present invention may be used alone or in combination of two or more. When two or more types are used, the particle sizes are preferably different. It is preferable that the difference between the particle sizes differs by 10% or more as the average particle side length.

The ratio of the combination of two or more silver halide emulsions used in the present invention is not particularly limited, but is preferably from 1: 1 to 1:20, more preferably from 1: 1 to 1 in terms of silver amount. :
It is 10.

It is also preferable to mix at least two kinds of emulsions having different addition amounts of a nitrogen-containing heterocyclic compound capable of forming a complex with silver as described in paragraphs 0020 to 0032 of Japanese Patent Application No. 2000-379706. Can be

The silver halide emulsion used in the present invention is:
It may contain a metal belonging to Group VIII. In order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound and the like. Preferred as these heavy metals are metal coordination complexes, and hexacoordinate complexes represented by the following general formula. [M (NY) _m L _6-m ] ^n- (where M is a heavy metal selected from Ir, Ru, Rh, Re, Cr and Fe. L is a bridging ligand. Y is oxygen or M = 0, 1, 2 and n = 0,
1, 2, and 3. Preferred specific examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanates Nate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. In order to increase the sensitivity, an iron compound is preferably contained, and a metal coordination complex having a cyan ligand as a ligand is particularly preferable. These compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the compounds, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid,
Hydrofluoric acid, etc.) or alkali halides (for example, K
Cl, NaCl, KBr, NaBr, etc.) can be used. It is also possible to add and dissolve another silver halide grain doped with these compounds in advance. Specific examples of the metal coordination complex are shown below. 1. _[Rh (H 2 O) Cl _5] ^2- 2. [RuCl _6] ^3- 3. [Ru (NO) Cl _5] ^2- 4. [RhCl _6] ^3- 5. _[Ru (H 2 0) Cl _5] ^2- 6. _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 7. ^{_{[Ru 2 Cl 10 O] 6- 8}} . [Re (NO) Cl _5] ^2- 9. [Ir (NO) Cl _5] ^2- 10. _[Ir (H 2 0) Cl _5] ^2- 11. _[Re (H 2 0) Cl _5] ^2- 12. [RhBr _6] ^3- 13. [ReCl _6] ^3- 14. [IrCl _6] ^3- 15. _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 16. [Cr (CN) ₆ ] ^3-17 . [Fe (CN) ₆ ] ^3-

In addition to the compounds mentioned above, compounds described in paragraphs 0027 to 0056 of Japanese Patent Application No. 2000-95144 can also be preferably used.

The addition amount of these compounds is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver of the silver halide emulsion. Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grains is not particularly limited, and may be a uniform distribution, a core-shell type having a different distribution between the surface and the inside, or a continuous distribution. The addition of these compounds can be appropriately performed during the production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them during emulsion formation and incorporate them into the silver halide grains. .

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, and sulfur sensitization, tellurium sensitization and gold sensitization are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain time. Known compounds can be used as the sulfur sensitizer, for example,
In addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used. Other U.S. Pat. Nos. 1,574,944 and 2,410,689
No. 2,278,947 and No. 2,728,66
No. 8, No. 3,501, 313, No. 3,656, 9
No. 55, German Patent 1,422,869, JP-B-56-24937, JP-A-55-45016 and the like can also be used. Preferred sulfur compounds are thiosulfates and thiourea compounds. The addition amount of the sulfur sensitizer pH during chemical ripening, the temperature, but varies depending on various conditions such as the size of the silver halide grains, per mol of silver halide ^10-7
-2 mol, more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1.
No. 3489, JP-A-4-25832, JP-A-4-1092
It is preferable to use the compounds described in JP-A Nos. 40 and 4-324855. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropions, 2-
Selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphineselenides, colloidal metal selenium, and the like. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. For those skilled in the art, speaking of unstable selenium compounds as sensitizers for photographic emulsions,
As long as selenium is unstable, the structure of the compound is not critical, and the organic portion of the selenium sensitizer molecule carries selenium and has nothing to do with it being present in the emulsion in an unstable form. Is generally understood to have no role. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. The non-labile selenium compound used in the present invention is disclosed in JP-B-46-4553.
No., JP-B-52-34492 and JP-B-52-34
No. 491 can be used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. In particular, JP-A-4-324855
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in the above. Further, a low-decomposition active selenium compound can also be preferably used. The low-decomposition active selenium compound includes AgNO ₃ 10 mmol, selenium compound 0.5
The selenium when a mixed solution (pH = 6.3) of 40 mmol of a 2-mmol, 2- (N-morpholino) ethanesulfonic acid buffer in water / 1,4-dioxane at a volume ratio of 1/1 was reacted at 40 ° C. A selenium compound having a compound half life of 6 hours or more. The selenium compound can be analyzed by HPLC or the like to determine the half-life. The low-decomposition active selenium compound is disclosed in JP-A-9-1668.
It is preferred to use 41 compound examples SE-1 to SE-8 compounds.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of the silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in No. 31284.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No.3, No.5-303157, Journal of Chemical Society Chemical Communication
(J. Chem. Soc. Chem. Commun.) 635 (1980), ibid 1102 (197
9), ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. So
c.Perkin.Trans.) 1,2191 (1980), S. Patai
Ed., The Chemistry of Organic Selenium and Tellurium Campounds
of Organic Serenium and Tellunium Compounds), Vol
1 (1986) and Vol. 2 (1987). In particular, the general formula (I) disclosed in JP-A-5-313284.
Compounds represented by I), (III) and (IV) are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, Preferably 10 ^-7 to 1
0 ^-3 mol is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, p
Ag is 6-11, preferably 7-10, and the temperature is 40-95 ° C, preferably 45-85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. As the gold sensitizer, the oxidation number of gold may be +1 or +3, and gold compounds generally used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate,
Examples thereof include potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and gold sulfide, and about 10 ^-7 to 10 ^-2 mol per mol of silver halide can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. The silver halide emulsion of the present invention can be prepared by the method described in European Patent Application (EP) -293,917.
A thiosulfonic acid compound may be added. The silver halide emulsion in the light-sensitive material used in the present invention, two or more in the same layer, the type, distribution, content of the metal complex is different,
Crystal habits, different shapes, types of chemical sensitizers, amounts added,
Different sensitization conditions, types of spectral sensitizing dyes, addition amounts,
Those having different spectral sensitization conditions and the like may be used in combination, and the layers may have a multilayer structure.

The light-sensitive silver halide emulsion of 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 depending on the use of the light-sensitive material. Good. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE
Item 17643 IV-A (p.2 December 1978
3), Item 18341X (p. 43, August 1979)
It is described in the literature described or cited in 7).
In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected. For example, A) for an argon laser light source, compounds of (I) -1 to (I) -8 described in JP-A-60-162247;
No. 8653, compounds I-1 to I-28, JP-A-4-330434, compounds I-1 to I-13, and Exam described in U.S. Pat. No. 2,161,331.
Compounds from ple1 to Example14, West German Patent 9
36,071; B) For helium-neon laser and red laser diode light source, compounds of I-1 to I-38 described in JP-A-54-18726; Compounds of I-1 to I-35 described in JP-A-6-75322 and JP-A-7-2873
No. 38, compounds I-1 to I-34, and JP-A-2822138, 2-1 to 2-14, 3-
(1) to 3- (14), compounds of 4-1 to 4-6,
C) For LED light sources, compounds of Dyes 1 to 20 described in JP-B-55-39818, compounds of I-1 to I-37 described in JP-A-62-284343, and JP-A-7-2
Nos. 87338 to I-34, 2-1 to 2-1 described in Patent Publication No. 2822138.
4, 3- (1) to 3- (14), compounds of 4-1 to 4-6; D)
Compounds of I-1 to I-12 described in JP-A-1901032 and compounds of I-1 to I- described in JP-A-60-80841.
Compound No. 22 described in I-I-6 described in JP-A-4-335342.
Compounds from 1 to I-29 and JP-A-59-19224
Compounds I-1 to I-18 described in No. 2, E) Tungsten and xenon light sources for plate making cameras are represented by the general formula [I] described in JP-A-55-45015 (1). To (19), JP-A-6-24247
4-A to 4-S, 5-A to 5-
Q compound, 6-A to 6-T compound and
The compounds of I-1 to I-97 described in -160185 are advantageously selected, but the present invention is not limited thereto.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Vol. 176, Volume 17643 (December 1978) Second
Section J on page 3, IV, or the aforementioned JP-B-49-2550
0, 43-4933, JP-A-59-19032, 5
9-192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye using a compound that causes red shift and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the step of forming silver halide grains and / or before desalting, during and / or after desalting. Previous period, Japanese Patent Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The addition amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ per 1 m ² of the surface area of the silver halide grain.
The molar amount is preferably 6.5 × 10 ^{−7 to} 2.0 ×.
An addition amount of 10 ⁻⁶ mol is more preferred.

In the present invention, "another hydrophilic colloid layer" refers to a hydrophilic colloid layer having a water-permeable or water-impermeable relationship with a silver halide emulsion layer. Examples of the former include a protective layer and an intermediate layer, and examples of the latter include a back layer.

The support used in the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
Glass plate, cellulose acetate, cellulose nitrate, for example, polyester film such as polyethylene terephthalate, JP-A-7-234478, and US
A support comprising a styrenic polymer having a syndiotactic structure described in JP-A-5,558,979;
-538, US4,645,731, US4,93
A support obtained by coating a polyester film described in US Pat. No. 3,267, US Pat. No. 4,954,430 with a vinylidene chloride copolymer can be used. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

Gelatin is preferably used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers in the present invention, but polymers described in paragraph 0025 of JP-A-10-268644 can also be used. The coating amount of the binder is such that the binder amount of all the hydrophilic colloid layers on the side having the silver halide emulsion layer is 3 g / m ² or less (preferably 1.0 to 3.0 g / m ² ), and the silver halide emulsion The total amount of the binder in the total hydrophilic colloid layer on the side having the layer and the total hydrophilic colloid layer on the opposite side is 7.
0 g / m ² or less, preferably 2.0 to 7.0 g / m ²
a m ^2.

In the present invention, for the purpose of controlling the surface roughness of the outermost layer surface of the silver halide photosensitive material, fine particles of inorganic and / or organic polymer (hereinafter referred to as a matting agent) are contained in a hydrophilic colloid layer. ) Is used. The surface roughness of the outermost layer surface of the light-sensitive material having the silver halide emulsion layer and the outermost layer surface opposite to the emulsion layer should be controlled by variously changing the average particle size and the amount of the matting agent. Can be. The layer containing the matting agent may be any layer of the light-sensitive material constituting layer, but the side having the silver halide emulsion layer is preferably contained in a layer farther from the support to prevent pinholes, particularly The outermost layer is preferred.

The matting agent used in the present invention may be any solid particles which do not adversely affect the photographic characteristics. Specifically, Japanese Patent Application Laid-Open No. 10-26846
No. 4, No. 4, pp. 0009-0013. In the present invention, the average particle size of the matting agent is preferably 20 μm or less, and particularly preferably in the range of 1 to 10 μm. In the present invention, the preferable addition amount of the matting agent is 5
４００400 mg / m ² , especially 10-200 mg / m ² . The surface roughness of the light-sensitive material of the present invention is such that the Bekk smoothness of at least one of the surface having the emulsion layer and the surface of the outermost layer opposite to the surface is preferably 4000 seconds or less, more preferably 10 to 4 seconds. 2,000 seconds.
The Beck smoothness can be easily obtained by Japanese Industrial Standard (JIS) P8119 and TAPPI standard method T479.

In the present invention, the matting agent sinks during the coating and drying of the silver halide light-sensitive material, or the pressure increases or decreases in handling during automatic conveyance, exposure, development, etc.
Colloidal inorganic particles can be used in a silver halide emulsion layer, an intermediate layer, a protective layer, a back layer, a back protective layer, and the like for the purpose of improving curl balance, scratch resistance, and adhesion resistance. Preferred colloidal inorganic particles include JP-A-10-268644, paragraphs 0008 and 0014.
Examples include the elongated silica particles described above, colloidal silica, and pearl-like (pearl necklace-shaped) colloidal silica manufactured by Nissan Chemical Industries, Ltd .: “Snowtex-PS”.

The amount of the colloidal inorganic particles used in the present invention is 0.01 to 2.0, preferably 0.1 to 0.1 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added. -0.6.

In the present invention, a polyhydroxybenzene compound described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5 is used for the purpose of improving the sense of pressure increase and decrease. Is preferred. In particular,
Compounds (III) -1 to 25 described in the publication are mentioned.

In the present invention, a polymer latex can be used for the purpose of improving the brittleness, the dimensional stability, the feeling of pressure fluctuation, and the like. As the polymer latex, U.S. Pat. Nos. 2,763,652, 2,852,382, JP-A-64-538, JP-A-62-115152, JP-A-5-66512, JP-A-5-80449, Tokiko Sho 60-
No. 15935, No. 6-64058 and No. 5-450
Polymer latexes composed of various monomers such as alkyl acrylates and alkyl methacrylates described in JP-B No. 14 and No. Sho.
7, JP-A-50-73625, JP-A-7-1521
12, a polymer latex copolymerized with a monomer having an active methylene group and a monomer such as an alkyl acrylate described in JP-A-8-137060. Particularly preferably, JP-A-8-248548,
It is a polymer latex having a core / shell structure having a repeating unit composed of an ethylenically unsaturated monomer having an active methylene group in a shell portion described in JP-A-8-208767 and JP-A-8-220669. Polymer latexes having a core / shell structure having an active methylene group in the shell portion do not decrease the wet film strength of the photographic light-sensitive material, and are difficult to adhere such as brittleness, dimensional stability, and photosensitive materials. And the latex itself has improved shear stability. The amount of the polymer latex to be used is 0.01 to 4.0, preferably 0.1 to 2.0 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added.

In the present invention, in order to reduce the pH of the coating film for the purpose of improving the storage stability of the silver halide light-sensitive material and improving the sensitivity to pressure fluctuation, the same method as described in JP-A-7-104413, p. It is preferable to use the acidic polymer latex described on line 30 on the right side of the page. Specifically, compounds II-1) to II-9) described on page 15 of the publication. JP-A-2-103
No. 536, page 18, lower right, line 6 to page 19, upper left, first line, compounds having an acid group. The pH of the coating film on the side having the silver halide emulsion layer is preferably from 6 to 4.

In the present invention, at least one of the constituent layers of the silver halide light-sensitive material has a surface resistivity of 25 ° C. and 25%.
It can have a conductive layer of 10 ¹² Ω or less in an atmosphere of RH. As the conductive substance used in the present invention,
Conductive substances described in JP-A-2-18542, page 2, lower left, line 13 to page 3, upper right, line 7; Specifically, the metal oxide described in the second page from the lower right line on page 2 to the 10th lower right line in the same publication, and the compounds P-1 to P-1 described in the same publication
A conductive polymer compound of P-7. USP5,575,95
7, paragraphs 0034- of JP-A No. 10-142738.
0043, JP-A-11-223901, paragraph 00
Acicular metal oxides described in 13 to 0019 can be used.

In the present invention, in addition to the above-mentioned conductive substance, JP-A-2-18542, page 4, upper right, second line to page 4, lower right, lower third line, JP-A-3-39948, twelfth line A better antistatic property can be obtained by using the fluorine-containing surfactant described in the sixth line from the lower left of the page to the fifth line on the lower right of the page 13 of the publication.

In the present invention, a coating aid, an additive dispersing / solubilizing agent, an improvement in lubricity, an anti-adhesion property and an improvement in photographic properties (for example, development acceleration) may be added to the silver halide emulsion layer or other hydrophilic colloid layer. Various surfactants can be used for the purpose of, for example, high contrast, sensitization, and storage stability). For example, surfactants described in JP-A-2-12236, page 9, upper right line, line 7 to lower right line, line 3 of the same page. JP-A-2-103
No. 536, page 18, lower left line, line 4 to lower left line, line 7, the PEG surfactant. Specifically, compounds VI-1 to VI-15 described in the publication. JP-A-2-1
No. 8542, page 4, upper right, second line to page 4, lower right, lower third line; JP-A-3-39948, page 12, lower left, line 6 to lower right, page 13 Fluorinated surfactant.

In the present invention, various slip agents can be used for the purpose of improving the transportability, scratch resistance, pressure increase / decrease sensitivity and the like of the silver halide photosensitive material in an automatic transporter.
For example, JP-A-2-103536, page 19, upper left 1
From the fifth line to the upper right line on page 19 of the publication, JP-A-4-21
A lubricant described in paragraphs 0006 to 0031 of No. 4551.

In the present invention, a compound described in JP-A-2-103536, page 19, upper left, line 12 to page 19, upper right, line 15 is contained as a plasticizer for the coating film of the silver halide photosensitive material. be able to.

In the present invention, as a crosslinking agent for the hydrophilic binder, JP-A-2-103536, page 18, upper right line, line 5 to line 17, upper right line, JP-A-5-297508
The compounds described in paragraphs [0008] to [0011] of JP-A No. 1993-0011 can be used. The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is preferably in the range of 50 to 200%, more preferably 70%.
１８０180%. The swelling ratio of the hydrophilic colloid layer is determined by measuring the thickness (d0) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material,
The silver halide photographic material was immersed in distilled water at 25 ° C. for 1 minute, the swelled thickness (Δd) was measured, and the swelling ratio (%) was measured.
= △ d ÷ d0 × 100.

In the present invention, the drying, drying and winding up in a roll after drying of the silver halide light-sensitive material are described in JP-A-10-26.
It is preferable to carry out the method described in paragraphs 0026 to 0032 of Japanese Patent No. 8464.

In the present invention, the coated photosensitive material is preferably subjected to a heat treatment at any time from coating to development. The heat treatment may be performed continuously immediately after the application or after a certain period has elapsed, but it is preferable to start the heat treatment within a short period, for example, within one day. The heat treatment is mainly for accelerating the hardening reaction to obtain a film strength that can withstand the development process, and the heat treatment conditions are appropriately determined according to the type of the hardener, the amount added, the film pH, the required film strength, etc. Although it has to be determined, it is preferably from 30 to 60C, more preferably from 35C to 50C. The period of the heat treatment is preferably 30 minutes to 10 days.

In the present invention, the nucleating agent preferably contains at least one hydrazine derivative represented by the general formula (D). General formula (D)

[0065]

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In the formula, R ₂₀ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ₁₀ represents a hydrogen atom or a block group, and G ₁₀ represents —CO—, —COCO—, —C (=
_{S) -, - SO 2 -} , - SO -, - PO (R 30) - group _{(R 30} is selected from the same range as the groups defined in _{R 10,} may be different from _{R 10),.} Or an iminomethylene group. A ₁₀ and A _{20 each} 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 the formula (D), the aliphatic group represented by R ₂₀ is preferably a substituted or unsubstituted, straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. is there. In the general formula (D), R
_The aromatic group represented by ₂₀ is a monocyclic or condensed-ring aryl group, such as a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₂₀ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group such as a pyridine ring, a pyrimidine ring, an imidazole ring, and a pyrazole ring. Quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, piperidine ring, triazine ring and the like. Preferred as R ₂₀ is an aryl group, and particularly preferred is a phenyl group.

The group represented by R ₂₀ may be substituted,
Representative substituents include, for example, halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl Group, heterocyclic group, quaternized nitrogen-containing heterocyclic group (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acyl group Rucarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy groups , A heterocyclic oxy group, Siloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfone Amide group, ureide group, thioureide group, isothioureide group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, N-acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, ( An alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an N-acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphate amide or a phosphate ester structure. Groups, and the like. These substituents may be further substituted with these substituents.

The substituent which R ₂₀ may have is preferably an alkyl group having 1 to 30 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group, a sulfonamide. Group, ureido group,
Sulfamoylamino group, imide group, thioureido group,
Phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocyclic ) Thio, sulfo (including its salts), sulfamoyl, halogen, cyano,
And a nitro group.

In the general formula (D), R ₁₀ represents a hydrogen atom or a block group.
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 R ₁₀ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, a trifluoromethyl group, a difluoromethyl group,
-Carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, methanesulfonamidomethyl group, benzenesulfonamidomethyl group, hydroxymethyl group, methoxymethyl group, methylthiomethyl group, Examples include a phenylsulfonylmethyl group and an o-hydroxybenzyl group. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, such as a vinyl group, a 2,2-dicyanovinyl group, a 2-ethoxycarbonylvinyl group, and a 2-trifluoro-2-methoxycarbonylvinyl group. . The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed-ring aryl group is preferable, and an aryl group containing a benzene ring is particularly preferable. For example, a phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 2
-Carbamoylphenyl group, 4-cyanophenyl group, 2
-Hydroxymethylphenyl group and the like. Preferably, the heterocyclic group is a 5- to 6-membered, saturated or unsaturated, monocyclic or fused-ring heterocyclic group containing at least one nitrogen, oxygen, and sulfur atom, and a quaternized nitrogen atom. May be a heterocyclic group including, for example, a morpholino group, a piperidino group (N-substituted), a piperazino group, an imidazolyl group, an indazolyl group (such as a 4-nitroindazolyl group), a pyrazolyl group, a triazolyl group, a benzimidazolyl group, Examples include a tetrazolyl group, a pyridyl group, a pyridinio group (such as an N-methyl-3-pyridinio group), a quinolinio group, and a quinolyl group. Particularly preferred are a morpholino group, a piperidino group, a pyridyl group, a pyridinio group and the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, such as a methoxy group, a 2-hydroxyethoxy group and a benzyloxy group. As the aryloxy group, a phenoxy group is preferable, and as the amino group, an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized (Including a nitrogen-containing heterocyclic group containing a nitrogen atom). Examples of the amino group include 2,2,6,6-tetramethylpiperidine-
4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-
And a 3-pyridinioamino group. As the hydrazino group, a substituted or unsubstituted hydrazino group, or a substituted or unsubstituted phenylhydrazino group (such as a 4-benzenesulfonamidophenylhydrazino group) is particularly preferred.

The group represented by R ₁₀ may be substituted, and preferred substituents include those exemplified as the substituents for R ₂₀ .

In the general formula (D), R ₁₀ is G ₁₀ -R
₁₀ part of to divide from the remaining _molecules, -G _{10 -R} 10
A cyclization reaction that generates a cyclic structure containing a partial atom may be performed, and examples thereof include those described in JP-A-63-29751.

The hydrazine derivative represented by the general formula (D) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such an adsorbing group include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups, which are described in U.S. Pat. Nos. 4,385,108 and 4,459,347; Nos. 195233, 59-200231, 59-201045, 59-201046, and 5
Nos. 9-201047, 59-201048, 59
JP-201049, JP-A-61-170733, and JP-A-61-170933.
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285
No. 344.

R ₁₀ or R _{20 in} the formula (D) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. In the present invention, the ballast group means a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), alkylthio group having 6 or more carbon atoms. Represents a group or a group having these as a partial structure, more preferably a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group) having 7 or more and 24 or less carbon atoms, It represents an alkylamino group (or an alkyleneamino group), an alkylthio group, or a group having these as a partial structure. Examples of the polymer include those described in JP-A-1-100530.

R ₁₀ or R ₂₀ in the general formula (D) may contain a plurality of hydrazino groups as substituents. And specifically, for example,
No. 86134, JP-A-4-16938, JP-A-5-1
No. 97091, WO95-32452, WO95-3
No. 2453, JP-A-9-179229, JP-A-9-2
No. 35264, JP-A-9-235265, JP-A-9-235
Compounds described in JP-A-235266 and JP-A-9-235267 are exemplified.

In the general formula (D), R ₁₀ or R ₂₀ represents a cationic group (specifically, a group containing a quaternary ammonium group, a group containing a quaternized phosphorus atom, or 4
A nitrogen-containing heterocyclic group containing a graded nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, (alkyl, aryl, or heterocycle)
A thio group or a dissociable group (means a group or a partial structure having a proton having a low acidity that can be dissociated in an alkaline developer, or a salt thereof, and specifically, for example, a carboxy group / —COOH, a sulfo group / _-SO 3 H, a phosphonic acid group / _-PO 3 H, phosphoric acid group / -OPO ₃ H, hydroxy group / -OH group, mercapto group / -SH, -SO
₂ NH ₂ group, N-substituted sulfonamide group / —SO ₂ N
H- group, -CONHSO ₂ - group, -CONHSO ₂ NH
— Group, —NHCONHSO ₂ — group, —SO ₂ NHSO ₂
-Group, -CONHCO- group, active methylene group, -NH- group inherent in nitrogen-containing heterocyclic group, or salts thereof)
May be included. Examples of these groups include, for example, JP-A-7-234471 and JP-A-5-33.
3466, JP-A-6-19032, JP-A-6-19
031, JP-A-5-45761, U.S. Pat.
4,365, U.S. Pat. No. 4,988,604, JP-A-7-259240, JP-A-7-5610, and JP-A-7
244348, German Patent 4006032, JP-A-1
Compounds described in 1-7093 and the like can be mentioned.

In the general formula (D), A ₁₀ and A _{20 each} represent a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group or a Hammett having a sum of substituent constants of -0.5. A phenylsulfonyl group substituted as described above), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; Alternatively, a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (here, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group. ))). A ₁₀ and A ₂₀ are most preferably a hydrogen atom.

Next, particularly preferred hydrazine derivatives in the present invention will be described. R ₂₀ is particularly preferably a substituted phenyl group. Examples of the substituent include a sulfonamide group, an acylamino group, a ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group,
An N-acylsulfamoylamino group or the like is particularly preferred,
Further, a sulfonamide group and a ureido group are preferred, and a sulfonamide group is most preferred. The hydrazine derivative represented by the general formula (D) is a group containing a ballast group, an adsorptive group to silver halide, or a quaternary ammonium group as a substituent at R ₂₀ or R ₁₀ ; A quaternary nitrogen-containing heterocyclic group containing a nitrogen atom, a group containing a repeating unit of an ethyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, a dissociable group that can be dissociated in an alkaline developing solution or it is particularly preferable that at least one of which is substituted hydrazino group capable of forming a multimer (group represented by _{-NHNH-G 10 -R} 10). Further, as a substituent of R ₂₀ , directly or indirectly,
It is preferred to have any one of the aforementioned groups, most preferably, R ₂₀ represents a phenyl group substituted with a benzenesulfonamide group, and directly or as a substituent on the benzene ring of the benzenesulfonamide group. Indirectly, it has any one of the groups described above.

Preferred groups among the groups represented by R ₁₀ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group when G ₁₀ is a —CO— group; More preferred are a hydrogen atom, an alkyl group and a substituted aryl group (an electron-withdrawing group or an o-hydroxymethyl group is particularly preferred as the substituent), and most preferred is a hydrogen atom or an alkyl group.
When G ₁₀ is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferred, and a substituted amino group, specifically, an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is particularly preferred. . When G ₁₀ is a —SO ₂ — group, R ₁₀ is preferably an alkyl group, an aryl group, or a substituted amino group.

In the general formula (D), G ₁₀ is preferably a —CO— group or a —COCO— group, particularly preferably a —CO— group.

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

[0084]

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[0085]

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[0086]

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[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

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[0094]

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As the hydrazine derivative used in the present invention, the following hydrazine derivatives are preferably used in addition to the above hydrazine derivatives. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized.

(Formula 1) described in JP-B-6-77138
And specifically the compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, from pages 8 to 1 of the publication
Compounds 1 to 38 described on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4-1 to 4-10 described on page 26, compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formulas (1) and (2) described in JP-A-6-289520, specifically from page 5 to
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H described on pages 8 to 15 of the same publication
-1 to H-44. JP-A-9-22082, which is a compound characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. , A compound represented by the general formula (B), the general formula (C), the general formula (D), the general formula (E), or the general formula (F), specifically, the compound N-1 described in the same publication ~ N-30. JP-A-9-2
A compound represented by the general formula (1) described in No. 2082,
Specifically, compounds D-1 to D-55 described in the publication. In addition, WO95-32452, WO95-32453
JP-A-9-179229, JP-A-9-23526
4, JP-A-9-235265, JP-A-9-2352
No. 66, JP-A-9-235267, JP-A-9-319
019, JP-A-9-319020, JP-A-10-1
No. 30275, JP-A-11-7093, JP-A-6-3
No. 32096, JP-A-7-209789, JP-A-8-208
No. 6193, JP-A-8-248549, JP-A-8-2
48550, JP-A-8-262609, JP-A-8-262609
JP-A-314044, JP-A-8-328184, JP-A-9
-80667, JP-A-9-127632, JP-A-9-127
-146208, JP-A-9-160156, JP-A-10-161260, JP-A-10-221800,
JP-A-10-213871, JP-A-10-25408
2, JP-A-10-254088, JP-A-7-120
864, JP-A-7-244348, JP-A-7-33
3773, JP-A-8-36232, JP-A-8-36
No. 233, JP-A-8-36234, JP-A-8-362
No. 35, JP-A-8-272022, JP-A-9-220
No. 83, JP-A-9-22084, JP-A-9-5438
No. 1 and JP-A-10-175946.

In the present invention, the hydrazine-based nucleating agent may be a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, It can be used by dissolving it in methylcellosolve or the like. Also, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare and use an emulsified dispersion. Alternatively, by a method known as a solid dispersion method, hydrazine derivative powder is ball milled in water,
It can be dispersed and used by a colloid mill or an ultrasonic wave.

In the present invention, the hydrazine-based nucleating agent may be added to the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support, or to any of the other hydrophilic colloid layers. It is preferable to add to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. Also, two or more hydrazine-based nucleating agents can be used in combination. In the present invention, the addition amount of the nucleating agent is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, and more preferably 2 × 10 ⁵ mol per mol of silver halide. ^{-5 to} 5 x ^10-3 mol is most preferred.

In the present invention, it is preferable to incorporate an amine derivative, an onium salt, a disulfide derivative or a hydroxymethyl derivative as a nucleation accelerator in the light-sensitive material. Examples of the nucleation accelerator used in the present invention are listed. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically compound A described in pages 49 to 58
-1) to A-73). Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in JP-A-7-84331, specifically, compounds described on pages 6 to 8 of the same.
Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, compounds of Na-1 to Na-22 described on pages 16 to 20 of the same publication And compounds of Nb-1 to Nb-12. JP-A-8-2
General formula (1), General formula (2), General formula (3), General formula (4), General formula (5), General formula (6) and General formula (7) described in 72023 Compounds, specifically, compounds 1-1 to 1-19 described in the same specification, 2-
1-2-2, 3-1-3-36, 4
Compounds of -1 to 4-5, compounds of 5-1 to 5-41, 6
-1 to 6-58, and 7-1 to 7-38. JP-A-9-297377, p55, column 10
The nucleation promoting agent described in line 8 to line 8 to p69 of column 136, line 44.

Specific examples of the nucleation accelerator used in the present invention are shown below. However, the present invention is not limited to the following compounds.

[0101]

Embedded image

[0102]

Embedded image

The nucleation promoting agent of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. A product can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleation accelerator of the present invention may be added to any layer of the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 mol per mol of silver halide.
× 10 ⁻² mol is preferred, and 1 × 10 ⁻⁵ to 2 × 10
^-2 mol is more preferred, and 2 × 10 ⁻⁵ to 1 × 10 ^−2.
Molar is most preferred. Further, two or more nucleation accelerators can be used in combination.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right line, line 11 to page 12, lower left line, line 5. Specifically, compounds (III) -1 to 25 described in the publication.

A compound represented by the general formula (I) described in JP-A-1-11832 and having substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, fourth line.

The polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. A polymer latex having an active methylene group represented by the general formula (I) described in JP-A-9-179228, specifically, compounds I-1 to I-l described in the same specification.
I-16. Polymer latex having a core / shell structure described in JP-A-9-179228, specifically, compounds P-1 to P-55 described in the same specification. JP-A-7-1
An acidic polymer latex described on page 14, left line 1 to page 30, right line of JP-A-04413, specifically, compounds II-1) to II-9) described on page 15 of the same.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

Hardening agents described in JP-A-2-103536, page 18, upper right line, line 5 to line 17, upper right line.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right, line 6 to page 19, upper left, first line.

JP-A-2-18542, page 2, lower left 1
The conductive substance described in the third line to the upper right line on page 3 of the publication. Specifically, the metal oxides described on page 2, right lower second line to page 10 lower right line, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right line, line 1 to line 18, upper right line.

Solid disperse dyes represented by formulas (FA), (FA1), (FA2) and (FA3) described in JP-A-9-179243. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
(II-2) to (II-24) described in JP-A-7-152
No. 112, (III-5) to (III-18);
(IV-2) to (IV-7) described in US Pat. Solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds VI-1 to VI-15 described in the publication.

Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1) described in the publication,
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

JP-A-2-18542, page 3, lower right 1
Binder from line 20 to line 20

The processing agents such as the developing solution and the fixing solution, the processing method and the like in the present invention will be described below, but it goes without saying that the present invention is not limited to the following description and specific examples.

For the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.

The developer used in the present invention (hereinafter, both the development starting solution and the development replenisher are collectively referred to as a developer).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonates, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene-based developing agent, and a combination of a dihydroxybenzene or an ascorbic acid derivative with 1-phenyl-3-pyrazolidone, or a dihydroxybenzene or the like. Examples include a combination of an ascorbic acid derivative and a p-aminophenol. As a developing agent used in the present invention, dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, etc., and hydroquinone is particularly preferred. Further, ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4 -Methyl-
4-hydroxymethyl-3-pyrazolidone and the like.
N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based developing agent used in the present invention;
There are o-methoxy-p- (N, N-dimethylamino) phenol and o-methoxy-p- (N-methylamino) phenol, among which N-methyl-p-aminophenol, Aminophenols described in JP-A-297377 and JP-A-9-297378 are preferred.

The dihydroxybenzene-based developing agent is preferably used usually in an amount of 0.05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.10 mol / l. It is preferable to use 0.5 to 0.5 mol / l and the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / l to 0.5 mol / l, preferably 0.05 mol / l to 0.5 mol / l.
0.3 mol / l is more preferred. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is used in an amount of 0.01 mol / liter or less.
It is preferable to use 0.5 mol / l, 1-phenyl-3-pyrazolidones or p-aminophenols in an amount of 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphorus Acid salts (eg, sodium salt, potassium salt) and the like are used, and preferably, carbonate and boric acid are used. The amount of buffer, especially carbonate, used is preferably 0.05 mol /
Liter or more, especially 0.08 to 1.0 mol / liter.

In the present invention, both of the developing solution and the replenishing solution are such that “the pH rise when 0.2 mol of sodium hydroxide is added to 1 liter of the solution is 0.2 to 1.5”.
It preferably has the following properties. As a method for confirming that the developing solution or replenisher used has this property, the pH of the developing solution or replenisher to be tested may be determined.
Was adjusted to 10.5, and then 0.1 mol of sodium hydroxide was added to 1 liter of the solution, and the pH value of the solution at this time was measured. It is determined that it has the properties specified above. In the present invention, it is particularly preferable to use a development start solution and a development replenisher whose rise in pH value in the above test is 0.3 to 1.0.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. The sulfite is preferably at least 0.2 mol / l,
In particular, it is used in an amount of 0.3 mol / l or more, but if it is added in an excessively large amount, it causes silver contamination in the developing solution. Therefore, the upper limit is preferably 1.2 mol / l. Particularly preferably, it is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The addition amount is from 0.03 to 0.07 in molar ratio to the dihydroxybenzene-based developing agent.
The range of 0.12 is preferred, and particularly preferably 0.05 to
It is in the range of 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Other additives to be used include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, 3-
(5-mercaptotetrazol-1-yl) sodium benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be used as an antifoggant or blackpe.
pper) may be included as an inhibitor. Specifically, 5
-Nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzo Imidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,
Sodium 3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole,
-Methylbenzotriazole, 2-mercaptobenzotriazole and the like. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, various kinds of organic,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of the aminopolycarboxylic acid include, for example,
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, etc.
Compounds described in 5-67747, 57-102624 and JP-B-53-40900 can be mentioned.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3,214,454 and 3,794,591 and German Offenlegungsschrift 2,227,369, and Research Disclosure, Vol. 181, Item 18170 (1979). May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. , 55-2
9883, 56-97347 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-112127, JP-A-55-4024, and JP-A-55-40.
25, 55-126241, 55-65555, 55-65556, and the compounds described in Research Disclosure 18170 described above.

The organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ per liter of developer.
Mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

Further, as a silver stain inhibitor in the developer,
For example, JP-A-56-24347, JP-B-56-465.
85, JP-B-62-2849, JP-A-4-36294
2. In addition to the compounds described in JP-A-8-6215, triazines having at least one mercapto group (for example,
-23830, JP-A-3-282457, JP-A-7-1
75178), the same pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4, 6
-Trimercaptopyrimidine, JP-A-9-274289
Pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,
5-dimercaptopyridine, 2,4,6-trimercaptopyridine, compounds described in JP-A-7-248587, and the like pyrazines (for example, 2-mercaptopyrazine,
2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, and the like pyridazines (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimer Mercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177,
The polyoxyalkyl phosphonate described in U.S. Pat. No. 5,457,011 can be used. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer.
Further, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, a color tone agent, a surfactant, an antifoaming agent, a hardener and the like may be contained as necessary.

The preferred pH of the developer is 9.0 to 12.0.
And particularly preferably in the range of 9.0 to 11.0, more preferably in the range of 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

If the specific gravity of the developer used is too high, the density of the blackened portion of the exposed photosensitive material tends to be low. The preferred specific gravity of the developer used is 1.1
00 or less, more preferably 1.020 or more and 1.1
00, and more preferably 1.040 or more.
100 or less.

As cations in the developer, potassium ions do not suppress development as compared with sodium ions, and have less jaggedness around a blackened portion called fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, it is preferable that the molar ratio of potassium ion and sodium ion in the developer is between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishing amount of the developing solution is 390 ml or less per 1 m ² of the photographic material, preferably 325 to 30 ml, and most preferably 250 to 120 ml. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration than the start solution.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be changed as appropriate, but is generally about 0.7 to 0.7.
It is about 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferred. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are 0.01 to 0.1 as an aluminum ion concentration in the working solution.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts having a hardening agent and the like as separate parts, or may be a one-part composition containing all components.

If desired, a preservative (for example, a sulfite, a bisulfite, a metabisulfite, etc.) may be used in the fixing treatment agent.
15 mol / l or more, preferably 0.02 mol / l to 0.3 mol / l), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid, adipic acid, etc.) 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), compounds having aluminum stabilizing ability or 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 and their derivatives and salts and saccharides thereof in an amount of 0.001 mol / L to 0.5 mol / L, preferably 0.005 mol / L to 0.3 mol. / Liter), but it is better not to include a boron-based compound from the viewpoint of environmental protection in recent years.

In addition, compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be contained. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and JP-A-57-6840.
The amphoteric surfactants described above can be used, and known antifoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681 and JP-B-45-35754, JP-A-58-122535, and JP-A-58-1.
22536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.
739, 1-159645 and 3-101728
And the mesoionic compound and thiocyanate described in 4-1-170539.

The pH of the fixing solution in the present invention is preferably 4.0 or more, more preferably 4.5 to 6.0. The fixing solution is mixed with a developer to increase the pH due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixing solution, and 7.0 or less for the non-hardened fixing solution. Is 6.7 or less.

The replenishing amount of the fixing solution is 500 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml per 1 m ² of the photographic material. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, FS-200 manufactured by Fuji Photo Film Co., Ltd.
0 and so on. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing agent in the present invention is a liquid, it is preferable to store it in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Even if the developing agent and the fixing agent in the present invention are solid, the same result as that of the liquid agent can be obtained. However, the solid processing agent will be described below. As the solid preparation in the present invention, known forms (powder, granule, granule, lump, tablet, compactor, briquette, plate, stick, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 48, line 48 to column 3, line 13 can be referred to.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets or briquettes. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921,
16841, 4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferable, and especially, the tablet is 1.0 to 5.0 g / c.
m ³ is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, JP-A-4-7884.
8, 5-93991, JP-A-4-85533, 4-
85534, 4-85535, 5-134362,
5-197070, 5-204098, 5-22
4361, 6-138604, 6-138605,
8-286329 and the like can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt coagulation, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, Japanese Patent Laid-Open No. 6-242 is disclosed.
585 to 6-242588, 6-247432, 6-247448, 6-301189, 7-566
4. It is also preferable to make it foldable as disclosed in 7-5666 to 7-5669 in order to reduce the storage space of the waste packaging material. For these packaging materials, a screw cap, a pull-top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and the limitation is particularly limited. do not do. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for storing a completed solution as described in JP-A-9-80718. A method of dissolving and replenishing from a stock part, JP-A-5-119454,
6-19102 and 7-261357. A processing agent is introduced into a circulating system of an automatic developing machine as described in
There are a replenishing method, a method of adding and dissolving a processing agent in accordance with the processing of the photosensitive material in an automatic developing machine having a dissolution tank therein, and any other known methods can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolution apparatus having an opening mechanism or an automatic developing machine as described in JP-A-9-138495. From the viewpoint of the latter, the latter is preferable. More specifically, a method of breaking through the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method described in JP-A-6-19102 and JP-A-6-9-9
5331.

The photosensitive material which has been subjected to development and fixing is then washed or stabilized (hereinafter, unless otherwise specified, this is referred to as washing including stabilization, and the liquid used for these is water or washing water. ). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. These replenishing amounts are generally 1 m ² of photosensitive material.
From about 17 liters to about 8 liters per volume, although lower replenishment rates can be used. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method for reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. The replenishing amount of washing is 200 to ⁵ per m ² of the photosensitive material.
0 ml is preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new liquid is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. Known means can be used as the scale preventive means, and is not particularly limited, but a method of adding a sunscreen (a so-called scale preventive agent), a method of energizing, a method of irradiating ultraviolet rays or infrared rays or far infrared rays, There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed according to the processing of the photosensitive material, may be performed at regular intervals irrespective of the state of use, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. As a water-saving scale device, an apparatus AC-1000 manufactured by Fuji Photo Film Co., Ltd. and AB-5 manufactured by Fuji Photo Film Co., Ltd. as an anti-scale agent may be used.
231485 may be used. The protective agent is not particularly limited, and known agents can be used. Other than the above-mentioned oxidizing agents, there are, for example, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (eg, 2-mercaptopyridine-N-oxide and the like). But it is good. As a method of energizing, Japanese Patent Application Laid-Open No.
4885, 3-224687, 4-162280, 4-18980 and the like.

In addition, known water-soluble surfactants and defoamers may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing system to prevent contamination by the dye eluted from the photosensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment.
JP-A-132435, JP-A-1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, Al, etc., a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a deodorant, an alkanolamine or a surfactant may be used in this stabilizing bath. Agents can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths may be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. These waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to condense or solidify with a concentrating device as described in S5, 439, 560, etc. before disposing.

To reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent the evaporation of the liquid and the oxidation of the air. U.S. Pat. No. 3,025,779 and U.S. Pat.
1 and the like, and are simply referred to as a roller transport type automatic developing machine in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stopping step), but most preferably follows these four steps. Further, a rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, the time from the start of processing to after drying (dry to dry) is preferably 25 to 160 seconds, and the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds. 25 to 50 ° C. is preferred, and 3
0-40 ° C is preferred. The temperature and time of washing are 0-5
It is preferably 40 seconds or less at 0 ° C. According to the method of the present invention,
The developed, fixed and washed photosensitive material may be dried by squeezing washing water, that is, passing through a squeeze roller.
Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.
89294, heat roller drying, drying by far infrared rays, and the like, and a plurality of methods may be used in combination.

[0166]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of Emulsion A 1 solution Water 750 ml Gelatin 20 g Sodium chloride 3 g 1,3-Dimethylimidazolidin-2-thione 20 mg Sodium benzenethiosulfonate 10 mg Citric acid 0.7 g 2 solutions Water 300 ml Silver nitrate 150 g 3 solutions Water 300 ml chloride Sodium 38 g potassium bromide 32 g potassium hexachloroiridate (III) (0.005 mass% KCl 20 mass% aqueous solution) 5 ml ammonium hexachlororhodate (0.001 mass% NaCl 20 mass% aqueous solution) 7 ml hexachloroiridium used for 3 liquids III) Potassium acid (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass)
20% by mass aqueous NaCl solution) were prepared by dissolving the powders in a 20% by mass aqueous solution of KCl and a 20% by mass aqueous solution of NaCl, respectively, and heating at 40 ° C. for 120 minutes.

One solution kept at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were respectively added in amounts corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Subsequently, the following liquids 4 and 5 were added over 8 minutes, and the remaining 10% of the liquids 2 and 3 were added over 2 minutes to grow to 0.21 μm. further,
0.15 g of potassium iodide was added and the mixture was aged for 5 minutes to complete the particle formation. Fourth liquid 100 ml Silver nitrate 50 g Five liquid 100 ml Sodium chloride 13 g Potassium bromide 11 g Yellow blood salt 5 mg After that, water was washed by flocculation according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated. (PH 3.
Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing).
Repeat the same operation as the second washing one more time (third washing)
The washing and desalting process was completed. To the emulsion after washing and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and pAg 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemical sensitization to obtain optimum sensitivity at ℃, 4-
100 mg of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) as a preservative were added. Finally, 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 variation coefficient of 9% was obtained. (Finally, as an emulsion, pH = 5.7, pAg = 7.5, conductivity = 40 μS
/ M, density = 1.2 to 1.25 × 10 ³ kg / m ³ , and viscosity = 50 mPa · s. )

Preparation of Emulsion B 1 solution water 750 ml gelatin 20 g sodium chloride 1 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 10 mg citric acid 0.7 g 2 solutions water 300 ml silver nitrate 150 g 3 solutions water 300 ml chloride Sodium 38 g Potassium bromide 32 g Potassium hexachloroiridate (III) (0.005% by mass KCl 20% by mass aqueous solution) 5 ml Ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) 15 ml Hexachloroiridium used for three liquids III) Potassium acid (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) each convert powder into KCl 20 % Aqueous solution and a 20% by mass aqueous NaCl solution, and heated at 40 ° C. for 120 minutes for preparation.

One solution kept at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were respectively added in amounts corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Thereafter, 4-hydroxy-6-methyl-1,
500 mg of 3,3a-tetrazaindene was added, followed by Liquids 4 and 5 described below over 8 minutes, and then the remaining 10% of Liquids 2 and 3 over 2 minutes.
It was grown to 0.18 μm. Further, 0.15 g of potassium iodide was added and the mixture was aged for 5 minutes to complete the particle formation. 4th liquid 100ml Silver nitrate 50g 5th liquid 100ml Sodium chloride 13g Potassium bromide 11g Yellow blood salt 2mg Thereafter, water was washed by flocculation according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated. (PH 3.
Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing).
Repeat the same operation as the second washing one more time (third washing)
The washing and desalting process was completed. To the emulsion after washing and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and the pAg to 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 2 mg of triphenylphosphine selenide, and 1 mg of chloroauric acid were added. Plus 55
Chemical sensitization was performed so as to obtain the optimum sensitivity at 4 ° C., and 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene and 100 mg of proxel as a preservative were added. Finally, 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 variation coefficient of 10% was obtained.
(Finally, as an emulsion, pH = 5.7, pAg = 7.
5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg
/ M ³ and viscosity = 50 mPa · s. )

Preparation of Non-Photosensitive Silver Halide Grain-I 1 solution 1 liter of water 20 g of gelatin 20 g of potassium bromide 0.9 g of citric acid 0.2 g of NH ₄ NO ₃ 20 g of hydrogen peroxide 3.5 g of sodium benzenethiosulfonate 15 mg 2 Liquid water 400 ml Silver nitrate 200 g 3 Liquid water 400 ml Potassium bromide 140.0 g Potassium hexachlorodimate (III) (0.001% by mass aqueous solution) 4000 ml

While stirring one solution maintained at 60 ° C.,
40 ml of OH (1N) was added, and 0.7 g of an aqueous silver nitrate solution was further added. After that, 1 /
Add two each by the control double jet method over a period of 20 minutes while keeping the silver potential at +24 mV, and after physical ripening for 2 minutes, use the same control double jet method for the remaining half of the second and third solutions. For 20 minutes to form particles.

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated.
(PH was in the range of 3.1 ± 0.2) Next, about 3 liters of the supernatant was removed (first water washing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. 45 g of gelatin was added to the emulsion after washing with water and desalting, pH 5.7, pAg
Was adjusted to 7.5, and phenoxyethanol was added as a preservative. Finally, it contained 30 mol% of average silver chloride and 0.08 mol% of silver iodide, and had an average particle diameter of 0.8 μm and a variation coefficient of 10%. A dispersion of unripe silver bromide tetradecahedral emulsion grains was obtained. (Finally, as an emulsion, pH = 5.7, pAg =
7.5, conductivity = 40 μS / m, density = 1.3 × 10 ³
kg / m ³ and viscosity = ³⁰ mPa · s. )

Preparation of Non-Photosensitive Silver Halide Grain-II By appropriately changing the conditions for forming the above non-photosensitive silver halide grain-I, an average particle size of 0.5 μm and a variation coefficient of 10% were obtained. A dispersion of unripe silver bromide tetradecahedral emulsion grains was obtained.

Preparation of Non-Light-Sensitive Silver Halide Grains In the following aqueous solutions X-1 to X-4, 1 mole of KBr was added per 1 mole of KBr.
× 10 ⁻⁵ mol of hexachlorodium (II
I) Particle formation was performed by adding potassium acid.

(Preparation of 1st solution) An aqueous solution 1 containing 0.6 g of KBr and 1.1 g of gelatin having an average molecular weight of 15,000.
300 mL was kept at 35 ° C. and stirred.

(Addition 1) 24 mL of an aqueous solution of Ag-1 (containing 4.9 g of AgNO ₃ in 100 mL) and X-1
Aqueous solution (containing 4.1 g of KBr in 100 mL) 2
4 mL and 24 mL of an aqueous G-1 solution (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 raised to 75 ° C. After an aging step for 12 minutes after the temperature rise, an aqueous solution of G-2 aqueous solution (100 ml of an alkali-treated ossein gelatin aqueous solution was added to trimellitic anhydride at 50 ° C. and pH 9.0) to cause a reaction. 300 mL (containing 12.7 g of gelatin obtained by removing trimellitic acid) was added, and then disodium 4,5-dihydroxy-1,3-disulfonate monohydrate was added.
1 g and 0.002 g of thiourea dioxide were sequentially added at intervals of 1 minute.

(Addition 2) Next, an aqueous solution of Ag-2 (100
157 mL containing 22.1 g of AgNO ₃ in mL)
And an X-2 aqueous solution (15.5 g of KBr in 100 mL)
Was added by the double jet method over 14 minutes. At this time, the addition of the Ag-2 aqueous solution accelerates the flow rate so that the final flow rate becomes 3.4 times the initial flow rate, and the addition of the X-2 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 3) Next, an Ag-3 aqueous solution (10
(Containing 32.0 g of AgNO ₃ in 0 mL) 329 m
L and X-3 aqueous solution (21.5 KBr in 100 mL)
g, 1.6 g of KI) by the double jet method.
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 4) Further, an Ag-4 aqueous solution (10
(Containing 32.0 g of AgNO ₃ in 0 mL) 156 m
L and X-4 aqueous solution (22.4 KBr in 100 mL)
g) was added over 17 minutes by the double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate, and the X-3 aqueous solution was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.3.

Thereafter, 0.0025 g of sodium benzenethiosulfonate, an aqueous G-3 solution (100 mL containing 12.0 of alkali-treated ossein gelatin) 12
5 mL was added sequentially at one minute intervals.

Next, 43.7 g of KBr was added, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.0.
73.9 g of AgI fine particles (containing 13.0 g of AgI fine particles having an average particle size of 0.047 μm in 100 g) were added.

(Addition 5) Two minutes later, 249 mL of an aqueous solution of Ag-4 and an aqueous solution of X-4 were added by a double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 16 minutes, and the X-4 aqueous solution was added so as to keep the pAg at 9.10.

(Addition 6) Subsequently, for 10 minutes, the addition was performed such that the pAg of the bulk emulsion in the reaction vessel became 7.5.

Thereafter, desalting is carried out by a usual flocculation method, and then water, NaOH and alkali-treated ossein gelatin are added with stirring, and the pH is adjusted at 56 ° C.
It adjusted so that it might be set to 5.8 and pAg8.9.

The obtained particles had an equivalent circle diameter of 1.2 μm, a particle thickness of 0.20 μm, and an average AgI content of 3.94.
Mole%, tabular silver halide grains whose parallel main plane was the (111) plane, and the coefficient of variation of the equivalent circle diameter of all grains was 24%.

Preparation of Non-Light-Sensitive Silver Halide Grains Tabular emulsions having different circle equivalent diameters / grain thicknesses as shown in the table by appropriately changing the grain growth conditions and the like of the non-light-sensitive silver halide grains. Was adjusted.

[0188]

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Preparation of Coated Sample A polyethylene terephthalate film support having both surfaces shown below having a moisture-proof layer containing vinylidene chloride undercoat was applied so as to have a structure of UL layer / emulsion layer / protective layer lower layer / protective layer upper layer. To prepare a sample. The preparation method, application amount and application method of each layer are shown below. <Emulsion Layer> Emulsion A and Emulsion B were mixed at a ratio of 1: 2 in terms of Ag amount, and sensitizing dye (SD-1) 5.7 × 10 ⁻⁴ mol / mol Ag was added thereto for spectral sensitization. did. Further KBr
3.4 × 10 ⁻⁴ mol / mol Ag, compound (Cpd-1)
2.0 × 10 ⁻⁴ mol / mol Ag, compound (Cpd-2)
2.0 × 10 ⁻⁴ mol / mol Ag, compound (Cpd-3)
8.0 × 10 ⁻⁴ mol / mol Ag was added and mixed well. Then 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag, hydrazine nucleation Agents D-2b, D-11g, and D-68 were each 1.5 × 10 ⁻⁴ mol / mol Ag, and the nucleation accelerator (Cpd-4) was 6.0 × 10 ⁻⁴ mol / mol Ag, 2, 4
-Dichloro-6-hydroxy-1,3,5-triazine sodium salt at 90 mg / m ² ,
% By mass of colloidal silica having a particle diameter of 10 μm, aqueous latex (Cpd-5) of 100 mg / m ² , polyethyl acrylate latex of 150 mg / m ² , methyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid sodium salt, and Acetoxyethyl methacrylate latex copolymer (weight ratio 88: 5: 7)
0 mg / m ² , core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63), shell: styrene / 2-acetoxyethyl acrylate (weight ratio 84/16), core / shell ratio = 50/50 ) To 1
50 mg / m ² , 4% by mass of the compound (Cp
d-6) was added, and the pH of the coating solution was adjusted to 5.6 using citric acid.
Was adjusted. The emulsion layer coating solution thus prepared was theoretically coated on the following support with Ag 2.9 g / m ² and gelatin 1.
Coating was performed so as to be 3 g / m ² . <Top layer of protective layer> Gelatin 0.3 g / m ² Solid particles of the present invention Amount shown in the table 3.5 μm average amorphous silica matting agent 25 mg / m ² Compound (Cpd-7) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm (Snowtex C manufactured by Nissan Chemical Industries, Ltd.) 30 mg / m ² compound (Cpd-8) 50 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² compound (Cpd-9) 20 mg / m ² compound (Cpd-10) 20 mg / m ² preservative (Proxel (trade name, manufactured by ICI Co., Ltd.)) 1 mg / m ² <Protective layer lower layer> Gelatin 0.5 g / m ² compound (Cpd -11) 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² Compound (Cpd-12) 3 mg / m ² Preservative (proxel) 1.5 mg / m ² <UL layer> Gelatin 0.5 g / m ² Solid particles of the present invention Amount shown in table Polyethyl acrylate latex 150 mg / m ² 5-Methyl-benztriazole 40 mg / m ^Two compounds (Cpd-6) 40 mg / m ² Compounds (Cpd-13) 10 mg / m ² Preservatives (proxel) 1.5 mg / m ²

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

[0191]

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The sample used in the present invention has a back layer and a conductive layer having the following compositions. <Back layer> Gelatin 3.3 g / m ² Solid particles of the present invention Amount shown in table Compound (Cpd-14) 40 mg / m ² Compound (Cpd-15) 20 mg / m ² Compound (Cpd-16) 90 mg / m ² compounds (Cpd-17) 40 mg / m ² compounds (Cpd-18) 26 mg / m ² compounds (Cpd-19) 5 mg / m ² 1,3-divinylsulfonyl-2-propanol 60 mg / m ² polymethyl methacrylate fine particles ( Average particle size 6.5 μm) 30 mg / m ² Liquid paraffin 78 mg / m ² Compound (Cpd-6) 120 mg / m ² Calcium nitrate 20 mg / m ² Preservative (Proxel) 12 mg / m ² <Conductive layer> Gelatin 0.1 g / M ² sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² preservative (Proxel ) 0.3 mg / m ²

[0193]

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[0194]

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[0195]

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<Support> A first layer and a second layer of an undercoat layer having the following composition on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were applied.

<One undercoat layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle diameter 3 μm) 0.05 g Compound (Cpd) -20) 0.20 g colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Industry Co., Ltd.) 0.12 g 100 g by adding water, and further adjusted to pH = 6 by adding 10% by mass of KOH. The coating solution was dried at a drying temperature of 180 ° C. for 2 minutes and the dry film thickness was 0.1 mm
It was applied so as to have a thickness of 9 μm.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound (Cpd-21) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Proxel 3.5 × 10 ^{− 3} g Acetic acid 0.2 g Water was added and 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness became 0.1 μm.

[0199]

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<Coating Method> On the support provided with the above-mentioned undercoat layer, four layers of an UL layer, an emulsion layer, a protective layer lower layer, and a protective layer upper layer were formed in this order from the side closer to the support as the emulsion surface side. At the same time while adding the hardener liquid by the slide bead coater method while maintaining the temperature at ℃, the cold air set zone (5
° C), and from the side closer to the support opposite to the emulsion surface, from the side closer to the support, a conductive layer and a back layer are simultaneously coated in the order of a hardener solution by a curtain coater method and a cold air set zone ( 5 ° C.). At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time was 200 m / min.

<Drying conditions> After setting, the mixture was dried with a drying air at 30 ° C until the mass ratio of water / gelatin became 800%.
After drying 200 to 200% with a dry air at 35 ° C and 30% RH, the air is directly applied, and 30 seconds after the surface temperature reaches 34 ° C (assuming the drying is completed), 48 ° C and 2% RH.
For 1 minute. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800%.
It takes 35 seconds from 0% to 5 seconds from 200% to the end of drying.

This photosensitive material is wound up at 25 ° C. and 55% RH.
Heat treatment was performed at 35 ° C. and 30% RH for 72 hours.
Next, after cutting at 25 ° C. and 55% RH and humidity-controlling at 25 ° C. and 50% RH for 8 hours in a barrier bag conditioned for 6 hours,
Sealed with cardboard conditioned at 50 ° C 50% RH for 2 hours,
The samples shown in Table 1 were prepared. For comparison, a sample not subjected to heat treatment after winding was also prepared. When the humidity inside the barrier bag was measured, it was 45% RH. Also,
The film surface pH of the emulsion layer side of the obtained sample was 5.5 to 5.8,
The pH of the film surface on the back side was 6.0 to 6.5. In addition,
The absorption spectra of the emulsion layer side and the back layer side were as shown in FIG. For the measurement of the absorption spectrum, a spectrophotometer U-3500 manufactured by Hitachi, Ltd. was used, and a sample whose surface on the side opposite to the measurement surface was removed was placed in a φ200 integrating sphere set in a sample chamber. A measurement was made.

The evaluation was performed by the following method. [Evaluation of Spectral Reflectance] To evaluate the spectral reflectance, a spectrophotometer U-3500 manufactured by Hitachi, Ltd. was used, and black paper was placed on the opposite side of the measurement surface in a φ200 integrating sphere installed in the sample chamber. The measurement was performed by irradiating a probe light to the sample provided with the sample and integrating the light reflected from the measurement surface with an integrating sphere. [Evaluation of Sensor Suitability] Samples were loaded into the following image setters, and an operation of actually performing exposure processing was performed to evaluate whether or not there was a sensor detection defect.・ Dolev450 manufactured by Nippon Cytex Co., Ltd. ・ F9000 manufactured by Fuji Photo Film Co., Ltd. ・ Lux setter RC56 manufactured by Fuji Photo Film Co., Ltd.
If the 00V sensor detection failure occurs, “NO FIL
An error such as "M" is displayed. 0.3 on sensor surface
The sensor suitability was evaluated by the error display frequency through an ND filter having a density of. It shows how many times a "NO FILM" error has occurred during the 10 tests. [Evaluation of Haze] Each sample was developed without being exposed,
The sheets were stacked and the haze was visually evaluated. The lower limit acceptable for practical use was set at 3, and the level at which there was no problem at all for practical use was set at 5. [Evaluation of photographic properties] The obtained sample was exposed to xenon flash light having an emission time of ^10-6 seconds through an interference filter having a peak at 633 nm and a step wedge. Then, using the developing solution (A) and the fixing solution (B) having the following formulations, processing was performed at 35 ° C. and 30 ″ using an AP-560 automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.).

Developer (A) Represents the composition per liter of concentrated solution. 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 2-mercaptobenzimidazole-5-sulfonic acid sodium 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 erythorbrate 9.0 g diethylene glycol 60.0 g potassium hydroxide was added, and water was added to make 1 liter.
Adjust H to 10.7. As a starting solution (mother solution), water 3 is added to the above solution 1 (pH is 10.4). As a replenisher, water 2 is added to the above solution 1 (pH is 10.45).

Fixing Solution (B) Formulation The formula per 1 L of the concentrated solution is shown. Ammonium thiosulfate 360 g Ethylenediamine tetraacetic acid 2Na 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 For use, dilute 2 parts of water to 1 part of the above concentrated liquid. The pH of the working solution is 4.8.

[Evaluation of Photographic Properties] The reciprocal of the exposure amount giving a density of 1.5 is expressed as sensitivity and expressed as relative sensitivity.
0.3) / log (exposure dose giving a density of 1.5) -lo
g (exposure amount giving a density of 0.3). [Evaluation of practical skill density] Using an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd. and an automatic developing machine AP-560 connected thereto, a test step was output while changing the light amount at 175 lines / inch, and The development processing was performed under the processing conditions, and the _Dmax portion when the exposure was performed at an LV value at which the intermediate halftone dot became 50% was measured, and the actual density was determined. Note that the net% and the actual skill concentration are Macbeth TD904.
It measured using. [Evaluation of Photographic Properties with Fatigue Developing Solution]
Each film sample of 80% blackening per day,
Use liquid 5 per large size (50.8cm x 61cm)
By processing 300 sheets of all-large size while replenishing 0 cc and performing this process continuously for 4 days, a large number of films were processed to obtain a developer in which the pH dropped to 10.2 and the bromine ion concentration increased. .

Using the above-mentioned fatigue developing solution, changes in the sensitivity and the practical density were evaluated.

[0208]

[Table 1]

[0209] Table 1 shows that the sample of the present invention has improved sensor suitability. Further, it can be seen that there is little influence on the change in performance when processing is performed with the fatigue developing solution, and it is good. When tabular silver halide was used, haze did not deteriorate and it was found to be preferable.

Example 2 The following emulsion C was used in place of the emulsions A and B in the coating solution for the emulsion layer in Example 1, and Ag 2.5 g / m ² and gelatin 1.1 g / g
except for coating so that in m ² is the same manner as in Example 1 to prepare a sample, and evaluated. As in Example 1, the sample of the configuration of the present invention showed good performance. Emulsion C 1 liquid 1 liter water 20 g gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml sodium chloride 19.0 g potassium bromide 31.5 g Potassium hexachloroiridate (III) (0.005 mass% KCl 20 mass% aqueous solution) 5 ml Ammonium hexachlororhodate (0.001 mass% NaCl 20 mass% aqueous solution) 7 ml 3 hexachloroiridium (III) used for the liquid ) Potassium (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) were used to prepare powders of KCl 20% by mass aqueous solution and NaCl 20% by mass, respectively. % Dissolved in an aqueous solution was prepared by heating at 40 ° C. 120 min.

Solution 1 and Solution 3 were added simultaneously to Solution 1 kept at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4 liquid water 400 ml silver nitrate 100 g 5 liquid water 400 ml sodium chloride 19.0 g potassium bromide 31.5 g potassium hexacyanoferrate (II) (0.1% by mass aqueous solution) 10 ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, and 1.0 mg of sodium thiosulfate, 4.0 mg of chloroauric acid, 1.5 mg of triphenylphosphine selenide, 8 mg of sodium benzenethiosulfonate, and 2 mg of sodium benzenethiosulfinate were added. In addition, chemical sensitization was performed at 55 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,
100 mg of 3,3a, 7-tetrazaindene and phenoxyethanol as a preservative were added, and finally a silver chloroiodobromide cubic emulsion A containing 55 mol% of silver chloride and having an average particle diameter of 0.19 μm was obtained.

Example 3 The same experiment as in Example 1 was performed using the samples of Examples 1 and 2 using the following solid developer (C) and solid fixing agent (D). Similarly to 2, the sample of the configuration of the present invention showed good performance.

Formulation of solid developer (C) Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 63.0 g Sodium sulfite (raw powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) Diethylenetriamine / pentaacetic 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 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g sodium erythorbate 6.0 g potassium bromide 6.6 g Dissolve in water to make 1 liter. pH 10.65

Here, in the form of raw materials, raw powders were used as general industrial products, and commercially available beads of alkali metal salts were used. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treating agent was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. Dissolution and replenishment are described in JP-A-9-80718,
A dissolution replenisher with an automatic opening mechanism as disclosed in US Pat.

Formulation of solid fixing agent (D) Formulation A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (raw powder) 19.0 g Sodium metabisulfite (raw powder) 18.0 g Anhydrous sodium acetate (raw) Powder) 42.0 g Agent B (liquid) Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.03 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make up to 50 ml. . The fixing solution (D) was prepared by dissolving the agent A and the agent B in water and adjusting the solution to 1 liter. pH was 4.8.

The ammonium thiosulfate (compact) was obtained by compressing and compressing a flake product prepared by a spray-drying method with a roller compactor and crushing into an amorphous chip having a size of about 4 to 6 mm, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the B agent container was sealed with a screw cap. For dissolving and replenishing, a dissolving and replenishing device having an automatic opening mechanism disclosed in JP-A-9-80718 and JP-A-9-138495 was used.

Example 4 The following developer (E) was used in place of the developer (A) of Example 1.
Alternatively, using (F), the same experiment as in Examples 1 and 2 was performed using the samples of Examples 1 and 2, and the photosensitive material having the structure of the present invention exhibited good performance as in Examples 1 and 2. showed that.

The composition of the developer (E) per liter of the concentrated solution is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic 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 2-mercaptobenzimidazole-5-sodium sulfonate 0.45 g Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g pH 10.7 For use, the starting solution (mother liquor) is prepared by adding water 3 to the above solution 1 (pH 10.4). As a replenisher, water 2 is added to the above solution 1 (pH is 10.45).

The composition of the developer (F) per liter of the concentrated solution is shown below. Water 600 ml potassium hydroxide 96.0 g diethylenetriamine-pentaacetic 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-mercaptobenzthiazole 0.18 g 1-phenyl-5-mercaptotetrazole 0.06 g sodium erythorbate 9.0 g diethylene glycol 40.0 g Potassium hydroxide was added, and water was added to make 1 liter.
Adjust H to 10.8. In use, water 2 is added to the above concentrated liquid 1 (pH is 10.45).

Example 5 In Examples 1-4, the developing temperature was 38 ° C. and the fixing temperature was 37.
When the processing was carried out at a temperature of 20 ° C. and a developing time of 20 seconds, the same results as in Examples 1 to 4 were obtained, and the effects of the present invention were not lost.

Example 6 In Examples 1 to 5, the automatic machine was replaced by FG-680AS manufactured by the company.
, The same processing was performed with the photosensitive material transporting speed set to a linear speed of 1500 mm / min to obtain similar results.

Example 7 Lux Setter RC-5 manufactured by Fuji Photo Film Co., Ltd.
Instead of using 600V, Dainippon Screen Co., Ltd.
Setter FT-R5055 manufactured by Agfage Balt Co., Ltd. Select set 5000, Avantra 2
5, or Accuset 1000, Dreb 450 or Dreb 800, manufactured by Cytex Co., Ltd., Rhino 630, Quasar, Hercules Elite, or Signa Setter, manufactured by Heidel Co., Ltd., or Laxel F-9000, or Prepress (trade name) The same evaluations as in Examples 1 to 6 were performed using any one of the Panther Pro 62 models manufactured by the Company), and the same effect was obtained with the sample of the present invention.

[Brief description of the drawings]

FIG. 1 shows absorption spectra of an emulsion layer side and a back side in Examples of the present invention.

[Explanation of symbols]

The vertical axis indicates absorbance (0.1 interval), and the horizontal axis is 350 nm.
From 950 to 950 nm. The solid line shows the absorption spectrum on the emulsion layer side, and the broken line shows the absorption spectrum on the back layer side.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shoji Yasuda 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2H016 AA00 AC00 BB00 BC03 2H023 AA00 BA00 GA03

Claims (10)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer having at least one photosensitive silver halide emulsion on a support, wherein the silver halide emulsion layer is the same layer or a different hydrophilic layer. Silver halide characterized in that the hydrophilic colloid layer contains solid particles in an amount to increase the average value of the integrated value of the spectral reflectance of the photosensitive material in the wavelength range of 850 to 1,000 nm by 1.5% or more. Photosensitive material. 2. The light-sensitive silver halide photographic material according to claim 1, wherein the refractive index of the solid particles is 1.54 or more. 3. The light-sensitive silver halide photographic material according to claim 1, wherein the solid particles are substantially light-insensitive silver halide particles. 4. The solid grains are substantially light-insensitive silver halide grains, and the light-insensitive silver halide grains are tabular grains having an average grain thickness of 0.02 to 0.20 μm. 3. The photosensitive silver halide photographic material according to item 3. 5. The photosensitive silver halide emulsion according to claim 1, wherein the coated silver amount is 3.0 g / m ² or less.
4. The photosensitive silver halide photographic material according to any one of the above. 6. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support,
In a method for processing a silver halide photographic light-sensitive material, which is exposed by using an image setter and then conveyed by an automatic conveyance system and automatically performed until development processing by an automatic developing machine, the same layer as the silver halide emulsion layer or another hydrophilic layer is used. Silver halide photographic light-sensitive material characterized by adding solid particles which increase the average value of the integrated value of the spectral reflectance of the light-sensitive material in the wavelength range of 850 to 1,000 nm by 1.5% or more to the ionic colloid layer. Material treatment method. 7. The method for processing a photosensitive silver halide photographic material according to claim 6, wherein the refractive index of the solid particles is 1.54 or more. 8. The method for processing a light-sensitive silver halide photographic material according to claim 6, wherein the solid particles are substantially light-insensitive silver halide particles. 9. The solid grains are substantially light-insensitive silver halide grains, and the light-insensitive silver halide grains are tabular grains having an average grain thickness of 0.02 to 0.20 μm. 9. The method for processing a photosensitive silver halide photographic material according to item 8. 10. The photosensitive silver halide emulsion according to claim 6, wherein the coated silver amount is 3.0 g / m ² or less.
4. A method for processing a photosensitive silver halide photographic material according to any one of the above.