JPH0566525A - Developing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a method for development by which blackness of silver in a picture image is improved without desensitization in the rapid treatment of a high sensitive emulsion using a highly active developer. CONSTITUTION:This method features in treating a silver halide photographic sensitive material with a developer containing a nitrogen-contg. heterocyclic mercapt compd. and a compd. expressed by formula. In formula I, R is an aryl group, R1, R2, R3, and R4 may be same or different, hydrogen atoms, alkyl groups, aryl groups, or aralkyl groups. However, if R is a unsubstd. phenyl group, all of R1, R2, R3, R4 are not hydrogen at one time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing and processing a silver halide photographic light-sensitive material, which is characterized by obtaining a high-quality image in which the blackness of image silver is improved, especially in rapid processing. ..

[0002]

2. Description of the Related Art Conventionally, the improvement of the covering power of a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) has been one of the important techniques for saving the amount of silver. On the other hand, in recent years, there has been an increasing demand for rapid processing in the development of photosensitive materials. The silver saving of the light-sensitive material can facilitate speeding up of processing by an automatic processor (hereinafter referred to as an automatic processor).

To increase the covering power of silver halide emulsions, it is possible to obtain significantly higher covering power by mixing a high iodine surface-sensitive emulsion with an emulsion consisting of small sized internally fogged grains. US Pat. No. 2,996,3
No. 22, No. 3,178,282, No. 3,397,
987, 3,607,278, British Patent 1,4
No. 26,277 and the like. Further, the use of a tabular emulsion having a high aspect ratio and a small grain thickness significantly increases the developed silver covering power.
No. 986, No. 4,434, 226, No. 4,41
No. 3,053 is disclosed. Furthermore, JP-A-58
No. -108,526 discloses that a so-called epitaxial tabular grain in which another silver salt is arranged at a specific site on a flat plate having a high aspect ratio and a small grain thickness can obtain remarkably high photosensitivity and covering power. There is. In addition to the above emulsions, when a high-sensitivity fine grain emulsion having a small average grain size or a high-sensitivity plate-shaped grain emulsion having a small average thickness is used, it has a higher silver covering power than an emulsion having a large average grain size or a large average grain thickness. well known.

On the other hand, in rapid processing, it is important to use a highly active developing solution because it is necessary to complete development in a short time. To design a highly active developer,
Although it is effective to raise the pH and the concentration of hydroquinone which is a developing agent, it is not a preferable method because the air oxidation stability of the developing solution is deteriorated. Increasing the concentration of the auxiliary developing agent, pyrazolidones, is an effective method without the above problems. Further, in the rapid processing, it is necessary to complete the fixing in a short time, so that it is essential to reduce the average grain size of the emulsion.

However, when the emulsion grains providing the above high silver covering power are treated with the above high activity developing solution,
The color tone of developed silver almost always depends on the grain size and grain thickness, but is yellowish and gives an unpleasant impression to the image observer. This yellowish tint is due to the fact that the size and thickness of developed silver also decrease with the phenomenon of grain size and grain thickness, and the scattering of blue light components increases, resulting in light with a strong yellow tint. Such a phenomenon becomes a particular problem when a fine grain emulsion is used as the silver halide emulsion. In general, in order to adjust the color tone of developed silver, the addition of well-known triazoles or thioureas to the developer or emulsion causes a desensitizing action, and the effect of improving the color tone should be satisfied. It is not a level and cannot be put to practical use.

[0006]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to develop a high-sensitivity emulsion in a rapid processing with a highly active developing solution in which the blackness of image silver is improved without desensitization. It is to provide a processing method.

[0007]

The above problems have been solved by the present invention described below. That is, the present invention is directed to a silver halide emulsion containing silver halide grains having a silver sphere-equivalent average grain diameter of 0.5 μm or less, or a tabular halogen having an average grain thickness of 0.25 μm or less and an average aspect ratio of 3 or more. At least one silver halide emulsion containing silver halide grains
A development processing method is characterized in that a silver halide photographic light-sensitive material using a seed is processed with a developing solution containing a nitrogen-containing heterocyclic mercapto compound and a compound represented by the following general formula (1). General formula (1)

[0008]

[Chemical 2]

(In the formula, R represents an aryl group. R ₁ ,
R ₂ , R ₃ and R ₄ may be the same or different from each other,
Each represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. However, when R represents an unsubstituted phenyl group, R ₁ , R ₂ , R ₃ , and R ₄ are not hydrogen atoms at the same time. The development processing method according to claim 1, wherein the compound represented by the general formula (1) is contained in an amount of 2 g or more per liter of the developing solution.
The nitrogen-containing heterocyclic mercapto compound used in the present invention, the nitrogen-containing heterocycle, imidazoline ring, imidazole ring, imidazolone ring, pyrazoline ring, pyrazole ring, pyrazolone ring,
Oxazoline ring, oxazole ring, oxazolone ring, thiazoline ring, thiazole ring, thiazolone ring, selenazoline ring, selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, indazole ring, benz Oxazole ring, benzthiazole ring, benzselenazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring, polyazaindene ring (for example, triazaindene ring, Tetrazaindene ring, pentazaindene ring, etc.) and the like. Among these, particularly preferable nitrogen-containing heterocyclic mercapto compounds are mercaptotetrazole, mercaptothiadiazole, and mercaptooxadiazoles, and most preferably mercaptotetrazole.
Specific examples of the compounds represented by mercaptotetrazoles, mercaptothiadiazoles and mercaptooxadiazoles are shown below, but the present invention is not limited thereto.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

The amount of these mercapto compounds used is 0.01 to 1 g, especially 0.05 to 1 liter, per liter of the developing solution.
It is preferably 0.5 g. Next, the compound represented by formula (1) will be described in detail. Here, R represents an aryl group (eg, phenyl or naphthyl group). R ₁ ,
R ₂ , R ₃ and R ₄ are each a hydrogen atom and have 1 to 12 carbon atoms.
Alkyl groups (eg, methyl, ethyl, propyl, isopropyl and higher alkyl groups), aryl groups having 6 to 12 carbon atoms (eg, phenyl, naphthyl groups, etc.), aralkyl groups having 7 to 13 carbon atoms (eg, benzyl group) Represents. Further, the aryl group of R and the alkyl group, aryl group and aralkyl group of R _{1 to} R ₄ may each have a substituent, and each substituent is, for example, a hydroxy group,
Examples thereof include an alkoxy group, a hydroxyalkyl group, an amino group, a nitro group, a sulfonic acid group, a carboxyl group and a halogen atom. The carbon number of these substituents is preferably 1 to 4. Of the above general formulas, R ₁ is preferably an alkyl group in which a hydrogen atom is substituted with an amino group, or a hydroxyalkyl group. R ₄ is preferably a hydrogen atom. More preferably, R ₂ is a hydroxyalkyl group, R ₃ is a hydroxyalkyl group, an alkyl group, or a substituted alkyl group, and R is an aryl or substituted aryl group. The alkyl group preferably has 4 or less carbon atoms. Examples of the compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto. (1) 1-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone (2) 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidone (3) 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone (4) 1-phenyl-4, 4-Dimethyl-3-pyrazolidone (5) 1-phenyl-2-hydroxymer-4,4-
Dimethyl-3-pyrazoline (6) 1-phenyl-2-morpholinomethyl-4,
4-Dimethyl-3-pyrazolidone (7) 1-phenyl-2-morpholimethyl-4-methyl-3-pyrazolidone (8) 1-phenyl-2-hydroxymethyl-4-methyl-3-pyrazolidone (9) 1 -Phenyl-5,5-dimethyl-3-pyrazolidone (10) 1-phenyl-5-methyl-3-pyrazolidone (11) 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (12) 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone (13) 1-o-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (14) 1-p-methoxyphenyl-4-methyl -4-
Hydroxymethyl-3-pyrazolidone (15) 1- (3,5-dimethyl) phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone These compounds are used as auxiliary developing agents, and all of them are It is stable in alkaline developers.
Further, the amount of the compound of the present invention to be used is 2 g or more per 1 liter of the developing solution in order to enhance the developing activity for rapid processing. Although the reason is not clear, the blackness of the developed silver is lost to some extent as the amount of the compound of the present invention used is reduced. Therefore, it is preferable to increase the amount used. The preferred amount used is 2 to 10 g, and particularly 4 to 7 per liter of the developing solution.

The hydroquinone type developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone,
There are 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, hydroquinone monosulfonate and the like, but hydroquinone is particularly preferable.

The hydroquinone type developing agent is usually 0.01
It is used in an amount of mol / liter to 1.5 mol / liter, preferably 0.05 mol / liter to 1.2 mol / liter.

As the sulfite used in the developing solution of the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The sulfite is preferably 0.1 mol / liter or more, particularly preferably 0.3 mol / liter or more. Further, the upper limit is preferably 2.5 mol / liter in the concentrated developer solution.

The pH of the developer used for the developing treatment of the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10-12. The alkaline agent used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

A buffer such as JP-A-62-186259 (borate), JP-A-60-93433 (eg saccharose, acetoxime, 5-sulfosalicylic acid), phosphate, carbonate or the like is used. Good.

In the present invention, the developer preferably contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is
LG Sillen, AE Martell, H "Stabillity Cons
tants of Metal-ion Complexes ", The Chemical Socie
ty, London (1964). S.Chaberek, AE Martell
Written by "Organic Sequestering Agents", Wiley (195
9). It means a commonly known constant such as. In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ). In the present invention, specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include, but are not limited to, the following compounds. That is, ethylenediaminedioltohydroxyphenylacetic acid,
Triethylenetetramine hexaacetic acid, diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1, 3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediamine-N, N, N ', N'tetrakismethylenephosphonic acid, nitrilo-N, N, N- Trimethylenephosphonic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,
Examples thereof include 3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate and sodium hexametaphosphate.

Further, a dialdehyde hardener or a bisulfite adduct thereof may be used in the developer, and specific examples thereof include glutaraldehyde or a bisulfite adduct thereof.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, Organic solvent such as ethanol and methanol: 1-phenyl-5-
Contains antifoggants such as mercapto-based compounds such as mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, and benztriazole-based compounds such as 5-methylbenztotaazole. But well, Re
search Disclosure Volume 176, No. 17643, XXI
(December issue, 1978) and further development accelerators and, if necessary, toning agents, surfactants, defoaming agents, water softeners, amino compounds described in JP-A-56-106244, and the like. May be included.

In the development processing of the present invention, a known silver stain inhibitor such as the compounds described in JP-A-56-24347 can be used in the developer. The developer of the present invention includes
European Patent Publication No. 136528, British Patent No. 958
678, U.S. Pat. No. 3,232,761, JP-A-56-
An amino compound such as alkanolamine described in No. 106244 can be used for the purpose of promoting development, increasing contrast and other purposes. In addition, LFA Mason's "Photographic Processing Chemistry," 226-229, published by Focal Press (1966)
Page, US Pat. Nos. 2,193,015 and 2,592.
No. 364, JP-A-48-64933, etc. may be used.

The fixer is an aqueous solution containing thiosulfate,
It has a pH of 3.8 or higher, preferably 4.2 to 7.0.
Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The use amount of the fixing agent can be appropriately changed and is generally about 0.1 to about 6 mol / liter. The fixer may contain water-soluble aluminum salts which act as hardeners, such as aluminum chloride, aluminum sulphate, potassium alum and the like. Tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more in the fixing solution. These compounds were added in an amount of 0.
It is effective to contain 005 mol or more, especially 0.01 mol /
L-0.03 mol / l is particularly effective.
Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents capable of softening water, and JP-A- The compounds described in JP-A-62-78551 may be included. The fixer may contain iodide ions in order to improve the stability and storability of the silver image.

In the present invention, the "development process time" or "development time" means the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of the developing machine until it is immersed in the next fixing solution. The "fixing time" is the time from the immersion in the fixing tank liquid to the immersion in the next water washing tank liquid (stabilizing liquid), and the "water washing time" is the time of immersion in the washing tank liquid. In addition, "drying time" usually means 35 ° C to 100 ° C for the automatic developing machine.
A drying zone in which hot air of 40 ° C. to 80 ° C. is preferably blown is provided, and it refers to the time in the drying zone. In the development processing of the present invention, the development time is 5 seconds to 1 minute, preferably 5 seconds to 30 seconds, and the development temperature is 25.
C. to 50.degree. C. is preferable, and 25.degree. C. to 40.degree. C. is more preferable. The fixing temperature and time are about 20 ° C. to about 50 ° C. and 5 seconds to 1
Minutes are preferable, and 5 seconds to 30 seconds at 25 ° C to 40 ° C is more preferable. Washing or stabilizing bath temperature and time are preferably 0 to 50 ° C for 5 seconds to 1 minute, and 15 ° C to 40 ° C for 5 seconds to 30 minutes.
Seconds are more preferred.

According to the method of the present invention, the developed, fixed and washed (or stabilized) photographic material is squeezed out of the washing water, that is, dried through a squeeze roller. The drying is carried out at about 40 ° C. to about 100 ° C., and the drying time is appropriately changed depending on the ambient conditions, but it is usually about 5 seconds to 1 minute, and particularly preferably 40 ° C. to 80 ° C. for about 5 seconds. ~ 3
0 seconds.

The light-sensitive material to which the present invention is preferably applied is not particularly limited, and besides general black-and-white light-sensitive materials being mainly applied, it can also be used as, for example, color light-sensitive materials. In particular, photosensitive materials for laser printers and scanners for printing, which record medical images, direct X-ray photosensitive materials for medical use, indirect X-ray photosensitive materials, CRT photosensitive materials,
Photosensitive material for X-ray cinema photography, black and white negative film for photography,
Black-and-white photographic paper and microfilm are available.

In the present invention, a silver halide emulsion (hereinafter referred to as a fine grain emulsion) containing silver halide grains having a sphere-equivalent average grain diameter of 0.5 μm or less or an average grain thickness of 0.
A silver halide photographic light-sensitive material is used in which at least one of silver halide emulsions containing tabular silver halide grains having an average aspect ratio of 25 μm or less (hereinafter referred to as tabular emulsion) is used as a light-sensitive component.

The silver halide grains in the fine grain emulsion may have a regular crystal form such as a cube, an octahedron or a tetrahedron, or an irregular crystal form such as a sphere, a plate or a potato. May be included. It may consist of a mixture of particles of various crystal forms. As the fine grain emulsion of the present invention, an emulsion having a sphere-equivalent mean grain diameter of 5% (projected area) or more, particularly 70% or more of all grains is preferable.

The fine grain emulsion of the present invention may contain iridium ions. To contain iridium ions, it is common to add a water-soluble iridium compound (eg, hexachloroiridium (IV) salt) in the form of an aqueous solution when preparing a silver halide emulsion. It may be added in the form of the same aqueous solution as the halide for grain formation, may be added before grain formation, during grain formation, or after grain formation until chemical sensitization, but is particularly preferable. Is addition at the time of grain formation. The iridium ion is preferably used in an amount of 10 ^-8 to 10 ^-5 mol per mol of silver halide, more preferably 10 ^-7 to 10 ^-6 mol.

For the tabular emulsion of the present invention, RESEAR
CH DISCLOSURE 225 published Item 22534P. 20 ~
P. 58, January issue, 1983, and JP-A-58-12.
No. 7921 and No. 58-113926. The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular emulsions include Cugnac and Chateau.
u) "Progress in the morphology of silver bromide crystals during physical ripening (Evolution of the Morphology of Silver Promide Crystals Dualing Physical Raising)" Science & Industry・ Photography, Vol. 33, No. (1962) pp.
121-125, Duffin, "Photographi emulsi chemistry"
on Chemistry) "Focal Press,
New York, 1966, p. 66-p. 72, A.
P. H. Trivelli, W. F. Smith
Protographic Journal
l), Volume 80, Page 285 (1940) and the like, but JP-A-58-127,921 and JP-A-58-11.
3, 927, JP-A-58-113,928, and U.S. Pat. No. 4,439,520 can be easily prepared. The projected area diameter of the tabular emulsion of the present invention is 0.
It is preferably 3 to 2.0 μm, and particularly preferably 0.5 to 1.2 μm. The distance between parallel planes (particle thickness) is 0.05 μm to 0.25 μm, and particularly 0.1 to 0.25 μm.
It is preferable that the aspect ratio is 3 or more and 20 or more.
It is preferably less than 4, and more preferably 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 3 or more account for 50% or more (projected area) of all grains,
In particular, it is preferable that 70% or more is present, and the average aspect ratio of the tabular grains is 3 or more, particularly 4 to 8. Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. Details of the structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are described in JP-A-63-15161.
Follow the description in 8.

During chemical sensitization during the process of preparing a tabular emulsion as in JP-A-2-68539, it is preferable that 0.5 mmol or more of a silver halide-adsorbing substance be present per mol of silver halide. This silver halide adsorptive substance is
It may be added during grain formation, immediately after grain formation, or before and after the start of post-ripening, but before addition of a chemical sensitizer (for example, gold or sulfur sensitizer), or with a chemical sensitizer. It is preferable to add them at the same time, and it is necessary that they are present at least during the process of chemical sensitization. The silver halide adsorptive substance may be added at any temperature of 30 ° C. to 80 ° C., but at 50 ° C. for the purpose of enhancing the adsorptivity.
The range of -80 ° C is preferred. The pH and pAg may be arbitrary, but at the time of chemical sensitization, the pH is 5 to 10, pAg
It is preferably from 7 to 9. The above-mentioned silver halide-adsorptive substance means a class of sensitizing dyes or photographic performance stabilizers. That is, azoles {for example, benzothiazolium salt, benzimidazolium salt, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc .; mercapto compounds {for example, mercaptothiazoles, Mercapto penzothiazoles, mercapto imidazoles, mercapto benzimidazoles,
Mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazole, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinthione; azaindenes {eg triazaindene , Tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7)
Many compounds known as antifoggants or stabilizers such as tetraazaindenes), pentaazaindenes, etc.) can be mentioned as the silver halide adsorbing material. Further, purines or nucleic acids, or Japanese Examined Patent Publication No. 61-36213, JP-A-59-90844.
Nos., Etc. are also adsorbable substances that can be used. Especially azaindenes and purines,
Nucleic acids are preferred and can be used in the present invention. The amount of these compounds added is 10 to 1 mol of silver halide.
300 mg, preferably 20-200 mg.

The silver halide emulsion of the present invention is preferably of the surface latent image type. The surface latent image type silver halide emulsion is an emulsion containing silver halide which mainly forms a latent image on the surface of silver halide grains. More specifically, the silver halide emulsion is a transparent support. Apply a certain amount on top,
When this was exposed to light for a fixed time of 0.01 to 10 seconds and developed in the following developer A (internal type developer) at 20 ° C. for 6 minutes, the sensitivity measured by a usual photographic density measuring method was A silver halide emulsion, which was coated in the same amount as above and similarly exposed, was added to the following developer B (surface type developer) to prepare a silver halide emulsion 18
It is preferably 1/2 or less, more preferably 1/4 or less, of the sensitivity obtained when developed at 5 ° C. for 5 minutes.

Surface developer B Metol 2.5 g l-Ascorbic acid 10 g NaBO ₂ .4H ₂ O 35 g KBr 1 g Water was added to 1 liter

Internal developer A Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water was added to 1 liter

The silver halide composition of the silver halide emulsion used in the present invention is, for example, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, chlorine, bromine and / or A silver halide composed of an iodide, and in the case of silver iodobromide or silver chloroiodobromide, the silver iodide content is 0 to 3 mol%, preferably 0 to 1 mol%, and the silver chloride content is 0 to 50 mol%. Mol%, preferably 0
It is 30 mol%. In the case of silver chlorobromide, the silver chloride content is 0 to 98 mol%, preferably 20 to 95 mol%.

When a monodisperse emulsion is used as an emulsion in the practice of the present invention, the rate of addition of the aqueous silver nitrate solution and the water-soluble halide should be increased in the preparation of the monodisperse emulsion as the silver halide grains grow. it can. By increasing the addition rate, the particle size distribution can be made more monodisperse, and the addition time can be shortened, which is advantageous for industrial production. Further, it is also preferable in that the chance of structural defects being formed inside the silver halide grain is reduced.

As a method for accelerating this addition rate, as described in JP-B-48-36890, JP-A-52-16364 and JP-A-55-142329, the addition rate of an aqueous silver salt solution and an aqueous halide solution is added. May be increased continuously or stepwise. The upper limit of the addition rate may be a flow rate just before the generation of new grains, and the values thereof include temperature, pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, distance between grains, or It depends on the type and concentration of protective colloid. A method for producing a monodisperse emulsion is known, for example, J. Phot. Sci. 12, 242-251.
(1963), JP-B-48-36890, 52-1.
6364 and JP-A-55-142329, and the technology described in JP-A-57-179835 can be employed. The silver halide emulsion used in the present invention may be a core / shell type monodisperse emulsion, and these core / shell emulsions are disclosed in JP-A-54-4.
It is known from No. 8521 and the like.

When a polydisperse emulsion is used as an emulsion in the practice of the present invention, a known method can be used for producing the polydisperse emulsion. Take TH James “The Theor”
y of the Photographic Process ”, 4th edition, published by Macmillan (1977), pages 38-104, etc., neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled Double jet method,
It can be manufactured by applying a method such as a conversion method or a core / shell method.

The amount of silver coated on the silver halide photographic light-sensitive material of the present invention is preferably 5 g or less, particularly 1 to 3 g, per one side of the support.
Is.

The emulsion of the present invention is preferably a monodisperse emulsion. The monodisperse emulsion according to the present invention has a coefficient of variation S / average r of 0.25 concerning the grain size of silver halide grains.
It is an emulsion having the following grain size distribution. Here, the average r is the average particle size, and S is the standard deviation regarding the particle size. That is,
When the grain size of each emulsion grain is ri and its number is ni, the average grain size average r is

[0041]

[Equation 1]

And its standard deviation S is

[0043]

[Equation 2]

Is defined as The term "individual grain size" as used in this definition refers to a silver halide emulsion as "The Theory of the Photogrp process" by TH James et al.
aphic Process) 3rd edition, pp. 36-43, published by Macmillan, Inc. (1966), the area projected when microscopically photographed by methods well known in the art (usually electron microscopy). Is the diameter equivalent to the projected area. Here, the projected equivalent diameter of a silver halide grain is defined by the diameter of a circle which is equal to the projected area of a silver halide grain as described in the above-mentioned book. Therefore, even when the shape of the silver halide grains is other than spherical (eg, cubic, octahedral, tetradecahedral, tabular, potato-like), the average grain size average r and its deviation S can be obtained as described above. Is. The variation coefficient relating to the grain size of the silver halide grains is 0.25 or less, preferably 0.20 or less, more preferably 0.15 or less.

In the silver halide emulsion of the present invention, as a spectral sensitization, at least one of tricarbocyanine dyes and / or 4-quinoline nucleus-containing dicarbocyanine dyes described in JP-A-63-89838 is used. One or a cyanine dye, a merocyanine dye or a mixture thereof can be used. The above-mentioned spectral sensitizing dye used in the present invention is contained in the silver halide photographic emulsion in a ratio of 10 ^-7 to 10 ^-2 mol, preferably 10 ^-6 to 10 ^-3 mol per mol of silver halide. ..

The spectral sensitizing dyes used in the present invention can be directly dispersed in the emulsion. Further, these are first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and can be added to the emulsion in the form of a solution. The dye is usually added after chemical sensitization in many cases, but it may be added during grain formation or before chemical sensitization. Ultrasonic waves can also be used for dissolution. The method described in US Pat. Nos. 2,912,343, 3,342,605, 2,996,287, and 3,429,935, etc. can be used for addition to the emulsion. .. The above-mentioned spectral sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but as described above, it may be dispersed at any stage of preparation in the silver halide emulsion. can do.

Furthermore, other sensitizing dyes can be used in the present invention. For example, US Pat. No. 3,703,
No. 377, No. 2,688,545, No. 3,39
No. 7,060, No. 3,615, 635, No. 3,6
28,964, British Patent Nos. 1,242,588, 1,293,862, Japanese Patent Publication Nos. 43-4936, 44-14030, 43-10773, and U.S. Patent No. 3,416. 927, Japanese Examined Patent Publication No. 43-4930, and U.S. Pat. Nos. 3,615,613 and 3,615,63.
No. 2, No. 3,617,295, No. 3,635,7
The spectral sensitizing dyes described in No. 21 and the like may be used, and the infrared sensitizing dyes and these spectral sensitizing dyes may be used in combination.

In the present invention, the compounds described in JP-A-63-89838 can be used together with the above-mentioned sensitizing dye for the purpose of further enhancing the supersensitizing effect. Furthermore, together with the above-mentioned sensitizing dye, JP-A-63-89838
A combination of preservative modifiers such as those described in US Pat. No. 4,096,839 can be used in an amount of about 0.01 to 5 g per mole of silver halide in the emulsion. The supersensitizer used in the present invention or the storage stability may be directly dispersed in the emulsion, and a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or It is also possible to dissolve them in a mixed solvent containing a plurality of these solvents and add them to the emulsion. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. The supersensitizer and storage stability improver may be added to the emulsion before or after the addition of the spectral sensitizing dye described above. Further, these may be dissolved separately from the spectral sensitizing dye, and these may be separately added to the emulsion at the same time, or may be mixed and then added to the emulsion.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, a coating aid, an antistatic agent, a slip property improving agent, an emulsifying dispersion agent, an adhesion preventing agent and a photographic characteristic improving agent (for example, development acceleration, high contrast). Various surfactants may be included for various purposes such as sensitization and sensitization). As the antistatic agent, especially US Pat. No. 4,201,586, JP-A-60
-80,849, 59-74,554, Japanese Patent Application No. 6
0-249,021 and 61-32,462, the fluorine-containing surfactants or polymers described in JP-A-60-7.
No. 6,742, No. 60-80846, No. 60-808
No. 48, No. 60-80, 839, No. 60-76, 74
1, No. 60-58-208, 743, Japanese Patent Application No. 61-1
3,398, 61-16,056, 61-3
No. 2,462, and the like, or quinion-based surfactants, or JP-A-57-204,540,
A conductive polymer or latex (nonionic, anionic, cationic, amphoteric) described in Japanese Patent Application No. 61-32,462 can be preferably used. As the inorganic antistatic agent, conductive tin oxide, zinc oxide described in JP-A-57-118242 or the like, or a complex oxide doped with antimony or the like described in these metal oxides can be preferably used.

As the hardener used in the present invention, mucochloric acid, mucobromic acid, mucophenoxycycloric acid, mucophenoxybromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, monomethylglyoxal, 2,3-dihydroxy-1. , 4
-Dioxane, 2,3-dihydroxy-5-methyl-
Aldehyde compounds such as 1,4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 1, 3,5-triacryloyl-hexahydro-s-triazine, 1,
3,5-trivinylsulfonyl-hexahydro-s-
Active vinyl compounds such as triazine bis (vinylsulfonylmethyl) ether and 1,3-bis (vinylsulfonylmethyl) propanol-2-bis (α-vinylsulfonylacetamido) ethane; 2,4-dichloro-6-hydroxy-s -Triazine sodium salt,
2,4-dichloro-6-methoxy-s-triazine,
2,4-dichloro-6- (4-sulfolinino) -s-
Triazine sodium salt, 2,4-dichloro-6-
(2-Sulfoethylamino) -s-triazine, N,
Active halogen compounds such as N'-bis (2-chloroethylcarbamyl) piperazine; bis (2,3-epoxypropyl) methylpropylammonium p-toluenesulfonate, 1,4-bis (2 ', 3) ′ -Epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ-
Epoxy compounds such as acetoxy-β-oxypropyl) isocyanate; 2,4,6-triethyleneimino-s-triazine, 1,6-hexamethylene-N, N '
-Ethyleneimine compounds such as bisethyleneurea and bis-β-ethyleneiminoethylthioether; 1,2-
Methanesulfonic acid ester compounds such as di (methanesulfonoxy) ethane, 1,4-di (methanesulfonoxy) butane, and 1,5-di (methanesulfonoxy) pentane; carbodiimide compounds; isoxazole compounds And an inorganic compound such as chrome alum.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101 and 2,701,245,
Nos. 4,142,894 and 4,396,706, homopolymers of polymethylmethacrylate or polymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide and sulfuric acid. Fine particles of an inorganic compound such as strontium and barium can be used. Particle size is 1-10μ
m, and particularly preferably 2 to 5 μm.

Silicone compounds described in US Pat. Nos. 3,489,576 and 4,047,958 are used as slip agents for the surface element of the photographic light-sensitive material used in the present invention.
In addition to the colloidal silica described in JP-B-56-23,139, paraffin wax, higher fatty acid ester, starch derivative and the like can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer of the photographic light-sensitive material used in the present invention. The hydrophilic colloid layer of the photographic light-sensitive material used in the present invention may contain a polymer latex for the purpose of improving pressure resistance. Examples of the polymer include a homopolymer of an alkyl ester of acrylic acid, a copolymer with acrylic acid, a styrene-butadiene copolymer, and a polymer or copolymer including a monomer having an active methylene group.

In the silver halide photographic emulsion layer, intermediate layer, protective layer, antihalation layer, back layer and the like used in the present invention, in addition to gelatin as a binder, acylated gelatin such as phthalated gelatin and malonated gelatin; Cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; soluble starch such as dextrin; hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid can be added. Of these, it is preferable to use dextran and polyacrylamide together with gelatin.

The silver halide photographic light-sensitive material used in the present invention may have a non-light-sensitive layer such as a surface protective layer, an intermediate layer, an antihalation layer and a back layer in addition to the light-sensitive silver halide emulsion layer. .. The number of silver halide emulsion layers may be two or more, and the sensitivity, gradation and the like of the two or more silver halide emulsions may be different. Further, it may have one or more silver halide emulsion layers or a non-photosensitive layer on both sides of the support.

The support is preferably a polyethylene terephthalate film or a cellulose triacetate film, and particularly preferably colored blue. In order to improve the adhesion of the support to the hydrophilic colloid layer,
It is preferable that the surface is subjected to corona discharge treatment, glow discharge treatment or ultraviolet irradiation treatment. Alternatively,
An undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex or the like may be provided, or a gelatin layer may be provided thereon. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrophilic colloid layer can be further improved.

The antihalation dye and / or antiirradiation dye used in the present invention is 750
A dye having substantial absorption at a long wavelength of nm or longer is used. Here, the antihalation dye is used in an intermediate layer, an undercoat layer, an antihalation layer, a back layer, an emulsion layer and the like, and the anti-irradiation dye is used in an intermediate layer and the like in addition to the emulsion layer. Further, these dyes are preferably 1
It is used in an addition amount of 0 ^{-3 to 1} g / m ^2, more preferably 10 ^{-3 to} 0.5 g / m ² . For example, US Pat. No. 2,895,
No. 955, No. 3,177,078, No. 4,851,3
25, the dyes described in JP-A Nos. 50-100 and 116, and JP-A-63-23148 and 63-8983.
The dyes described in No. 8 are preferably used. These dyes may be used alone or in combination of two or more. Further, instead of the above-mentioned dyes, these dyes may be used in combination with other dyes. Examples of dyes used instead or in combination include pyrazolone oxonol dyes described in US Pat. No. 2,274,782, diarylazo dyes described in US Pat. No. 2,956,879, and US Pat. 3,423,207
No. 3,384,487, styryl dyes and butadienyl dyes, US Pat. No. 2,527,583, merocyanine dyes, US Pat. No. 3,486,89.
No. 7, No. 3,652,284, No. 3,718,4
No. 72 merocyanine dye and oxonol dye,
The enaminohemioxonol dyes described in U.S. Pat. No. 3,976,661 can be used.

[0058]

The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. Example 1

1. Preparation of silver halide emulsion 40 g of gelatin was dissolved in 1 liter of water, and each was heated at 53 ° C. for 6 hours.
6 g of sodium chloride in a container heated to 3 ° C and 70 ° C,
0.4 g of potassium bromide and compound [I]

[0060]

[Chemical 6]

After 60 mg of was added, 600 ml of an aqueous solution containing 100 g of silver nitrate and 600 ml of an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride were added by the double jet method to form a core portion of 20 mol% silver chloride. ,
Thereafter, 500 ml of an aqueous solution containing 100 g of silver nitrate and 500 ml of an aqueous solution containing 40 g of potassium bromide, 14 g of sodium chloride, and potassium hexachloroiridium (III) (10 ⁻⁷ mol / mol silver) were added by the double jet method, So-called core / shell type cubic monodispersed silver chlorobromide grains having different average grain sizes were prepared by forming a shell portion of 40 mol% of silver chloride. The average size of the particles obtained is summarized in Table 1.

[0062]

[Table 1]

40 g of gelatin after desalting each emulsion
Was added to adjust the pH to 6.0 and pAg to 8.5, and 2 mg of triethylthiourea, 4 mg of chloroauric acid and 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene 0.
2 g was added and chemically sensitized at 60 ° C.

2. Preparation of emulsion coating solution A container in which 850 g of each emulsion was weighed was heated to 40 ° C, and additives were added by the method described below to prepare an emulsion coating solution.

(Formulation of Emulsion Coating Solution) a. Emulsion 850 g b. Spectral sensitizing dye [II] 1.2 × 10 ⁻⁴ mol c. Supersensitizer [III] 0.8 × 10 ⁻³ mol d. Shelf life improver [IV] 1 × 10 ⁻³ Morpho. Polyacrylamide (molecular weight 40,000) 7.5 g f. Trimethylolpropane 1.6 g. Polystyrene sulfonate Na 2.4 g h. Poly (ethyl acrylate / methacrylic acid) latex 16 g Re. N, N'-ethylenebis- (vinyl sulfone acetamide) 1.2 g Spectral sensitizing dye [II]

[0066]

[Chemical 7]

Supersensitizer [III]

[0068]

[Chemical 8]

Preservation improver [IV]

[0070]

[Chemical 9]

3. Preparation of Surface Protective Layer Coating Solution for Emulsion Layer The container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution.

(Formulation of Coating Solution for Surface Protection Layer of Emulsion Layer) a. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 10 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. N, N'-ethylenebis- (vinyl sulfone acetamide) 1.5 g e. 2.2 g of polymethylmethacrylate fine particles (average particle size 2.0 μm) f. Sodium t-octylphenoxyethoxyethane sulfonate 1.2 g. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 2.7 g Chi. Sodium polyacrylate 4 g Re. C ₈ F ₁₇ SO ₃ K 70 mg Nu. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 70 mg. 4 ml of NaOH (1N). 60 ml of methanol

4. Preparation of Back Layer Coating Liquid A container was heated to 40 ° C., and additives were added according to the formulation shown below to prepare a back layer coating liquid. (Back layer coating liquid formulation) a. Gelatin 80 g b. Dye [V] 3.1 g c. Polystyrene sodium sulfonate 0.6 g d. Poly (ethyl acrylate / methacrylic acid) latex 15 g e. N, N'-ethylenebis- (vinyl sulfone acetamide) 4.3 g Dye [V]

[0074]

[Chemical 10]

5. Preparation of Back Surface Protective Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating liquid. (Prescription of back surface protective layer coating solution) a. Gelatin 80 g b. Polystyrene sodium sulfonate 0.3 g c. N, N'-ethylenebis- (vinyl sulfone acetamide) 1.7 g d. Polymethylmethacrylate fine particles (average particle size 4.0 μm) 4 g e. t-octylphenoxyethoxyethanesulfonic acid sodium salt 3.6 g f. 6 ml of NaOH (1N). Sodium polyacrylate 2 g H. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.6 g Li. C ₈ F ₁₇ SO ₃ K 50 mg Nu. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 50 mg. 130 ml of methanol

6. Preparation of coating sample The coating solution for the back layer described above was coated together with the coating solution for the surface protective layer of the back layer on the side of the polyethylene terephthalate support so that the total coating amount of gelatin was 3 g / m ² . Following this, the emulsion coating liquid and the surface protective layer coating liquid described above were applied to the opposite side of the support at a coating Ag amount of 2.5 g / m ² and a gelatin coating amount of the surface protective layer of 1 g / m ^2. Was applied so that Thus, coated samples 1 to 3 were obtained.

7. Developer composition (A) Potassium hydroxide 24 g Sodium sulfite 40 g Potassium sulfite 50 g Diethylenetriaminepentaacetic acid 2.4 g Boric acid 10 g Hydroquinone 35 g Diethylene glycol 50 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 5-methyl Benzotriazole 60 mg Potassium bromide 3 g Acetic acid 1.8 g 2,3,5,6,7,8-Hexahydro-2-thioxo-4 (1H) quinazolinone 0.18 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.28 g Add water to adjust upto 1000 ml pH 10.5 Developer composition (B) Composition of developer composition (A) in which 4-hydroxymethyl-4-methyl-1-phenyl-3pyrazolidone was changed to 6 g.

8. Fixer composition Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 25 mg Sodium hydroxide 6 g Potassium iodide 0.5 g Water was added to adjust upto 1000 ml pH 5.10.

Next, a sample was prepared by adding 1 mmol of the compound 1.20 of the present invention to 1 liter of each of the developing solutions (A) and (B) described above. As a comparative example, a sample containing no compound of the present invention was prepared. Automatic machine is FPM
-2000 (manufactured by Fuji Photo Film Co., Ltd.) was modified, and a developing process was carried out by a 30 second process (Dry to Dry) using the above-mentioned coated sample. The coated sample was kept at 25 ° C. and 60% temperature and humidity, left for 7 days after coating, and subjected to scanning exposure for 10 ⁻⁷ seconds using a semiconductor laser of 780 nm at room temperature. The developing temperature was 35 ° C., the fixing temperature was 32 ° C., and the replenishment amount was 25 ml per B4 size for both the developing solution and the fixing solution. The number of processed sheets was 600 sheets of B4 size for each developer. Table 2 shows the results of the photographic properties, the color tone of the image silver, and the fixability. The fog value in the photographic properties was measured as a net increase in density with the base density corrected. The gradation G bar is represented by the slope of a straight line connecting the density point of fog +0.25 and the density point of fog +2.00. The sensitivity was obtained as a relative value of the reciprocal of the exposure amount required to obtain a blackened density of fog + 1.0. Dm represents the maximum density.

[0080]

[Table 2]

From the results of Table 2, the following can be said. Exam N
o.1 to 6 (average particle size 0.75μ), the color tone of the developed silver image is not a problem, but the G bar and Dm are low in terms of photographic properties, and improper fixing occurs. Absent. Test No. 7-12 (Average particle size 0.5
Even if it is 5 μ), fixing failure occurs and it is not at a usable level. On the other hand, in Test Nos. 17 to 18 (average particle size: 0.35 μ) of the present invention, the photographic properties are at a level that can be sufficiently satisfied, and the color tone and fixability of the developed silver image are satisfactory and practically usable. I got the result.

Example 2 1. Preparation of tabular grains 4.5 g of potassium bromide and 2 g of gelatin in 1 liter of water.
0.6 g, 5 of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and stirred in a container kept at 60 ° C. while stirring 37 cc aqueous solution of silver nitrate (3.43 g of silver nitrate), 33 cc of aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide by the daffle jet method. For 37 seconds. Next, an aqueous solution containing 0.9 g of potassium bromide was added, and the temperature was raised to 70 ° C. to 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at that temperature, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method over 35 minutes. The thickness of the grains was changed by changing the growth potential at this time. Next, 10 cc of a 2N potassium thiocyanate solution and 0.10 mol% of AgI fine particles having a diameter of 0.07 μm were added with respect to the total amount of silver. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, tabular grains having a total silver iodide content of 0.3 mol% were obtained. The average projected area diameter and thickness of the obtained grains are summarized in Table 3.

[0083]

[Table 3]

After that, soluble salts were removed by a precipitation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 and pAg was adjusted to 8.25 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 500 mg of a sensitizing dye were added. Further, 0.83 g of calcium chloride was added. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T-1 to T-3 was completed.

[0085]

[Chemical 11]

2. Preparation of coating sample The following chemicals were added to 1 mol of silver halide of T-1 to T-3 to prepare a coating liquid.・ 2,6-bis (hydroxyamino) -4-diethylamino 1,3,5-triazine 72 mg ・ Gelatin The total coating amount with gelatin used in the surface protective layer described later was 2. Prepared to be 4 g / m ²・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1,2-bis (Vinylsulfonylacetamide) ethane Adjust the amount added so that the swelling rate will be 230%.

[0087]

[Chemical formula 12]

3. Preparation of Surface Protective Layer Coating Liquid The surface protective layer was prepared and prepared so that each component had the following coating amount. Contents coating weight Gelatin 0.966 g / m ² · sodium polyacrylate surface protective layer (average molecular weight 400,000) 0.023 - 4-hydroxy-6-methyl-1,3,3a, 7 - tetrazaindene 0 .015

[0089]

[Chemical 13]

Polymethylmethacrylate (average particle size 3.7 μm) 0.087 Proxel (adjusted to pH 7.4 with NaOH) 0.0005

4. Preparation of Support (1) Preparation of Dye for Undercoat Layer The following dyes were ball milled by the method described in JP-A-63-197943.

[0092]

[Chemical 14]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
00 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observation of the obtained dye dispersion revealed that the crushed dye had a wide range of particle diameters from 0.05 to 1.15 μm, and the average particle diameter was 0.37 μm. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. A dye dispersion was thus obtained.

(2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoat liquid having the following composition was applied at an amount of 5.1 cc / m ² . Was applied by a wire bar coater so as to obtain the above, and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained 0.04 wt% of the dye having the following structure.

[0095]

[Chemical 15]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc Distillation Water 900.5cc

[0097]

[Chemical 16]

A second undercoat layer having the following composition was coated on each of the above-mentioned first undercoat layers one by one so that the coating amount would be the amount described below, and 150 on each side by a wire bar coater system. Coated and dried at ℃.・ Gelatin 160 mg / m ²・ Dye dispersion (26 mg / m ² as a solid dye component)

[0099]

[Chemical 17]

Matting agent Polymethyl methacrylate having an average particle size of 2.5 μm 2.5 mg / m ²

5. Preparation of photographic material On the prepared support, the above emulsion layer and surface protective layer were coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . The amount of coated gelatin and the swelling ratio obtained by the freeze-drying method using liquid nitrogen were adjusted to 230% by adjusting the amount of gelatin added to the emulsion layer and the amount of hardener. Thus, photographic materials 1 to 3 were obtained.

6. Preparation of developer (A) Diethylenetriaminepentaacetic acid 2g Potassium hydroxide 29.1g Potassium sulfite 44.2g Sodium hydrogen carbonate 7.5g Boric acid 1g Hydroquinone 30g Diethylene glycol 12g 5-Methylbenzotriazole 20mg Potassium bromide 1.5g Tri Ethylene glycol 20 g Glacial acetic acid 4 g 5-Nitroindazole 0.25 g 4-Hydroxymethyl-4-methyl-1-phenyl 1.5 g-3-Pyrazolidone Glutaraldehyde (50 wt%) 10 g Sodium metabisulfite 12.6 g Water was added. Upto 1000ml pH adjusted to 10.50

Developer (B) 4-hydroxymethyl-4-methyl-1 of developer (A)
-Phenyl-3-pyrazolidone was changed to 6g Starter Glacial acetic acid 150g Potassium bromide 300g Water was added to make 1.5 liters Developers (A) and (B) as development replenishers. 20 ml of the starter was added to 1 liter of the replenisher. This solution is the developing solution.

A sample was prepared by adding 1 mmol of the compound 1 of the present invention to 1 liter of this developing solution. Next, using the above-mentioned photographic materials 1 to 3, the green light of 500 to 600 .mu.m having an intensity peak at 545 .mu.m is used to perform exposure through a continuous wedge or uniform exposure.
A 30 second treatment (Dry to Dry) was performed with M-9000 (manufactured by Fuji Photo Film Co., Ltd.). The developing temperature is 35 ° C, the fixing temperature is 32 ° C, and the replenishment amount is 2 pieces of developer per 1 sheet of quarter size.
5 ml and 25 ml of fixer. In addition, it is Fuji F for fixation
(Manufactured by Fuji Photo Film Co., Ltd.) was used. Table 4 shows the results of color tone and fixability of photographic and image silver.

[0105]

[Table 4]

The following can be said from Table 4. Testing of the invention
By using No. 8 and No. 12, the photographic properties, the color tone of the developed silver image, and the fixing property became practically sufficient levels, and ultra-rapid processing became possible.

[0107]

According to the present invention, the blackness of the silver image in the ultra-rapid development process is improved and a high quality image can be obtained. Further, there was almost no adverse effect on the photographic property and fixing property, and favorable performance was obtained for speeding up the processing.

Claims (2)

[Claims] 1. A silver halide emulsion containing silver halide grains having a silver sphere-equivalent average grain diameter of 0.5 μ or less, or a tabular halogen having an average grain thickness of 0.25 μ or less and an average aspect ratio of 3 or more. Processing a silver halide photographic light-sensitive material using at least one kind of silver halide emulsion containing silver halide grains with a developing solution containing a nitrogen-containing heterocyclic mercapto compound and a compound represented by the following general formula (1). And a development processing method. General formula (1) (In the formula, R represents an aryl group. R ₁ , R ₂ , R ₃ ,
R _{4 s} may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
However, when R represents an unsubstituted phenyl group, R ₁ ,
R ₂ , R ₃ and R ₄ are not hydrogen atoms at the same time. ) 2. The development processing method according to claim 1, wherein the compound represented by the general formula (1) is contained in an amount of 2 g or more per liter of the developing solution.