JPS6147941A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance high illumination sensitivity of a silver halide photographic sensitive material and to improve storage stability by forming silver halide grains each composed of two layers of a core, and a shell contg. a specified amt. or more of silver chloride, and iridium. CONSTITUTION:Each silver halide grain is of a 2-layer core-shell type structure, and the shell contains silver halide composed of silver chloride, bromide, iodide, etc., contg. >=80mol% silver chloride, and further, iridium is incorporated in both layers, and iridium and silver chloride are incorporated higher in the shell than in the core. These silver halide grains of laminate structure can be prepared by first forming silver halide in the core, and successively laminating silver halide in the shell, and incorporating silver halide grains to obtain photosensitive material high in sensitivity. Since a prescribed silver chloride and iridium are incorporated in the shell, the obtained photosensitive material is high in sensitivity and can form a photograph low in fog and high in contrast.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention uses as a developing agent a lithium developer consisting of a single hydroquinone developing agent or a hydroquinone developing agent and a superadditive developing agent. This article relates to a silver halide photographic material suitable for being processed with a general high contrast black and white developer, and more specifically, does it have good storage stability?
The present invention relates to a silver halide photographic material that has high gradations and high sensitivity (especially sensitivity to high illuminance).

[Conventional technology]

It is known to dope iridium atoms inside silver halide grains in order to obtain silver halide grains with high sensitivity under high illuminance.Silver halide photography is possible by increasing or decreasing the amount of iridium doped inside the grains. This technology is widely admired because it allows the high-intensity characteristics of photosensitive materials to be controlled.

Silver halide photographic materials doped with iridium salts inside the grains can provide photographic properties with high sensitivity to high illuminance, but their photographic properties have the drawbacks of increased capri and difficulty in obtaining high-contrast xmu properties. there were.

In order to eliminate this drawback, for example,
As described in No. 81, a method is known in which a ronium salt is added simultaneously during the production of silver halide grains containing an iridium salt. However, although the manufacturing method that adds rhodium salts provides high contrast characteristics, the sensitivity is low (and the stability that the customization is lost during storage).
There are two shortcomings.

In order to improve this drawback, for example, JP-A-52-110
As described in Japanese Patent No. 29, a method of stabilizing the composition by incorporating a compound such as hydroquinone is known.

However, even with this method, when the high-light, high-sensitivity effect of the iridium atoms is brought out, the capri is high and the storage stability is not sufficient, so a method for further improvement is desired.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material that has high sensitivity to high light and excellent storage stability.

A further object of the present invention is to provide a silver halide photographic material with high contrast and high sensitivity, in which increase in capri during storage is suppressed without adversely affecting other photographic properties.

[61st aspect of the invention] The present invention which achieves the above object has a laminated structure composed of at least 2fvj of a core part and a grain part in a hydrophilic colloid layer, and has a halogenated colloid which is aged without being fogged. In a silver halide photographic light-sensitive material containing silver grains, silver lodenide in the grain part of the grains has a silver chloride content of 80 mol % or more and contains iridium atoms; The silver chloride content and iridium content of the 1T2 silver denride are characterized in that they are higher than those of the inner core of the grains.

The following techniques are known as techniques related to the present invention having such 5rjt.

That is, the inner core is chemically aged as a halogenated lta grain having a laminated structure of at least 1,2/If, and a silver halide layer is deposited thereon to form a grain member, that is, an outer shell (layer).
A silver halide photographic light-sensitive material is known in which a blurred image is obtained by fogging the surface of the outer shell (layer) with a reducing agent (for example, hydrazine, tin salt, 7-scorbic acid, etc.). There is.

However, this method differs from the present invention in its structure and operation and effect because it has capri properties when the particle surface is fogged.

The present invention will be explained in detail below.

The silver halide grains of the present invention are silver halide grains in which a grain part (/1 it) having a silver halide composition different from that of the core part is laminated on a silver halide constituting a core part within the grain. . The silver halide forming the grain may be any of silver chlorobromide, silver chloroiodobromide, and pure silver chloride, but
The content of silver chloride is higher than that of the grain core, and the composition of the silver halide photographic light-sensitive material is 80% as chloride ja tit.
It has a mole of X or more and also contains an iridium atom.

The silver iodide content in the core and grain of the grains is 5% or less, preferably 2 mol% or less, and the respective contents may be different from each other.

In addition to laminating the shell directly on the core of the silver halide grain, the intermediate shell of silver halide (/1
The grain part (outermost shell part) having the above composition may be laminated through the silver halide part (it) of the core part or the outermost shell part, and the intermediate shell part may be the same as or different from the silver halide part of the core part or the outermost shell part. The core may be halogenated ff1jfl, pure silver bromide, silver chlorobromide or silver chloroiodobromide, but silver chlorobromide or silver chloroiodobromide is preferred.

In order to obtain the desired performance of the present invention, the grains are produced so that the grains of the silver halide grains contain iridium atoms (the outermost shell if the grain has an intermediate shell, the same shall apply hereinafter). However, the content of iridium atoms in the core is lower than the content of iridium atoms in the shell.

To contain metal atoms including iridium atoms, form metal salts in any form of single salt, double salt, or complex salt and use particles W4D.
J, may be added at times, such as potassium hexachloroirinoate, sodium hexachloroiridium salt, ammonium hexachloroirinoium, etc. (alkali metal ions, alkaline earth metal ions,
7 ammonium ion, etc.

The content of iridium atoms in the grain part is 1 x 10-1 to IXIG per mole of halide/silver oxide in the grain part.
-4 mol is preferable, and the core contains 1 x 10-
5 moles or less, less than the grain (contains).

The silver halide grains constituting the inner core of the present invention have an average grain size of 0.02μ+1 to 1.0μ, preferably 0.02μ+1 to 1.0μ.
Particles with a narrow particle size distribution of 0.05 μm to 0.6 μm and a deviation of particle size from the average particle size of less than ±20% are preferable,
The final silver oxide grains produced by laminating on the inner core of the grains of the present invention have an average grain size of 0.05 μm to 1.5 μm;
Silver halide grains are preferably 0.1μ to 0.8μ and have a laminated structure with a narrow particle size distribution in which the particle size deviation from the average grain size is less than ±20%, similar to the core part. .

The inner core of the particle of the present invention may contain atoms of a metal such as puffusium, rhodium, platinum, metal, thallium, alligator, lead, osmium, etc., so that the atoms are localized on the surface of the inner core of the particle. The content of these tt group atoms, which may be precipitated, is preferably IXIG-' mole or less per mole of silver halide in the core of the grain.

The optimum amount of 4 can be determined depending on the atomic species, the state of the particles, and the desired performance.

In order to prepare the silver halide grains of the present invention, the mixing conditions are 35°C to 80°C, preferably 50°C to 70°C1p.
H2-p118, preferably high-pA with sufficient stirring speed to mix uniformly in the protective colloid solution using inert gelatin, preferably pl+4-6.5, 6-9
Preferably, it is prepared in

In order to form silver halide grains having a laminated structure according to the present invention, first, a silver halide grain serving as a core is formed,
Subsequently, the grains were laminated by adjusting the temperature and pH1ilAlt, and the core silver halide grains were formed, followed by washing with desalinated water, and the temperature, pH and pATl were adjusted again to form the silver halide grains. It's okay.

The volume ratio of the core part and grain part of the particle is 1:100 to 10.
It can be arbitrarily selected between 0:1, but 1:10
Preferably, the ratio is between 10:1 and 10:1.

The silver halide grains of the present invention are 'I! 4, the molar excess of halide when forming the core and shell is 5 to 60% molar excess based on the amount of silver halide to be reacted to form a precipitated layer of silver halide. In particular, the molar excess of halide is preferably in the range of 10 to 40 mol %.

Further, the time for forming the silver halide in the core and the V grain is at least 30 seconds, preferably at most 60 minutes, and particularly good results are obtained when the time is from 1 minute to 30 minutes.

The monodispersity of the a-sized rice grains having a structure of m/1!16 according to the present invention is such that the fluctuation coefficient of the particle size distribution is preferably 20% or less. The particle diameter is expressed as a square, and when it is a cube, it is calculated as the edge IX-, and the average is determined by algebraic averaging. Moreover, the above-mentioned fluctuation coefficient is a value expressed in % of the value obtained by dividing the Kufu deviation of the particle diameter by the average particle diameter.

The iridium atom used in the present invention may be an iridium salt such as an iodide, a bromide, a urea compound, or a pigmented compound in addition to those listed above, but a water-soluble salt of a chloride or bromide is preferable.

In order for the silver halide particles to exist in the silver halide grains, it is preferable to add the silver salt to the water-soluble silver salt or to the halide solution when simultaneously mixing the water-soluble silver salt and the water-soluble halide solution, or to add the silver salt to the water-soluble silver salt or to the halide solution. and halide solution are mixed simultaneously, 38! as a solution of ill'13! Silver halide grains may be mixed with i8I* by a simultaneous mixing method,
゛In order to selectively contain iridium in the shell portion of the silver halide grains of the present invention, when simultaneously mixing an aqueous halide solution as a silver salt as a grain portion, the above water-soluble iridium is dissolved in a /1ride solution. It is desirable to keep it.

The laminated silver halide grains of the present invention are ripened with the following sulfur compounds and all compounds to form finally shaped grains.

This ripening is usually called chemical ripening, which is widely known in detail in the photographic field and can be easily carried out.

Sulfur compounds used in the present invention include sodium thiosulfate, furyl thiourea, alliruna 1+rea, phenylthiourea, thiosemical/<nod, thioacetamide,
Examples include alkylthiocarbamates.

Gold compounds used in the present invention include sodium tetrachloro'itate, potassium nato-dichloroaurate, potassium nobromate, potassium dibroaurate, sodium trichromeaurate, notiosul 7y) total a sodium, notiosul 7
7) Examples include potassium acid.

The amount of the chemical sensitizer used is not particularly limited, but the amount of gold compound added is IX 10-' per mole of silver halide.
~IXI (1-' mol, the weight of the sulfur compound added is preferably QIXlo--IX 10-' mol per 1 mol of silver halide, and the molar ratio of both is 1
:10 to 10:1 is preferable.

The chemical sensitization using the gold-sulfur compound of the present invention has high surface sensitivity with less capri, and the photosensitive nucleus is silver-total sulfide.
It is distinguished from reduction sensitization and capri ripening.

The hydrophilic colloid used in the hydrophilic colloid layer of the present invention is
It is most preferable to use gelatin as the protective colloid in the silver halide photographic emulsion, and gelatin derivatives and synthetic hydrophilic polymers may also be used in combination.

The photographic light-sensitive material of the present invention is formed by coating on a support at least one silver halide photographic emulsion layer containing silver halide grains according to the present invention. In addition, photographic constituent layers such as a subbing layer, an intermediate layer, and a protective MLWi may be coated.

Supports used in the photographic light-sensitive material of the present invention include, for example, Bahuita paper, polyethylene-coated paper, polypropylene synthetic paper, lath board, polyester film such as 7-alpha-sulfontate, cellulose nitrate, and polyethylene terephthalate. Typical examples include polyamide film, polypropylene film, polycarbonate film, polystyrene film, etc., and these supports are appropriately selected depending on the intended use of the silver halide photographic material.

In order to further improve storage stability, the hydrophilic colloid layer used in the present invention may contain a polyhydroquine benzene compound (typical examples include, but are not limited to) The polyhydroxybenzene compound preferably used in the present invention is a compound based on a structure having at least two hydroxyl crystals in the benzene ring, and any part other than the hydroxyl group is substituted with a hydroxyl group. substituents, such as halogen atoms,
The use of this polyhydroxybenzene compound, which may be optionally substituted with a furkyl group, a substituted furkyl group, an alkoxy group, a sulfonic acid group, a carboxy group, etc., varies depending on the MiM of the silver halide photographic light-sensitive material and the purpose of use. However, in general, 0.1 to 30 mff 1 part is preferable per 100 parts by weight of hydrophilic colloid, and these compounds may be added in the same manner as for dyes having acidic groups. ] When the above-mentioned non-photosensitive calendar is grooved, a polyhuman 10-oxybenzene compound may be added to the wood-philic colloid layer adjacent to the hydrophilic colloid layer containing the dye having an acidic group, or the same It may also be added to the hydrophilic colloid layer.

[Exemplary compounds]

0Ji @) CH.

(Ii Hatake L; Jig OH The photographic emulsion containing the silver halide grains of the present invention is
3-17720. The sensitizing dye described in the above publication may be added, and by spectral sensitization in this manner, higher sensitivity characteristics can be obtained.

Hydrophilic colloid I'/i! containing an emulsion layer containing silver halide grains of the present invention! l contains various photographic additives as necessary, such as gelatin plasticizer, hardener, surfactant, image stabilizer, ultraviolet absorber, 7/thisteine agent, pH adjustment 5
! Scraping, antioxidant, 417m inhibitor, thickener, graininess improver, dye, mordant, brightener, development speed! pl! i
Agent E, matting agent, etc. can be used within the range that does not impair the effects of the present invention.

Among the various additives mentioned above, those that can be particularly preferably used in the present invention include, for example, thickeners or plasticizers such as those described in US Pat. No. 2,960,404, Japanese Patent Publication No. 43-4939, West Germany's Rokkō Announcement No. 1.904
, 604 specification, JP-A-48-63715, JP-A-45-15462, Belgian Patent No. 762
．． No. 833, US Pat. No. 13.7G7.410, Belgian Patent Nos.
Various hardening agents such as dextran sulfate, aldehyde type, epoxy type, ethyleneimine type, active halogen type, vinyl sulfone type, sulfonic acid ester type, carbodiimide type, mufuchloric acid type, acyloyl type, etc., UV rays As an absorbent, for example, Hikokumachi RF No. 3,253.

No. 921, British Patent No. 1.309,349 Specifications 8
In particular, 2-(2'-hydroxy-5-3M butylphinyl)benzotriazole, 2
-(2'-hydroxy-3',5'-no-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-3abutyl-5'-butyl7enyl)-
Examples of dyes include 5-chlorobenzotriazole, 2-(2'hydroxy-3'.5'-no-tertiary butylphenyl)-5-chlorobenzotriazole, and dyes such as U.S. Pat. No. 908, Monkey Patent No. 107,990, U.S. Patent No. 3.048.487, U.S. Patent No. 515.998, etc. can be used, and these compounds are Baochu eyebrows,
It may be contained in an emulsion or an intermediate layer. Furthermore, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and various physical properties of photosensitive materials can be controlled.
Examples of surfactants used for coating include British Patent No. 548.532, British Patent No. 1,216,389, and U.S. Patent No. 3.026.202, British Patent No. 3,514,29.
Specifications of No. 3, Japanese Patent Publication No. 44-26580, No. 43
- No. 17922, No. 43- No. 17926, No. 43-
13166, French Patent No. 48-20785, French Patent No. 202,588, Belgian Patent No. 773.
Anionic, cationic, nonionic, or amphoteric compounds described in the specifications of No. 459 and Vf Patent Publications No. 48-101118 can be used.
In addition, antistatic agents are disclosed in Japanese Patent Publication No. 4B-24159, Japanese Patent Application Laid-Open No. 48-89979, and U.S. Patent fj
Specifications of S2,882,157 and 2,972.535, JP-A-48-20785, and JP-A-4B-43H
No. 30! :! ! Approved No. 90391, Special Publication No. 1973-2
No. 4159, No. 46-39312, No. 48-4
3809, U.K. 47-33627, etc., and as matting agents, for example, British Patent No. 1,221.980, U.S. Patent No. 2
．． Specifications of No. 992,101, No. 2,956.884, French Painting Patent No. 1,395゜544, Japanese Patent Publication No. 1973
Compounds described in -43125, etc., especially 0
．． Nricadel with a particle size of 5 to 20 μ◎, 0.5 to 2
Examples include polymers of polymethyl methacrylate having a particle size of 0 μI.1 The photographic light-sensitive material of the present invention contains a Liss developer consisting of a single hydroquinone developing agent or a hydroquinone developing agent and a hydroquinone developing agent as a developing agent. Suitable for processing with a general high contrast black and white developer containing a additive developing agent.

Examples of the developer that can be included in the developer used for developing the photographic material according to the present invention include the following.

Typical HO-(C8=C11)n-OB type developers include catechol, pyrogallol and its derivatives, and ascorbic acid, as well as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-nochlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-nohydroxyacetophenone, 2,5-methyl/1hydroquinone, 2,5-no p-7enethyl 1-hydroquinone, 2,5-nobenzoylhydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-722-catechol, 3-methoxy-catechol, 4-7 cetyl-pyrorolyne, 4-(2
゛-Hydroxybenzoyl)pyrogallol, 7-sodium scorbate, etc.

Typical HO-(C=C)n-NHz type developers include ortho and rose 7-minophenols or aminopyrazolones, such as 4-7 minophenol, 2-7 mino-6-7 dynylphenol, and 2-7 minophenol. -7mi/-4-chloro-6
-722phenol, 4-7minor-2-phenyl7er/-l, 3,4-noamino7er/-l, 3-methyl-4
, 6-lyamino7enol, 2,4-noamylzoldial, 2.4.6-)lyamino7enol, N-methyl-9-7mino7enol, N-β-hydroxyethyl-p -7minol, p-human phenylamine/acetic acid, 2-amino/su7tol, etc.

Examples of the 1(2N-(CI=CH)n-82N type developer include 4-amino-2-methyl-N, N-noditylaniline, 2.4-77 minnow N, N-noethylaniline, N -(4-7mi/-3-methylphenyl)-morpholine, p-phenylenenoamine, 4-ami/-N,N
trimethyl-3-hydroxyaniline, N, N, N, 'N
'-Tetranotyl paraphenylenenoamine, 4-amino-N-ethyl-N-(β-hydroquinethyl)-aniline, 4-7mi/-3-methyl-N-(β-hydroxyethyl)-aniline , 4-7minor N-ethyl-(β-nodoxyethyl)-3-7thylaniline, 4-7min/-
3-Methyl-N-ethyl-N-(β-methylsulfonamidoethyl)-aniline, 4-amino-N-butyl-N
-γ-sulfobutyl 7niline, 1-(4-7mi/phenyl)-pyrrolinon, 6-7minor 1-ethyl, 1,2,
3.4-tetrahydroquinoline, etc.

Examples of the heterogeneous developer include 1-phenyl-3
-Pyrazolidone (phenidone), 1-7znyl-4-7
Minnow 5-pyrazolidone, 1-(p-7 minophenyl)
-3-7mi/-2-pyrazoline, 1-phenyl-3-methyl-4-7mi/-5-pyrazolone, 4,4'-tumethyl-1-phenyl-3-pyrazolidone (thumesin), 5
-Aminouracil, 1-phenyl-4-methyl-4'-
Hydroxynotyl-3-pyrazolidone and the like.

The theory of the photographic process, 4th edition (The Theo
ry of the Photographic Pr
cess, Fourth Edition) No. 291~
334 pages and Journal of the American Chemical Society.
American C1+emical 5oci
The developer described in Vol. 73, p. 3100 (1951) of E.Ly)tjS can be effectively used in the present invention. These developers may be used alone or in combination of two or more, but 2! It is preferable to use a combination of lIi or more. A preferable combination is a combination of hydroquinone and 7-enidone or hydroquinone and tunosin, and hydroquinone is used in an amount of 5 g to 50 g/
Q. Also, phenidone or thumecin is 0.05-5g/
It is suitable to use within the range of 'l.

Furthermore, even if sulfites such as sulfite, potassium sulfite, and ammonium sulfite are used as preservatives in the developer used in the present invention, the effects of the present invention will not be impaired.
This can be mentioned as one of the features of the present invention. ! [1
, the sulfur a salt concentration is preferably 0.06 to 1 gram ion/Il. In addition, hydroxyamines and hydrofuside compounds may be used as preservatives, and other additives such as caustic alkali, carbonate alkali, or amines used in general high-contrast black and white developers may be used to provide pH att and baffle functions. Inorganic development inhibitors such as ethylene no.
Metal ion scavengers such as minotetraacetic acid, metal ion scavengers such as methanol, ethanol, benol alcohol, polyalkylene oxide, etc., sodium alkyl 7-lylsulfonates, natural saponins, sugar M or furkyl esters of the above compounds. It is optional to add surfactants such as esters, hardeners such as glutaraldehyde, formalin, glyoxal, and ionic strength regulators such as sulfuric acid. pll can be set arbitrarily from 9 to 12, but from the viewpoint of preservation and photographic performance, it is preferable to use pll in the range of p +t to ~11.Alkanolamines or alkanolamines may be optionally added as a growth solvent in the developer. Glycols can be contained.

Examples of the alkanolamine include monoethanolamine, jetanolamine, triethanolamine, etc., and triethanolamine is preferred. The preferred usage amount of these flukanolamines is as follows:
10-500g per liter, especially 30-500g per developer IQ
300g is preferred.

Examples of glycols include ethylene glycol, queethylene glycol, propylene glycol, triethylene glycol, 1,4-butanol, 1,5-bentanol, etc., with noethylene glycol being preferred. The preferred amount of these glycols to be used is 10 to 500 g per developing unit.
30 to 300 g per i11 is preferred.

The above alkanolamines and glycols may be used alone or in combination of 2 m or more.

In the present invention, 5-nitroingzole, 6-nitroingzole, 5-methylbenztrizole, 6-nonalpenzotriazole, 5-nitrobencyimigzole, 5-nitrobencyimigzole, 1-phenyl -5
- A development inhibitor such as mercaptotetofuzole can be used, and the preferred amount used is 1X per ill of developer solution.
10-1 to 1x to-' mole, especially developer solution 1n
The amount of the development inhibitor is preferably from 1.times.10@-2 to 1.times.10@-' mole per developer, and it is preferred that the development inhibitor is dissolved in the alkanolamine and glycol before being added to the developer.

The photographic material of the present invention can be processed under various conditions. For example, the processing temperature is 50℃ or less/'J
: Preferably, particularly preferably around 38°C, and the development time is generally completed within 2 minutes, but particularly preferably within 30 seconds often brings about good results, and processing steps other than development, e.g. It is optional to adopt steps such as water washing, stopping, stabilization, fixing, and if necessary, pre-hardening and neutralization, and these steps can be omitted as appropriate. , so-called manual development such as frame development, or mechanical development such as roller development or hanger development.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples. The technical scope of the present invention is not limited in any way by the following Examples, and various implementations = a are possible.

Example 1 Comparative emulsion 3Wsl (EM-1) Solvents QB and C were simultaneously added over 50 minutes to solution A kept at 40°C while maintaining pH 3 and pAg 7.
After continuing to stir for another 10 minutes, 1 lk 1.2 Q of a 20% aqueous magnesium sulfate solution and 1.5 g of a 5% aqueous solution of polynaphthalene sulfonic acid were added, and the emulsion was 70 chelated at 40°C. Decant the mixture and wash with water to remove excess water-soluble salts. Next, add 2.22 g of water and disperse. Add 83 g of inert gelatin and disperse. This resulted in 35 mol% silver bromide and 65 mol% silver chloride.
, particles with an average particle diameter of 0.20° C. are obtained.

80% sodium thiosulfate aqueous solution. ll, 8011u of 10.2% chloroauric acid aqueous solution, and 100+all of 1% potassium iodide water Sa, and then heated to 50℃~6
The emulsion is ripened at a temperature of 0° C. and a GIH of 5.5-6.5 for maximum sensitivity.

Add 4-hydroxy-6-methyl-1,3°3m to the above emulsion.
, 1% methanol solution of 7-chitra7zaindene 830
-1 As a sensitizing dye, (1) having the following GIH structure is used as a sensitizing dye.
．． 7g, 0.5g of (b), 20% saponin aqueous solution 100+all as a spreading agent, styrene as a thickener.
4% aqueous t166+IQ of maleic acid copolymer, polyethylene glycol (molecule 13000) as development accelerator
1.7g.

300 ethyl acrylate high grade latex polymer
g, 8 g of hydroquine as a capri inhibitor, 0.7 g of 1-phenyl-5-mercaptotetofuzole and 5 g.
-Add 0.5g of methylbenzotriazole and use 2,4-fuchloro6-oxy-S- as a hardening agent +77
Non-sodium salts and formalin were added, and the above emulsion was deposited on a subbed polyethylene terephthalate support with an amount of silver of 3 and an amount of Og/-"s gelatin of 1.5 g/
The sample was heated at 320 C.
MS tungsten was subjected to wedge exposure and developed in a developer having the composition shown below.

Preparation of the emulsion of the present invention (EM-2) Solution B and C were simultaneously added over 40 minutes to molten tA kept at 40°C while maintaining pH 3 + pAg 7.
After further aging for 5 to 11 times with continued stirring, the solution solution kept at 40°C and VE were added at the same time for 10 minutes while maintaining the pH at 13, pA, and 7, and then for another 10 minutes.
After continuing aging for a minute, 20% magnesium sulfate water tF
Solution I 1.2Q and a 5% aqueous solution of polynaphthalene sulfonic acid 11!1,511 were added and the emulsion was brought to 40°C to flocculate, followed by decantening and washing to remove excess water-soluble salts. Remove 1 and then add 2.2 liters of water to disperse it and add 166 g of inert gelatin and disperse. As a result, grains having an average grain size of 0.20° C. were obtained, in which the core was composed of 30 mol % of silver bromide and 70 mol % of silver chloride, the grain was composed of gAML chlorobromide, and was doped with ilinium atoms. The volume Mi composition ratio of the core part and the grain part of the particles was 1:1. Samples of EM-1 particles were No. 1,
The results obtained with the EM-2 particle sample as 80.5! -1.

[Developer treatment method]

A commercially available fixer for quick processing was used as the fixer, and the processing was carried out under the following conditions.

The two types of sensitizing dyes added to the emulsion are as follows.

(b) Addition of water-soluble heloid melt 1 of EM-2 and addition amount of water-soluble iridium salt to prepare samples as shown in Table A below and conduct sensitometry (xenon flash discharge tube,
Exposure time 10-' seconds) was performed. Results Table 1 Funcirus F was expressed as a numeral value for the exposure amount giving densities of 0.2 and 1.5. Storage test was conducted at 25℃ and 50% relative humidity for 12 hours after application. ! After moistening, it was tightly packaged and stored under harsh conditions at a constant temperature of 50°C for 30 days, and the performance immediately after application was compared.

As is clear from Table 1, the samples of the present invention (No. 14,
L, L9-12.14-16) are comparative samples (No.
1-3.5° 8.13.17-19), the sensitivity is higher, and it can be seen that storage stability can be improved without particularly adversely affecting photographic performance.

Example 2 An experiment was conducted in the same manner as in Example 1, but in this experiment, samples No., Z, No. 4 of Example 1 were used. No.8 and No.1
1 and processed with a developer having the following composition. The developing process was carried out under the same conditions as in Example 1. The results are shown in Table-2.

[Developer prescription]

Pure water
500. σEthylenoaminetetraacetic acid/Nina)ium salt 2g Potassium sulfite 50% aqueous solution 190g Hydroquinone 20° Potassium carbonate
30! +5-methylbenzotriazole 30mH5-nitroingzole 1ootB1-phenyl-5-mercaptotetrazole 50 ethylene glycol 30g potassium bromide
Add 2g polyethylene glycol (molecular weight 3000) and 2g water
1 standing (p in potassium hydroxide) 112
．． (adjusted to 0) As is clear from Table 2 2!22, sample No. 4 of the present invention
Ogami (/No. 11 is comparative sample No. 2 and V No. 8
It can be seen that even a halide quinone single-drug developer is effective against this.

〔Effect of the invention〕

The silver halide rX photosensitive material according to the present invention has high sensitivity to high illuminance, low capri, high contrast photographic characteristics, and excellent storage stability.

Agent: Patent Attorney No. 1) Written amendment to parent-in-law proceedings January 30, 1985 Manabu Shiga, Commissioner of the Japan Patent Office Patent Application No. 170937, filed in 1982 2, Title of invention: Silver halide photographic light-sensitive material 3.111 Correct. Name of the person making the amendment (127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 〒191 6, “Detailed explanation of the invention” column 7 of the memorandum of amendment countermeasures, Contents of the amendment (1) Details of the invention in the description Corrected the explanation as shown in the table below (2
) Page 31 of the specification, lines 15 to 18 rr [Furthermore, make the sensitivity higher. 5. Add 100 ml of 5% aqueous potassium potassium solution and heat to 62°C.
The emulsion is ripened in 9H of 5. ” he corrected.

(3) Page 32, line 9 - 1B13th “0.51+
...3.0 g/ring 2, was added to make an emulsion preparation g, a liquid. Separately, a gelatin aqueous solution was prepared as a protective film liquid, and noethylhexyl was added to this aqueous solution as an aM. Sulfosuccinate sodium salt and silica with an average particle size of 3.5 microns were added as a matting agent.

Using the above emulsion adjustment solution and protective film adjustment solution, an emulsion layer and a protective layer were coated simultaneously on a polyethylene tetralate support using a simultaneous multilayer coating machine. Apply 2.4-fuchloro6-oxy-S-cyanone sodium salt and formalin as a hardening agent just before application! added to the membrane solution. ffl amount 3. O+r/-2,'' is corrected.

(4) 9th to 11th stroke rE M on page 34 of the same tlS
Samples of rEM-1 particles shown in -1...- are designated as No. 1, and the halide composition of the particles was changed in accordance with the preparation of EM-1 particles to obtain samples No. 2 and V No. ,
3 was created. *Sample No. 5 was created from the EM-2 particles, and the sample No. 4 was prepared by removing ilinium during the preparation of EM-2 particles. The remaining samples up to No. 19 were prepared with the configurations shown in Table 1 while changing the halide composition of the grain and the amount of iridium added.

The above sample was exposed to light through a W1 stepped wedge using a xenon WLlfF light source and an exposure time of 10-s seconds.

The processing was carried out according to the developer formulation and processing process shown below. The results obtained are shown in Table 1.''

(5) Structure of the following sensitizing dye (,) on page 35, line 15 of the same page (6) Lines 3 to 8 of page 36 of the same page ``Additionally, the above sample No. 1...'' ...Results are shown in Table 1.'' is deleted.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having a laminated structure consisting of at least two layers, a core part and a shell part, in a hydrophilic colloid layer, and containing silver halide grains that have been aged without being coupled. , the silver halide in the shell part of the grain has a silver chloride content of 80 mol % or more containing iridium atoms, and the silver chloride content and iridium content of the silver halide composition in the shell part of the grain are equal to A silver halide photographic light-sensitive material characterized in that the inner core is larger than that of the inner core.