JPH0922079A - Silver halide photographic sensitive material and developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material which exhibits high covering power and excellent properties against roller mark fog and residual colors and can be used for a ultrafast processing. SOLUTION: This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on a supporting body. The coating amt. of a hydrophilic colloid on the surface where the silver halide emulsion layer is formed is 1.5-3.0g/m<2> . Within two minutes after the swelling rate of the material on the surface where the silver halide emulsion layer is formed reaches the max., the swelling thickness is decreased to <=50% and >=20% of the max. swelling thickness. Also, the photosensitive material contains such silver halide particles that have >=20 aspect ratio and >=10mol% average silver chloride content and that spectral sensitizing dyes are adsorbed to the particle surface by >=60% and <=100% of the saturation adsorption amt.

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, and more particularly to a super-quick silver halide light-sensitive material having high covering power, excellent pressure in liquid and excellent residual color.

[0002]

2. Description of the Related Art Recently, in the field of medical X-ray photographic light-sensitive materials, development processing has been accelerated and processing time has been greatly shortened. As a result, it is required that the added sensitizing dyes, dyes, etc. efficiently escape from the light-sensitive material in the process of processing, and those colors do not remain and that the color tone of the formed silver image is cold black tone. ing. On the other hand, when tabular silver halide grains having an aspect ratio of 8 or more as described in JP-A Nos. 58-113926, 58-113927 and 58-113928 are used, the color sensitization efficiency is improved. It is known that it is effective in reducing the amount of the sensitizing dye and reducing the color residue because it can be increased. However, even with tabular silver halide, which is particularly advantageous in terms of residual color, there is a problem in that the developed silver tone is yellowish and roller mark fog is likely to occur during development processing. By increasing the hardness, roller mark fog is improved, but conversely color remains and CP (covering power)
Will deteriorate. The color residue is not limited to tabular silver halide and is a problem that frequently occurs when the processing time is shortened.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide light-sensitive material which has a high CP and is excellent in roller mark fog and residual color and which can be processed very quickly.

[0004]

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

1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the total gelatin coating amount on the side having the silver halide emulsion layer is 1.5 to 3.0 g / m ^2, which is ² after the swelling degree on the side having the silver halide emulsion layer becomes maximum.
Within a minute, the swelling thickness is reduced to 50% or less and 20% or more of the maximum swelling thickness, and the spectral sensitizing dye is adsorbed on the particle surface in an amount of 60% or more and 100% or less of the saturated adsorption amount. A silver halide photographic light-sensitive material comprising silver halide grains having a silver chloride content of 10 mol% or more.

2) The silver halide photographic light-sensitive material as described in 1 above, wherein colloidal silica is contained in the silver halide emulsion layer.

3) A development processing method characterized in that the silver halide photographic light-sensitive material described in 1 or 2 above is developed in a total processing time of 30 seconds or less.

The present invention will be described in more detail. In the present invention, the coating amount of total gelatin on the side having the silver halide emulsion layer is 1.5 to 3.0 g / m ² , but 1.8 to ² .
6 g / m ² is preferred. If the total gelatin coating amount is higher than this, the covering power is reduced. On the other hand, if it is less than this range, roller mark fog increases.

The swelling degree of the silver halide photographic light-sensitive material of the present invention on the side having the silver halide emulsion layer is 50% of the maximum swelling thickness within 2 minutes after the maximum swelling degree.
% Or less 20% or more. More preferably, the swelling thickness is reduced to 45% or less and 30% or more of the maximum swelling thickness within 2 minutes after the maximum swelling degree is reached. In the present invention, the swelling thickness means 25 ° C. on a silver halide photographic light-sensitive material that has been allowed to stand.
The amount of increase in the film thickness when the swelled thickness swollen with water at 25 ° C. was measured (the amount of increase in the film thickness measured before and after the addition of distilled water). Further, the maximum swelling thickness is a value of the swelling thickness when the swelling film becomes maximum for the first time after dropping. The film thickness is continuously measured at intervals of 5 seconds or less from the beginning of dropping.

One means for adjusting the degree of swelling of the present invention can be achieved by adjusting the amount of water-soluble polymer added and the amount of hardener added. At that time, the water-soluble polymer preferably has a molecular weight of 1,000 to 50,000. The water-soluble polymer is a polymer that is dissolved in 100 g of water at 20 ° C. in an amount of 0.05 g or more.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has tabular silver halide grains having an average silver chloride content of 10 mol% or more, preferably 20 mol% or more and an average aspect ratio of 2 or more. And silver bromochloride, silver iodobromochloride emulsion or silver chloride emulsion. The halogenated grains may be of any crystal type as long as they have the constitution of the present invention, and may be, for example, a single crystal such as a cube, an octahedron, or a tetrahedron, and have various shapes. It may be crystalline particles.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (1
(Dec. 1978), pp. 22-23, "Emulsion".
Preparation and Types ”, or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, T.W. H. James "The The
Theory of the Photographi
C. Process "4th edition, published by Macmillan (1977), pages 38-104, GF.
Duffin's "Photographic Emul"
"Sion Chemistry" Focal Pres
s company (1966), P. "C by Glafkides
himie et Physique Photogr
aphique "Paul Montel company published (196
7 years) or V. L. Zelikman et al., "Makin"
g And Coating Photographi
c Emulsion "Focal Press, Inc. (1964) and the like.

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The term "monodisperse" as used herein means that when the average grain diameter is measured by a conventional method, at least 95% of the grains in number or weight are within ± 40%, preferably within ± 30% of the average grain size. It is a particle.

The crystal structure of silver halide may have a silver halide composition in which the inside and the outside are different. For example, it is clear that the core portion of high silver iodide is coated with a shell layer of low silver iodide. It may be a core / shell type monodisperse emulsion having a layer structure.

The method for producing the above-mentioned monodisperse emulsion is known, and is described in, for example, J. Photo. Sci, 12.242-251, (19
63), JP-A-48-36890, and JP-A-52-1636.
No. 4, No. 55-142329, No. 58-49938
No. 1,413,748, U.S. Pat.
No. 4,628, 3,655,394 and the like.

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, as a method for obtaining the above monodisperse emulsion, for example, a seed crystal is used, and this seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion may be used.

The method for producing the above core / shell type emulsion is known, and is described in, for example, J. Photo. Sci, 24.198. (1
976), U.S. Pat. Nos. 2,592,250 and 3,50
5,068, 4,210,450, 4,44
4,877 or JP-A-60-143331 can be referred to.

The tabular grains according to the present invention are said to have improved spectral sensitization efficiency and improved graininess and sharpness of images. For example, British Patent 2,112,157 and US Pat. No. 4,434,226 and the like, and the emulsion can be prepared by referring to the methods described in these publications.

Preferred tabular grains of the emulsion according to the present invention have an aspect ratio of 2 or more and 10 or less, more preferably 3 or more and 8 or less.

Emulsion grains having an aspect ratio of 2 or less have a circle equivalent spherical diameter of 0.8 to 2.0 μm, and more preferably 1.0 to 2.0 μm.
1.5 μm. Further, the thickness of the particles is preferably 0.8 μm or less, more preferably 1.0 μm or less.

The equivalent spherical diameter of emulsion grains having an aspect ratio of 2 or more is 0.1 to 1.5 μm, and more preferably 0.2 to.
1.0 μm. Further, the thickness of the particles is preferably 0.8 μm or less, more preferably 0.5 μm or less.

For chemical sensitization, usual sulfur sensitization, reduction sensitization, noble metal sensitization and combinations thereof are used. Further specific chemical sensitizers are allylthiocarbamide, thiourea, thiosulfate, Examples thereof include sulfur sensitizers such as thioether and cystine, precious metals such as palladium, and reduction sensitizers such as tin chloride and phenylhydrazine.

The colloidal silica according to the present invention is added and contained in the photosensitive silver halide emulsion layer of the silver halide photographic light-sensitive material according to the present invention.

The colloidal silica has an average particle size of 5 to 5000 μm, preferably 10 to 1000 μm,
The main component is silicon dioxide, and may include an aluminate as a minor component. Examples of the aluminate include sodium aluminate and potassium aluminate.
These colloidal silica may contain, as a stabilizer, inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium ion.

Specific examples of the colloidal silica include, for example, E.I. I. Du Pont de Nemours &
Co. Ludox AM, Ludox from (USA)
AS, Ludox LS, Ludox ™, Lud
ox HS and other product names such as Snowtex 20, Snowtex 30, Snowtex C, and Snowtex O from Nissan Chemical Co., Ltd.
(USA) System C-30, System
Trade name such as 200, Nalco Chem. C
o. To Nalcoag-1060, Nalcoag-
It is commercially available under trade names such as ID21 to ID64, and these are easily available.

The amount of the above colloidal silica added to the emulsion according to the present invention is based on the amount of gelatin in the emulsion layer.
The dry weight ratio may be 0.01 to 2.0%, more preferably 0.1 to 1.0%. At the time of addition, an emulsion layer appropriately diluted with water or a hydrophilic solvent may be added,
The timing of addition to the emulsion is not particularly limited, but it is preferably added at an arbitrary step after coating after the chemical ripening and before coating.

In the present invention, 60% or more 10
The fact that the spectral sensitizing dye is adsorbed at 0% or less means that the amount of adsorbing the dye is 60% or more and 100% or less with respect to the saturated adsorption amount of the spectral sensitizing dye on the silver halide grain. Specifically, it means that the amount of the spectral sensitizing dye added to the saturated adsorption amount is 60% or more and 100% or less. It is preferably 70 to 80%. The amount of dye adsorbed can be determined by a method of centrifuging an emulsion adsorbing a dye to precipitate silver halide grains and colorimetrically determining the dye concentration of the solution.

Examples of the spectral sensitizing dye that can be adsorbed on the silver halide grains of the present invention include cyanine, carbocyanine, dicarbocyanine, complex cyanine, hemicyanine, styryl dye, merocyanine, complex merocyanine, and holopolar dye. The spectral sensitizing dyes used in 1. can be used alone or in combination.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of nuclei usually used for cyanine dyes can be used as the basic heterocyclic nucleus. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus And a quinoline nucleus. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, and a thiazolidine-2,4 are used.
-5- to 6-membered heterocyclic nuclei such as dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination. In particular, combinations of sensitizing dyes are often used for supersensitization.

To incorporate these sensitizing dyes in the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl cellosolve, 2,2,3,3. -It may be added to the emulsion by dissolving it in a solvent such as tetrafluoropropanol alone or in a mixed solvent. Further, as described in JP-B-44-23389, JP-B-44-27555, JP-B-57-22089, etc., an acid or a base is allowed to coexist to form an aqueous solution, or US Pat. No. 3,822,135 and US Pat. 4,000
An aqueous solution or colloidal dispersion prepared by coexisting a surfactant such as sodium dodecylbenzenesulfonate as described in No. 6,025 may be added to the emulsion.
Alternatively, the emulsion may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol and then dispersed in water or a hydrophilic colloid to add to the emulsion. JP-A-53-102733
And JP-A-58-105141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion.

When these compounds are added to the emulsion, a mixture may be added or they may be added separately.

A hydrophilic colloid can be used as a binder in the silver halide emulsion of the present invention. Examples of the colloid used for this purpose include gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins such as polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, and other hydrophilic colloids generally used in the field of photography. .

The silver halide photographic light-sensitive material of the present invention may contain a latex. Normal latex is dispersed in water by a surfactant, but the latex is preferably dispersed and stabilized by gelatin bonded to a polymer latex. The polymer constituting the latex and the gelatin may have some kind of bond. In this case, the polymer and gelatin may be directly bonded, or may be bonded via a crosslinking agent. Therefore, the monomers that make up the latex include carboxyl groups,
Contain reactive groups such as amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, ester group, methylol group, cyano group, acetyl group and unsaturated carbon bond. Is desirable. When a cross-linking agent is used, those used as a cross-linking agent for ordinary gelatin can be used. For example, aldehyde-based, glycol-based, triazine-based, epoxy-based, vinylsulfone-based, oxazoline-based, methacryl-based, and acrylic-based crosslinking agents can be used.

For the silver halide photographic light-sensitive material of the present invention, a commonly used hardener, thickener, gelatin plasticizer, matting agent, coating aid and the like can be used.

Particularly as a hardener, Japanese Patent Application No. 6-1466
(1) to (2) on page 10 to page 13 of the specification No. 78.
It is preferable to use the carbonylpyridinium type hardener of 5).

In the silver halide photographic emulsion according to the present invention, various photographic additives can be used in addition to the metal salt or its complex salt in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (December 1978
No.) and the same No. No. 18716 (November 1979) and the same No. 308119 (December 1989). The types and locations of the compounds shown in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page classification Page classification Page classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic Agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX As the support that can be used in the light-sensitive material according to the present invention, for example, the above-mentioned support can be used. RD-17643, page 28 and RD
The thing described in page 1009 of -308119 is mentioned.

A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge or ultraviolet irradiation in order to improve the adhesion of the coating layer.

The processing method of the silver halide light-sensitive material of the present invention is processed by an automatic processor including the steps of development, fixing, washing and drying, and the processing step from development to drying is within 30 seconds, preferably. Within 25 seconds.

That is, from the time when the tip of the photosensitive material begins to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing step (so-called Dry to Dry).
Time) is within 30 seconds, more preferably this Dr
The y to Dry time is within 25 seconds.

The fixing temperature and time are about 20-50 ° C. and 6-
20 seconds is preferable, and 6 to 15 seconds is more preferable at 30 to 40 ° C.

The developing time with the developer of the present invention is 5 to 45 seconds, preferably 6 to 20 seconds. Development temperature is 25 ~
50 ° C is preferred, and 30 to 40 ° C is more preferred.

Drying is usually 35 to 100 ° C., preferably 4
A drying zone in which hot air of 0 to 80 ° C. is blown or a heating means such as far infrared rays or a heat roller is provided may be installed in the automatic processor.

Further, the automatic developing machine is equipped with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during each of the developing, fixing and washing steps (special feature). Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device capable of adjusting a developing solution and a fixing solution.

The developer of the present invention contains 1,4 as a developer.
It is based on the inclusion of dihydroxybenzenes or, if necessary, p-aminophenol compounds and / or pyrazolidone compounds.

As 1,4-dihydroxybenzenes, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
There are dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. N as a p-aminophenol-based developing agent
-Methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-
There are methyl-p-aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable.

Examples of the pyrazolidone compound that can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-ethyl-3-pyrazolidone. ,
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxy Methyl-3-
Pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4 -Dimethyl-
3-pyrazolidone, 1- (2-benzothiazolyl) -3
-Pyrazolidone, 3-acetoxy-1-phenyl-3-
Pyrazolidone compounds such as pyrazolidone may be mentioned.

The amount of 1,4-dihydroxybenzene added may be 0.01 to 0.7 mol per liter of the developing solution,
0.1 to 0.5 mol is preferable.

The amount of the p-aminophenol compound and the pyrazolidone compound added is 0.
The amount is 0005 to 0.2 mol, preferably 0.001 to 0.1 mol.

Examples of the sulfite used in the developing solution of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metasulfite and the like.

The developer may contain a chelating agent having a chelate stability constant for iron ions of 8 or more. The iron ion here means ferric iron (Fe ³⁺ ).

Examples of the chelating agent having a chelate stability constant of 8 or more for iron include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents and polyhydroxy compounds.

Specific examples of these include ethylenediaminedioltohydroxyphenylacetic acid, triethylenetetramineacetic acid, diaminopropanetetraacetic 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, glycoletheraminetetraacetic 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-
Phosphonobtan-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, hexametaphosphoric acid Examples include sodium.

The developing solution of the present invention may contain a hardening agent that strengthens the physical properties of the film by undergoing a hardening reaction with gelatin in the light-sensitive material during the development processing. Examples of the hardener include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-
Isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butyl maleic dialdehyde,
Alternatively, these bisulfite adducts and the like are used.

As additives used in addition to the above components, development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, Organic solvent such as methanol or 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-
Mercapto compounds such as 5-sulfonic acid sodium salt,
An antifoggant such as a benztriazole compound such as 5-methylbenztriazole may be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent and the like may be contained.

The pH of the developer may be 9.0 to 12, preferably 9.0 to 11.5. The alkaline agent or buffer used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium triphosphate and potassium triphosphate.

In the present invention, a fixing solution containing a fixing agent such as sodium thiosulfate or ammonium thiosulfate can be used as the fixing solution. Of these, ammonium thiosulfate is preferable from the viewpoint of fixing speed. These fixing agents are generally used in an amount of about 0.1-6 mol / l.

The fixing solution may contain an aqueous solution aluminum salt as a hardening agent, and further includes aluminum chloride, aluminum sulfate, potassium alum and the like.

As the fixing solution, malic acid, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination. It is effective that these compounds are contained in an amount of 0.001 mol or more per liter of the fixer,
0.005-0.03 mol is particularly effective.

The pH of the fixing solution is 3.8 or more, preferably 4.2 to 7.0. Considering the fixing dura or odor of sulfite, 4.3 to 4.8 is more preferable.

P by running the fixing solution according to the present invention
The H increase rate width is preferably 0.21 or less, and 0.21 to 0.
05 is more preferable.

In the processing method according to the present invention, it is preferable to use a starter for the developing solution or the developing replenishing solution. The decrease in pH during running due to the reduction in the aperture ratio is improved by keeping the pH of the replenisher liquid higher than that of the mother liquor. As a method of preparing a mother liquor having a low pH, a method of lowering the pH by adding a starter to the replenisher to obtain a mother liquor is preferable.

The starter used in the present invention is an acidic additive and may be either an organic acid or an inorganic acid, or a mixture thereof. The starter may be solid or solution as long as it is soluble in the developing solution, and the solution state is preferably easy to use. Specific components of the starter include, for example, acetic acid, citric acid, boric acid, sulfuric acid, salicylic acid, and salts thereof may be used.

These acids may be used alone or in combination of two or more. The amount of the starter added is 0.1 to 100 g, preferably 0.5 to 50 g, per liter of the developing solution. The range in which the pH of the developer is lowered by the addition of the starter is preferably 0.2 or more, more preferably 0.2 to 1.0.

In the present invention, the starter may contain a component other than an acid, and in particular, it may contain a component such as halogen which increases in the development reaction and hydroquinone monosulfonate. KBr, KCl as halogen
0.1-10g per liter of developer
Is preferred.

The light-sensitive material which has been developed and fixed is subsequently washed with water or stabilized. Washing or stabilizing treatment,
Not only the water saving process becomes possible with the replenishment amount of 3 liters or less per 1 m ^{2 of the} silver halide photographic light-sensitive material (including 0, that is, it can be performed by washing with water with a reservoir), and the piping for installing an automatic processor is unnecessary. can do.

When washing with water is carried out with a small amount of water, JP-A-63-63
It is more preferable to provide a squeeze roller cleaning tank described in JP-A-18350, JP-A-62-287252 and the like. Further, in order to reduce the pollution load which becomes a problem when washing with a small amount of water, various oxidizing agents may be added and filter filtration may be combined. Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with anti-molding water according to the treatment is described in JP-A-60-235133. As described above, it can also be used for a processing solution having a fixing ability, which is a processing step before that.

In addition, the treatment agent component that prevents unevenness of water bubbles and / or adheres to the squeeze roller, which is likely to occur when washing with a small amount of water,
A water-soluble surfactant or an antifoaming agent may be added to prevent transfer to the treated film. Further, for prevention of contamination by dyes eluted from the light-sensitive material, JP-A-63-1
The dye adsorbent described in No. 63456 may be installed in the washing tank. In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos. 2-201357 and 2-1
32435, 1-102553, JP-A-46-4
A bath containing the compound described in No. 4446 may be used as the final bath of the light-sensitive material. If necessary, ammonium compounds, metal compounds such as Bi and Al, fluorescent whitening agents, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, antifungal agents, alkanolamines and surface active agents can be used in this stabilizing bath. Agents can be added.

As the water used in the washing step or the stabilizing step, tap water, deionized water, halogen, ultraviolet germicidal lamp, and various oxidizing agents (ozone, hydrogen peroxide,
It is possible to use water that has been sterilized by chlorate, etc.).

[0074]

The present invention will be described below in more detail with reference to examples.

Example 1 <Preparation of silver halide photographic light-sensitive material> Preparation of seed emulsion 1 A 0.05 N aqueous solution of potassium bromide containing hydrogen peroxide-treated gelatin vigorously stirred at 40 ° C. was added to an aqueous solution of silver nitrate and hydrogen peroxide. An equimolar aqueous solution of potassium bromide containing processed gelatin was added by the double jet method, and the temperature was lowered to 25 ° C over 30 minutes after 1.5 minutes, and then 80 ml of ammonia water (28%) per 1 mole of silver nitrate was added. Was added and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous demol N solution and an aqueous magnesium sulfate solution, and then an aqueous gelatin solution was added and redispersed. The obtained seed emulsion had an average grain size of 0.23 μm and a coefficient of variation of 0.2.
It was 8 spherical particles.

Growth from Seed Emulsion 1 Grains were grown as follows using the above seed emulsion. 75
To an aqueous solution containing ossein gelatin vigorously stirred at ℃ and propyleneoxy-polyethyleneoxy-disuccinate-disodium salt, an aqueous solution of potassium bromide and potassium iodide and an aqueous silver nitrate solution were added by a double jet method.

During this period, pH was kept at 5.8 and pAg was 9.0. After the addition was completed, the pH was adjusted to 6.0 and 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydride was added per mol of silver halide. 400 mg was added. 4 more
After desalting with a demol N aqueous solution at 0 ° C., a gelatin aqueous solution was added and redispersed.

By this method, the average silver iodide content is 1.5 mol%, the grain size is 0.4 μm, the projected area diameter is 1.20 μm,
A tabular silver iodobromide emulsion (A-1) having a coefficient of variation of 0.25 and an aspect ratio of 4.0 was prepared.

<Preparation Method of Silver Chloride Emulsion> (Emulsion B-1) Distilled water containing 90 g of high methionine gelatin (containing 59 micromoles of methionine per 1 g of gelatin) in a reactor equipped with a stirrer, 6000 g, 0.5 mol CaCl ₂ 2H ₂ O and 9.3 g of NaBr were added. Adjust the pH to 5.1 at 40 ℃, NaOH or HN
The pH was maintained as it was by adding O ₃ . 1.6% of total Ag used, 0.5M AgN over 4 minutes
O ₃ solution was added. Next, as the addition time, the addition was performed at a flow rate that was linearly accelerated (9.32 times from the start to the end) over 55 minutes, during which the remaining 98.4% of Ag was consumed. After the start of precipitation, 30 cc of 37 mmol adenine solution was added at 4, 16, and 36 minutes. 3M at 10 minutes
3.7 g of CaCl ₂ solution of was added to the precipitate. During the addition of the adenine and CaCl ₂ solution, the silver flow was stopped for 1 minute and the precipitate was mixed evenly. A total of 1.44 moles of silver were precipitated.

By this method, a tabular silver chlorobromide emulsion (B-1) having an average silver chloride content of 94 mol%, a grain size of 0.4 μm, a projected area diameter of 2.0 μm and a coefficient of variation of 0.25 and an aspect ratio of 12 is used. Was prepared.

(Emulsion B-2) An emulsion (B-1) was prepared except that NaBr was not added to the reaction kettle. A tabular silver chloride emulsion (B-2) having a grain size of 0.4 μm, a projected area diameter of 1.8 μm, a coefficient of variation of 0.25 and an aspect ratio of 9.0 was prepared by this method.

(Emulsions B-3, B-4) NaBr was added to a reaction kettle.
It was prepared in the same manner as Emulsion (B-1) except that 75 g was added. However, 30 mmol of the 37 mmol adenine solution that had been added 36 minutes after the start of precipitation was not added to B-4. According to this method, the average silver chloride content was 50 mol%, the grain size was 0.4 μm, and the projected area diameter was 1.4 μm.
A tabular silver chloride emulsion (B-3, B-4) having a coefficient of variation of 0.25 and an aspect ratio of 4.0 and 2.5 at 2 μm, respectively.
Was prepared.

(Preparation of Sample) Next, the above-mentioned emulsions A-1 and B-1 to B-4 were heated to 60 ° C. and then the spectral sensitizing dyes were added to Table 1.
After addition as a solid fine particle dispersion so as to achieve the adsorption amount described in 1 above, a mixed solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and a dispersion of triphenylphosphine selenide were added to give a total of 2
Aged for hours. At the end of ripening, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Sensitizing dye (A) 5,5'-dichloro-9-
Ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydride Sensitizing dye (B) 5,5'-di- (butoxycarbonyl)
Anhydrous of -1,1'-diethyl-3,3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine-sodium salt The above additives and their addition amounts (per 1 mol of AgX) are shown below.

Sensitizing dye (A) 430 mg Sensitizing dye (B) 4.3 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg 4-Hydroxy-6 -Methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg A solid dispersion of a sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes to obtain the dye.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C,
It was stirred and completely dissolved. On the other hand, photographic gelatin 3.8k
g was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of Photosensitive Material) The following coating solutions were prepared. The addition amount is 1 on one side of the silver halide photographic light-sensitive material.
The addition amount per m ² is shown.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-dichloro-6-hydroxy-1,3 5-Triazine sodium salt 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 35 mg styrene-anhydrous Maleic acid copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylol propane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 20 mg 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 500 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 5mg compound _{(H) 0.5mg nC 4 H 9} OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg compound (M) 5mg compound (N) mg Colloidal silica (Ludox AM: manufactured by DuPont, average particle size 0.013μ) Amount shown in Table 1 Latex (L) 0.2 g Dextrin (average molecular weight 1000) 0.2 to 1.0 g (at the swelling thickness shown in Table 1) Amount to be adjusted) (However, the second layer was coated with the amount of gelatin adjusted so that the total amount of gelatin on the side having the emulsion layer was the amount shown in Table 1.) Third layer (protective layer) Gelatin 0 Matting agent consisting of polymethylmethacrylate (area average particle size 7.0 μm) 50 mg Hardener (HA) 10 to 100 mg (amount adjusted to swelling thickness shown in Table 1) 2,4-dichloro-6-hydroxy- 1,3,5-Triazine sodium salt 10 mg Bis-vinylsulfonylmethyl ether 36 mg Latex (L) 0.2 g Polyacrylamide (average molecular weight 10000) 0.1 g Sodium polyacrylate 30 mg Compound (SI) 20 mg Compound (I) 12 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound (K) 15 mg Compound (O) 50 mg Compound (S-2) 5 mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1 mg

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<Preparation of Support> As the support, glycidyl methacrylate 50 wt% and methyl acrylate 1 were used.
175 μm blue-colored polyethylene coated with an aqueous copolymer dispersion obtained by diluting the copolymer consisting of three kinds of monomers, 0 wt% and 40 wt% butyl methacrylate, to be 10 wt% A terephthalate film was used.

<Coating of Sample> One slide of the above coating solution was applied to both sides of the above-mentioned undercoated polyethylene terephthalate support in the order of the transverse light shielding layer, the emulsion layer and the emulsion protective layer from the support side. Sample No. 1 shown in Table 1 was obtained by simultaneous multilayer coating using a hopper type coater at a speed of 100 m / min for 2 minutes and 20 seconds and drying. 1-21 were created. The coated silver amount was adjusted to be 1.6 g / m ² for one side.

The compositions of the developing solution and fixing solution used in the present invention are shown below.

Developer composition Part-A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriaminepentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 1.4 g 1-phenyl- 5-Mercaptotetrazole 0.25 g 4-Hydroxymethyl-4-methyl-1-phenylpyrazolidone 102 g Hydroquinone 390 g Diethylene glycol 550 g Add water to make 6000 ml Part-B (for 12 l finishing) Glacial acetic acid 70 g 5-Nitroindazole 0 .6g glutaraldehyde (50% solution) 8.0 g N-acetyl -DL- penicillamine 1.2g starter glacial acetic acid _{120g HO (CH 2) 2 S} (CH 2) 2 S (CH 2) 2 OH 1 g Potassium bromide 225 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 1.0 g Add pure water to make 1.0 l Fixer formulation Part-A (for 18.3 l finishing) Thio Ammonium sulfate (70 wt / vol%) 4500 g Sodium sulfite 450 g Sodium acetate 450 g Boric acid 110 g Tartaric acid 60 g Sodium citrate 10 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Glacial acetic acid 330 g Aluminum sulfate 62 g Finishing to 7200 ml with pure water To prepare a developing solution, Part A and Part B were simultaneously added to about 5 liters of water, and while stirring and dissolving, water was added to 12 liters and the pH was adjusted to 10.53. This is used as a development replenisher.

20 ml / l of the above-mentioned starter was added to 1 liter of this development replenisher to adjust the pH to 10.30 to prepare a working solution.

The fixing solution was prepared by adding Part A to about 5 liters of water and adding water while stirring and dissolving to make 18.3 liters.
The pH was adjusted to 4.6 with sulfuric acid and NH ₄ OH. This is used as a fixing replenisher.

Processing Step Process Processing Temperature (° C.) Processing Time (sec) Development + Crossover 35 7.2 Fixing + Crossover 33 5.8 Rinsing + Crossover 18 3.8 (Supply Water 7 liters / min Supply) Squeeze 40 2.8 Dry 50 5.4 Total --25.0 <Measurement of swelling thickness> Each of the obtained samples was measured at 25 ° C and 55% R
After measuring the film thickness in the atmosphere of H, distilled water at 25 ° C. was continuously dropped and the film thickness was measured at 5 second intervals while standing still. The increase in the film thickness measured before and after the addition of distilled water was taken as the swelling thickness.

The film thickness was measured with an electronic micrometer (K306 type) manufactured by Adachi Electric Co., Ltd. Table 1 shows the value when the film thickness is maximum (maximum swelling thickness) and the lowest swelling thickness (minimum swelling thickness) within 2 minutes after the maximum swelling thickness is shown.

<Measurement of Covering Power (CP)> After exposing each of the obtained samples to the maximum density,
A development sample was obtained by performing processing for 25 seconds at 35 ° C. with the above-mentioned processing solution using an automatic developing machine modified from the automatic developing machine SRX-503 manufactured by Konica Corporation. The silver amount mg / dm ² of the developed sample thus obtained was measured by a fluorescent X-ray analysis method, and the density (blackening density minus the base density) was divided by the silver quantity to obtain the covering power.

<Evaluation of Color Remaining> The unexposed sample was subjected to the above-mentioned S.
With the RX-503 modified automatic developing machine
The treatment was carried out at 25 ° C. for 25 seconds, and the following 5-level visual evaluation was performed for residual color contamination.

5: No residual color contamination 4: Slightly 3: There is residual color contamination, but practical use 2: Some residual color contamination, but practical limit of range 1: Large amount of residual color contamination, not practical <Evaluation of roller mark > Pressure resistance during development (pressure mark by roller of automatic processor, ie roller mark)
Processed the unexposed samples on an X-ray automatic processor with a special roller with strong relief with a counter roller.

The roller marks generated at that time were classified into 5 grades according to their grades and evaluated.

5: No roller mark 4: Slightly generated 3: Slightly generated, but practically usable 2: Many, but limited in practical range 1: Very many, not practical

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[Table 1]

As is clear from Table 1, the sample of the present invention is a silver halide light-sensitive material which has a high covering power, is excellent in roller mark fog, and has excellent residual color, and which is capable of ultra rapid processing.

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According to the present invention, a silver halide photographic light-sensitive material which has a high covering power, is excellent in roller mark fog, and is excellent in residual color, and which is capable of ultra-fast processing was obtained.

Claims (3)

[Claims] 1. In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the total gelatin coating amount on the side having the silver halide emulsion layer is 1.5 to 3.0 g / m ² , the swelling thickness was reduced to 50% or less and 20% or more of the maximum swelling thickness within 2 minutes after the swelling degree on the side having the silver halide emulsion layer was maximized, and The spectral sensitizing dye has a saturated adsorption amount of 6 on the grain surface.
Adsorb 0% or more and 100% or less, aspect ratio 2 or more,
A silver halide photographic light-sensitive material comprising silver halide grains having an average silver chloride content of 10 mol% or more. 2. The silver halide photographic light-sensitive material according to claim 1, wherein colloidal silica is contained in the silver halide emulsion layer. 3. A development processing method, which comprises developing the silver halide photographic light-sensitive material according to claim 1 or 2 for a total processing time of 30 seconds or less.