JPH08272021A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material high in sensitivity and low in fog and small in desensitization owing to time lapse and capable of ultrahigh speed development processing by specifying the contents of a silver halide emulsion. CONSTITUTION: At least one of the silver halide emulsion layers contains silver halide grains having an average silver chloride content of >=10mol% and an average aspect ratio of >=3, and the emulsion layer contains a compound represented by the formula and multivalent metal ions, and the photosensitive material is packaged with the polyethylene sheet containing at least the one having a density of >=0.95g/cm<3> . In the formula, each of Z1 and Z2 is a nonmetallic atomic group necessary to form an optionally substituted benzene or naphthalene ring: each of R1 and R2 is an optionally substituted alkyl, alkenyl, or aryl group; R3 is an alkyl group; X is an anion; and (n) is 1 or 2, but when an intramolecular salt is formed, (n) is 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. In particular, the present invention relates to a silver halide light-sensitive material which has high sensitivity, low fog, and little desensitization with time and which can be processed extremely rapidly.

[0002]

2. Description of the Related Art In recent years, in the field of medical X-ray photographic light-sensitive materials, development processing has been accelerated and processing time has been greatly shortened.
It is necessary to develop a silver halide photographic light-sensitive material excellent in processability (progress of development). In recent years, it has been found that the developability can be improved by using tabular grains.
Many are disclosed such as 4,434,226 and 4,413,053. Further, it is disclosed, for example, in JP-A-63-305343 or JP-A-1-770474 that the developability can be improved by controlling the development starting point of silver halide grains having a (111) plane. However, although these technologies have their respective characteristics, they are not suitable for silver halide photographic light-sensitive materials with a relatively small silver halide grain size and high sensitivity, and have low fog, and therefore have a rapid processing suitability. It wasn't enough about giving it.

Usually, in the packaging of a photographic light-sensitive material, for example, in the case of a sheet-shaped film such as a diagnostic X-ray light-sensitive material, a packaging unit in which a predetermined number of gripped sheets are sandwiched by U-shaped cardboards is protected from external impact. Then, in order to provide light shielding, it is suctioned and deaerated in a barrier bag made of a polyethylene sheet in which carbon black is dispersed to keep it light-tight. The barrier bag is made by using a polyethylene sheet with aluminum vapor-deposited or laminated, and it is a composite material rather than a single material, so it is necessary to separate each single material for recycling. There was a drawback that the man-hours for recycling were high.

In a single material packaging of a polyethylene sheet which is vapor-deposited or not laminated with aluminum, the moisture permeability of the polyethylene sheet affects the light-sensitive material, and the photographic characteristics such as decrease in sensitivity and increase in fog due to storage over time. Influence. If the thickness of the sheet is increased in order to suppress the moisture permeability of polyethylene, the flexibility of the packaging form will be impaired and the handling will be inconvenient. Therefore, there has been a demand for a photographic light-sensitive material in which the photographic characteristics are not deteriorated during long-term storage and the packaging material can be easily recycled.

In addition, even when packaged in the above-mentioned barrier bag,
High-sensitivity silver halide photographic light-sensitive materials are likely to suffer from sensitivity deterioration during long-term storage, and the difference becomes even greater when rapidly processed. Therefore, it has been desired to develop a silver halide photographic light-sensitive material having high sensitivity and low fog, which provides stable photographic processing suitability even after long-term storage.

[0006]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material which has high sensitivity, low fog, and little desensitization with time and which can be processed extremely rapidly.

[0007]

The objects of the present invention have been solved by the following.

1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers comprises
It contains silver halide grains having an average silver chloride content of 10 mol% or more and an average aspect ratio of 3 or more, and further contains a compound represented by the following general formula [1] and a polyvalent metal ion in the emulsion layer. A silver halide photographic light-sensitive material, wherein at least one of the silver halide light-sensitive materials is packaged with a polyethylene sheet containing polyethylene having a density of 0.95 g / cm ³ or more.

[0009]

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(In the formula, Z ₁ and Z ₂ each represent a nonmetallic atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. R ₁ and R ₂ are each substituted or unsubstituted. A substituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, at least R ₁ ,
Any one of R ₂ is a sulfoalkyl group or a carboxyalkyl group. R ₃ represents an alkyl group. X ⁻ represents an anion, and n represents 1 or 2. However, n is 1 when forming an intramolecular salt. 2) A method for processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material described in 1 above in a total processing time of 35 seconds or less.

3) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers comprises
A non-photosensitive layer containing silver halide grains having an average silver chloride content of 10 mol% or more and an average aspect ratio of 3 or more, and further outside the silver halide emulsion layer (away from the support). The amount of gelatin is 0.9 g / m ² or less, and the silver halide light-sensitive material has a temperature of 15 to 30 ° C. and a relative humidity of 40 to
A silver halide photographic light-sensitive material characterized by being packaged under the condition of 60%.

4) A method for processing a silver halide photographic light-sensitive material, characterized in that the silver halide photographic light-sensitive material described in 3 above is processed within a total processing time of 35 seconds.

The present invention will be described in detail below.

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 (December 1978), 22
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 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 described in, for example, "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

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,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or 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 monodisperse referred to here, when the average particle diameter is measured by a conventional method, at least 95% of the particles by number or weight are within ± 40% of the average particle diameter, preferably ±
It is a silver halide grain within 30%.

The crystal structure of silver halide may have a silver halide composition in which the inside and the outside are different. For example, the core portion of high silver iodide is coated with a shell layer of low silver iodide to give a clear 2 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 for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like.

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

A method for producing the above-mentioned core / shell type emulsion is known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

The tabular grains are said to improve spectral sensitization efficiency and image graininess and sharpness. For example, British Patent No. 2,112,157, US Patent Nos. 4,414,310 and 4,434,
No. 226, etc., and the emulsion can be prepared by referring to the methods described in these publications.

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

A method for producing the above core / shell type emulsion is well known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

The silver halide emulsion used in the practice of the present invention can be adjusted to a pAg ion concentration suitable for chemical sensitization by a suitable method after the growth of silver halide grains is completed. For example, the method described in Research Disclosure 17643, such as the agglutination method or the noodle washing method, can be used.

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.

The equivalent spherical diameter of emulsion grains having an aspect ratio of 2 or less is 0.8 μm to 2.0 μm, more preferably 1.0 μm to 1.5 μm.
Is. 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 the emulsion grains having an aspect ratio of 2 or more is 0.1 μm to 1.5 μm, more preferably 0.2 μm to 1.0 μm.
Is. Furthermore, 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.

Next, the spectral sensitizing dye represented by the general formula [1] used in the present invention will be described.

In the general formula [1], Z ₁ and Z ₂ each represent a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent, and as a substituent for the benzene ring, Examples thereof include a halogen atom (chlorine, bromine, iodine, fluorine, etc.), trifluoromethyl group, cyano group, lower alkyl group, lower alkoxy group, phenyl group, acylamino group, alkoxycarbonyl group, aryloxycarbonyl group and the like.

R ₁ and R ₂ include those each having a substituent, and are preferably alkyl groups having 8 or less carbon atoms, such as methyl, ethyl, propyl, vinylmethyl, butyl, pentyl, hexyl, heptyl, octyl groups, and the like. Examples of aralkyl groups having 10 or less carbon atoms include benzyl and phenethyl groups, examples of alkenyl groups include vinyl, allyl and 1-propenyl groups, and aryl groups such as phenyl group.

Each of these groups may be substituted with a halogen atom, a hydroxy group, a carboxy group, a sulfo group or the like as a substituent, and any one of R ₁ and R ₂ is a sulfoalkyl group such as sulfoethyl, Examples of carboxyalkyl groups such as sulfopropyl, 4-sulfobutyl, and 3-sulfobutyl groups include carboxymethyl and carboxyethyl groups. R ₃ represents an alkyl group. X ⁻ represents an anion, and n represents 1 or 2. However, n is 1 when forming an intramolecular salt.

Specific examples of the compound represented by the general formula [1] used in the present invention are shown below.

[0036]

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[0037]

[Chemical 4]

[0038]

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The spectral sensitizing dye represented by the above general formula [1] according to the present invention includes, for example, British Patents 521,165 and 745,546.
No., Belgium Patent 615,549, Soviet Patent 412,218
No. 432,166, etc., Japanese Patent Publication No. 38-7828, No. 42
-27165, 42-27166, 43-13823, 43-14497
No., No. 44-2530, No. 45-27676, No. 45-32740, etc., FM Hamer "The Cyaninedyes and related com"
pounds ”John Wiley & Sons (New York, London) 1964
It can be synthesized according to the method described in annual publications and the like.

It should be noted that any of the above general formulas [1] shows only one state of the resonance structure, and even if it is expressed in an extreme state where the + charge enters a symmetrical heterocyclic nitrogen atom, it means the same substance. To do.

The appropriate amount of the above dye according to the present invention per mol of silver halide varies depending on the total surface area of silver halide grains in the emulsion, but the total amount of the general formula [1] is preferably less than 600 mg. Further, less than 300 mg is particularly preferable.

Other cyanine dyes and merocyanine dyes may be used in combination in the silver halide emulsion of the present invention, if necessary.

As the solvent for the sensitizing dye, conventionally used water-miscible organic solvents can be used. For example, alcohols, ketones, nitriles, alkoxy alcohols, etc. have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,
Examples include 3-propanediol, acetone, acetonitrile, 2-methoxyethanol and 2-ethoxyethanol.

The silver halide photographic light-sensitive material of the present invention contains a polyvalent metal ion, but Ca ⁺⁺ or Mg ⁺⁺ ion is preferable, from the addition of the compound of the general formula [1] to the completion of coating. It is preferable to add 100 ppm or more. It is more preferable to add 500 ppm or more.

The polyethylene sheet used for packaging the light-sensitive material of the present invention is a polyester such as polyethylene terephthalate, which is a high-density polyethylene film containing polyethylene having a polyethylene density of 0.95 g / cm ³ or more and imparts light-shielding property. Therefore, the carbon black powder is dispersed and processed into a sheet.

The thickness of the polyethylene sheet is preferably 15
It is 0 μm or less, and more preferably 100 μm or less.
When the thickness of the polyethylene sheet exceeds 150 μm, the rigidity is increased, and it becomes inconvenient to handle the package or the silver halide photographic light-sensitive material therein.

The density of polyethylene of the polyethylene sheet of the present invention is 0.95 g / cm ³ or more, but two or more polyethylene sheets having different densities may be laminated to form one sheet. However, the composition of the sheet at that time is that the density of at least one polyethylene sheet of the structural unit is 0.95.
It should be g / cm ³ or more.

The polyethylene sheet of the present invention can be manufactured by a usual method.

The preferred packaging form of the light-sensitive material of the present invention is
Using 50 or more sheets of photosensitive material cut into a certain size as one packaging unit, the polyethylene sheet of the present invention is used for bag making, packaging and vacuum suction to keep the inside of the polyethylene bag anaerobically and light-tightly sealed. At this time, it is preferable that nothing other than the photosensitive material is enclosed in the polyethylene bag, but an oxygen absorber or the like may be enclosed.

A so-called no-interleaf package may be used, in which a predetermined number of sheets are used as a packaging unit and protected by U-shaped cardboard, and a single leaf interleaf sheet is applied only to the surface in contact with the cardboard. Alternatively, interleaf packaging may be used in which one sheet is held by interleaf paper made of thin paper folded back and a predetermined number of the held sheets are sandwiched by U-shaped cardboard. Further, it is preferable to store these photosensitive material packages in an outer box made of cardboard from the viewpoint of preventing external pressure.

In another embodiment, the silver halide photographic light-sensitive material of the present invention is packaged under the conditions of a temperature of 15 to 30 ° C. and a relative humidity of 40 to 60%. More preferably, it is carried out under the condition of 55%.

In the silver halide photographic light-sensitive material of the present invention, the non-light-sensitive layer outside the silver halide emulsion layer (on the side farther from the support) preferably has a gelatin content of 0.9 g / m ² or less, It is more preferably 0.75 g / m ² or less.

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

The silver halide photographic light-sensitive material of the present invention may contain a latex. Ordinary latex is dispersed in water by a surfactant, but latex is preferably dispersion-stabilized by gelatin bonded to polymer latex. The polymer constituting the latex and 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 monomer constituting the latex is a carboxyl group,
It must have a reactive group such as amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, ester group, methylol group, cyano group, acetyl group, unsaturated carbon bond, etc. Is desirable. When a cross-linking agent is used, those used as a cross-linking agent for ordinary gelatin can be used. For example, an aldehyde-based, glycol-based, triazine-based, epoxy-based, vinyl sulfone-based, oxazoline-based, methacrylic-based, acrylic-based, or other crosslinking agent can be used.

In 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.

As the hardener, it is preferable to use the carbonylpyridinium type hardeners (1) to (25) described in Japanese Patent Application No. 6-146678, pp. 10-13.

For the above photographic emulsion, the process for producing a light-sensitive material,
Various known compounds can be added in order to prevent sensitivity deterioration and fog generation during storage or processing.

The development processing method of the silver halide photographic light-sensitive material according to the present invention, when processed by an automatic processor including the steps of development, fixing, washing and drying, completes the steps from development to drying within 45 seconds. Preferably. That is, the time 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 passing through the processing steps (so-called Dry To Dry time) is preferably within 90 seconds, more preferably Is within 45 seconds, more preferably within 30 seconds.

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

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 preferable, and 30-40 degreeC is more preferable.

The drying time is usually 35 to 100 ° C., preferably 40.
The automatic developing machine may be provided with a drying zone in which hot air of -80 ° C is blown or a heating means by far infrared rays or a heat roller is provided.

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 the developing, fixing and washing steps (special features). Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device capable of preparing a developing solution and a fixing solution.

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

Examples of 1,4-dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2, There are 5-dimethylhydroquinone, hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. P-aminophenol-based developing agents include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which 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, 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- Dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy Phenyl-4,4-
Dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-
Examples thereof include pyrazolidone compounds such as pyrazolidone and 3-acetoxy-1-phenyl-3-pyrazolidone.

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

The addition amount of the p-aminophenol compound and the pyrazolidone compound is 0.0005 per 1 l of the developing solution.
.About.0.2 mol, preferably 0.001 to 0.1 mol.

Examples of the sulfite used in the developer 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 referred to here means ferric iron (Fe ³⁺ ).

Examples of chelating agents 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 are, for example, 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-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, tetrapolyline Examples thereof include sodium acid salt and sodium hexametaphosphate.

The developing solution of the present invention may contain a hardening agent which 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, butylmaleindialdehyde, or a bisulfite adduct thereof is 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, Antifoggants such as organic solvents such as methanol or mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and benztriazole compounds such as 5-methylbenztriazole May be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent, etc. may be contained.

The pH of the developing solution may be 9.0-12, preferably 9.0-11.5. The alkaline agent or buffer used for setting the pH is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium triphosphate or potassium triphosphate.
Contains regulators.

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 mol to 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 fixing solution.
0.03 mol is particularly effective.

The fixing solution has a pH of 3.8 or more, preferably 4.2.
Those having .about.7.0 are preferred. Considering the fixing dura or odor of sulfite, 4.3 to 4.8 is more preferable.

The rate of increase of the fixing solution according to the present invention due to running is preferably 0.21 or less, more preferably 0.21 to 0.05.

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 decrease in aperture ratio is improved by keeping the pH of the replenisher solution higher than that of the mother liquor. As a method for preparing a mother liquor having a low pH, a method of lowering the pH by adding a starter to a 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 developer pH 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, can contain a component such as halogen which increases in the development reaction and hydroquinone monosulfonate. As halogen, KBr, KCl, etc. are preferably added in an amount of 0.1 to 10 g per liter of the developing solution.

The photosensitive material which has been developed and fixed is subsequently washed with water or stabilized. Washing or stabilizing treatment,
Not only does water saving become possible with a replenishment amount of 3 liters or less per 1 m ^{2 of} silver halide photographic light-sensitive material (including 0. That is, it can be carried out by washing with water with a reservoir), and 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-63-1 is used.
It is more preferable to provide a squeeze roller cleaning tank as described in No. 8350 and No. 62-287252. 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, which is produced by supplementing the washing or stabilizing bath with antifungal 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 the occurrence 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. Also, to prevent contamination by dyes eluted from the light-sensitive material, see Japanese Patent Laid-Open No. 63-16345.
The dye adsorbent described in No. 6 may be installed in the washing tank. or,
In some cases, a stabilizing treatment may be carried out following the water washing treatment, and examples thereof include JP-A-2-201357, JP-A-2-132435, and JP-A-1-102553.
A bath containing the compound described in JP-A-46-44446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines and surface active agents. 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.).

[0088]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 <Preparation of silver halide photographic light-sensitive material> Preparation of seed emulsion 1 Including a hydrogen peroxide-treated gelatin vigorously stirred at 40 ° C.
To the 05N potassium bromide aqueous solution, an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin was added by the double jet method, and after 25 minutes, it took 25 minutes.
After the liquid temperature was lowered to ℃, 80 ml of ammonia water (28%) was added per 1 mol of silver nitrate, 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 resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

Growth from Seed Emulsion 1 Grains were grown as follows using the above seed emulsion. 75 ° C
A double jet method was used to add an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate to an aqueous solution containing ossein gelatin and propyleneoxy-polyethyleneoxy-disuccinate-disodium salt vigorously stirred at.

During this period, the pH was kept at 5.8 and the pAg was 9.0. After the addition was completed, the pH was adjusted to 6.0, and 5,5'-dichloro-9-ethyl-3,
Anhydrous of 3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt was added in an amount of 400 mg per mol of silver halide. Further, the mixture was desalted at 40 ° C. with an aqueous solution of Demol N, and then an aqueous gelatin solution was added to re-disperse.

According to 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, and the variation coefficient is 0.2.
5, tabular silver iodobromide emulsions (A-1) and (A-2) having aspect ratios of 4.0 and 9.0 were prepared.

<Preparation Method of Silver Chloride Emulsion> (Emulsion B-1) 6000 g of distilled water containing 90 g of high methionine gelatin (containing 59 micromoles of methionine per 1 g of gelatin) and 0.5 mol of CaCl in a reactor equipped with a stirrer. ₂ 2H
₂ O and 9.3 g of NaBr were added. The pH was adjusted to 5.1 at 40 ° C. and the pH was maintained by adding NaOH or HNO ₃ . 1.6% of total Ag used, 0.5M Ag over 4 minutes
NO ₃ was added. Next, as the addition time, it was added at a flow rate that accelerated linearly over 55 minutes (9.32 times from the start to the end), during which the remaining 98.4% of Ag was consumed. 37 mM adenine solution 30 at 4 minutes, 16 minutes and 36 minutes after the start of precipitation
cc was added. At 10 minutes, 3.7 g of 3M CaCl ₂ solution was added to the precipitate. During the addition of adenine and CaCl ₂ solution, a silver inflow of 1
After stopping for a minute, the precipitate was mixed uniformly. A total of 1.44 moles of silver were precipitated.

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

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

(Emulsions B-3, B-4) 75 g of NaBr in a reaction kettle
Was prepared in the same manner as Emulsion (B-1) except that was added. However, 30 ml of the 37 mmol adenine solution which had been added 36 minutes after the start of precipitation was not added to B-4. By this method, a tabular silver chloride emulsion (B-3, B-3, having an average silver chloride content of 50 mol%, a grain size of 0.4 μm, projected area diameters of 1.4 μm and 1.2 μm, a coefficient of variation of 0.25, and aspect ratios of 4.0 and 2.5, respectively)
B-4) was prepared.

(Preparation of sample) 50 for each emulsion
While maintaining the temperature at ℃, after adding the amount of calcium chloride shown in Table 1, the spectral sensitizing dye Exemplified I-4 was added at 150 mg per mol of silver halide. Next, ammonium thiocyanate was added to 7.0 × 10 ^-4 mol per mol of silver, and an appropriate amount of chloroauric acid and hypo were added for chemical ripening to prepare 6 × 10 ^-4 AgI fine grain emulsion having an average particle size of 0.06 μm. After the addition of 1 mol of Ag / AgI, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added for stabilization by adding 3 × 10 ^-2 mol per mol of silver halide.

Additives used in the obtained emulsion are as follows. The amount of addition is shown in an amount per mole of silver halide.

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 mg styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl-triphenylphosphonium chloride 50 mg 2-anilino-4,6-di Mercaptotriazine 60mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 4g 2-Mercaptobenzimidazole-5-sulfonic acid sodium 1.5mg

[0101]

[Chemical 6]

NC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g The additives used in the protective layer liquid are as follows. The added amount is shown as an amount per 1 g of gelatin.

Polymethylmethacrylate (matting agent having an area average particle size of 7 μm) 7 mg Silicon dioxide (matting agent having an area average particle size of 1.2 μm) 0.5 g Ludox AM (DuPont colloidal silica average particle size 0.013 μm) 70 mg 2,4 - dichloro-6-hydroxy-1,3,5-triazine sodium salt _{30mg (CH 2 = CHSO 2 CH} 2) 2 O
36 mg

[0104]

[Chemical 7]

F ₁₉ C ₉ —O— (CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₂ OH
A sample was prepared as follows using 3 mg or more of the coating liquid. That is, the emulsion in the photographic emulsion layer is 2.0 g / m ^{2 on} one side and the protective layer is 1.15 on one side in the amount of gelatin.
Two slide hopper type coaters were used at a speed of 80 m / min to achieve g / m ^2, and both sides were simultaneously coated on the support prepared by the method shown below and dried in 2 minutes and 20 seconds to obtain a sample. It was

<Preparation of Support> As the support, glycidyl methacrylate 50 wt% and methyl acrylate 10 wt
%, Butyl methacrylate 40 wt% Copolymer consisting of 3 monomers diluted to 10 wt% Copolymer aqueous dispersion obtained as a subbing liquid and applied as 175 μm blue colored polyethylene terephthalate It was a film.

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

Developer Composition Part-A (for 12 liter finish) 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 0.25g 4-Hydroxymethyl-4-methyl-1-phenylpyrazolidone 102g Hydroquinone 390g Diethylene glycol 550g Add water to make 6000ml Part-B (12l finish) Glacial acetic acid 70g 5-Nitroindazole 0.6g Glutar Aldehyde (50% liquid) 8.0 g N-acetyl-DL-penicillamine 1.2 g Starter glacial acetic acid 120 g 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 1.0g fixer formulation Part-a (18.3l finishing) ammonium thiosulfate finished to pure water were added 1.0l (70wt / vol%) 4500 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 sulphate 62 g Developer with 7200 ml of pure water For the preparation of, Part A and Part B were added to about 5 liters of water at the same time, and while stirring and dissolving, water was added to 12 liters and the pH was adjusted to 10.
Adjusted to 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, adding water while stirring and dissolving to make 18.3 liter, and adding sulfuric acid.
The pH was adjusted to 4.6 using NH ₄ OH. This is the fixing replenisher.

<Evaluation of Sensitometry>
After leaving it in an environment of 23 ° C and 50% RH for 1 day, it is sandwiched between fluorescent intensifying screens for X-ray photography NR-160 (manufactured by Konica Corporation), and penetrometer B type (manufactured by Konica Medical Corporation). X-ray irradiation, automatic processor SRX-503 remodeling machine (manufactured by Konica Corporation)
Was used in the following steps to determine sensitivity and fog.
The sensitivity was obtained as the reciprocal of the X-ray required to obtain the density of fog +1.0, and the relative sensitivity was shown when the sensitivity of Sample No. 1 was 100.

Treatment process Treatment temperature (° C) Treatment time (sec) Development + crossover 35 7.2 Fixing + crossover 33 5.8 Washing + crossover 18 3.8 (washing water 7 liters / min supply) Squeeze 40 2.8 Drying 50 5.4 Total − −25.0 <Evaluation of storability> The obtained sample was cut into four pieces and left in an atmosphere of 40% RH and 25 ° C for 12 hours.
In an environment of 23 ° C and 50% RH, 50 sheets of non-interleaf packaging is made into a packaging unit, and the degassing pressure is 50 mmHg in a polyethylene sheet moisture-proof seal bag with a thickness of 100 μm and carbon black dispersed as a light-shielding agent. It was vacuum-sealed and light-tightly packaged. The densities of the polyethylene sheets shown in Table 1 were used.

To evaluate the storability, each packaged sample was left for 3 months in an environment of 23 ° C. and 80% RH, and the sensitivity and fog were determined by the sensitometric evaluation described above. The results obtained above are shown in Table 1 below.

[0114]

[Table 1]

As is clear from the table, the sample of the present invention has excellent storage stability and no deterioration in sensitivity or fog is observed after 3 months.

Example 2 Using the coating solution prepared in Example 1, a sample was prepared as shown in Table 2 so that the amount of gelatin on the protective layer per one side is shown in Table 2.
Was prepared in the same manner as in. However, 1500 ppm of calcium ion was added to the emulsion layers of all the samples.

The obtained sample was cut into four pieces and left for 12 hours in an atmosphere of 40% RH and 25 ° C.
Under the packaging conditions (environment) shown in, a non-interleaf package with 50 sheets as a packaging unit is created, and deaeration is performed in a barrier bag in which polyethylene sheet is laminated with aluminum.
The product was hermetically sealed under a vacuum of mmHg.

The sensitometric evaluation of these samples was carried out in the same manner as in Example 1, and the relative sensitivity is shown when the sensitivity of Sample No. 21 is 100.

As to the evaluation of storability, each packaged sample was left in an environment of 40 ° C. and 50% RH for 3 months, and the sensitivity and fog were determined in the same manner as in Example 1. The results obtained above are shown in Table 2 below.

[0120]

[Table 2]

As is clear from Table 2, the samples of the present invention are excellent in preservability and show no deterioration in sensitivity or fog after 3 months.

[0122]

According to the present invention, the sensitivity is high and the fog is low,
A silver halide photographic light-sensitive material capable of ultra-rapid processing with little desensitization with time was obtained.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has an average silver chloride content of 10 mol. % And average aspect ratio is 3
Including the above silver halide grains, further in the emulsion layer,
The silver halide light-sensitive material containing a compound represented by the following general formula [1] and a polyvalent metal ion, and at least one of which is packaged in a polyethylene sheet containing polyethylene having a density of 0.95 g / cm ³ or more. A silver halide photographic light-sensitive material characterized in that Embedded image (In the formula, Z ₁ and Z ₂ each represent a non-metal atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. R ₁ and R ₂ are each a substituted or unsubstituted alkyl group. Base,
It represents a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group, and at least _one of R ₁ and R ₂ is a sulfoalkyl group or a carboxyalkyl group. R ₃ represents an alkyl group. X ⁻ represents an anion, n
Represents 1 or 2. However, n is 1 when forming an intramolecular salt. ) 2. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 1 within a total processing time of 35 seconds. 3. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has an average silver chloride content of 10 mol. % And average aspect ratio is 3
The amount of gelatin in the non-photosensitive layer containing the above silver halide grains and being outside the silver halide emulsion layer (on the side farther from the support) is 0.9 g / m ² or less, and The silver halide photosensitive material has a temperature of 15 to 30 ° C and a relative humidity of 40 to 60%.
A silver halide photographic light-sensitive material characterized by being packaged under the conditions of. 4. A method of processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 3 within a total processing time of 35 seconds or less.