JPS62275236A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the scratch and a change in the sensitivity by stress and to improve the stress characteristics by forming a negative type silver halide emulsion layer contg. specified particles and an outer hydrophilic colloidal layer contg. a matting agent of >=2.0mum average particle size. CONSTITUTION:This silver halide photographic sensitive material has a negative type silver halide emulsion layer contg. multilayered silver halide particles having <5 ratio of diameter to thickness by projection and an outer hydrophilic colloidal layer contg. a matting agent of >=2.0mum average particle size. The iodine content in the 1st coating layers of the silver halide particles is higher than that in the cores by >=10mol%, preferably 40-100mol%, the amount of silver in the 1st coating layers is 0.01-30mol%, preferably 0.05-10mol% of the amount of all the particles and the iodine content in the 2nd coating layers is 0.001-10mol%, preferably 0.005-5mol%. When a silver halide emulsion layer is of negative type, the surface sensitivity is equal to or higher than the internal sensitivity, preferably >=2 times the internal sensitivity.

Description

[Detailed Description of the Invention] 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photographic photoluminescent material (hereinafter sometimes abbreviated as "photographic window material"), and in particular to a negative-working halogen emulsion. The present invention relates to a silver halide photographic material containing a layer.

[Conventional technology]

Various mechanical stresses are applied to photographic materials coated with a silver halide emulsion.For example, when photographic negative film is rolled into a cartridge or loaded into a camera, it is folded and There are opportunities for it to be touched, pulled for frame-by-frame progress, and subjected to friction as it comes into contact with various parts.

In addition, all window materials are subject to large stress and r! during cutting and processing. ! subject to frictional force.

As described above, when various stresses are applied to the photographic window material, stress is applied to the silver halide grains through gelatin, which is a holder (binder) for the silver halide grains, and plastic film, which is a support, as a medium. It is known that when stress is applied to silver halide grains, changes occur in the photographic properties of photographic materials, such as K.H.'? Buzzer K, Il,
Mather), Journal of the Optical Society of America (J, Opt, Soc.
, Am, ), 38.1054 (1948),
P Feelens and P de Sumenot (
P, Faelens and P, de 5rne
t), Chance/Industrial Photography 4 - (Sci, et Ind, Photo
, ) , 25 , Δ! i5,178(1
954), P. Faelens
), Journal of Photographic Science (J, Phot, Sci), 2.105(1
954) and others.

Desensitization of the stressed areas causes sensitization or fogging, which not only significantly impairs image quality but also poses a risk of misdiagnosis in the case of X-ray sensitive materials.

Therefore, it is strongly desired to provide a photographic material whose photographic properties are not affected in any way by these stresses.

Measures to improve pressure characteristics include adding plasticizers such as polymers and emulsions, and reducing the silver halide/gelatin ratio in silver halide emulsions to prevent pressure from reaching the grains. something is known.

For example, British Patent No. 738,618 describes heterocyclic compounds, British Patent No. 738,637 describes alkyl phthalates)4, British Patent No. 738,639 describes alkyl esters, and U.S. Patent No. 2,960,404 describes polycyclic compounds. alcohol, 3,1
No. 21,060 contains calzexialkyl cellulose,
Japanese Patent Publication No. 49-5017 discloses a method using .xi. roughin and calzenate, and Japanese Patent Publication No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

However, since the method of adding a plasticizer reduces the mechanical strength of the emulsion layer, there is a limit to the amount of plasticizer that can be used, and increasing the amount of gelatin causes drawbacks such as slowing down the processing speed. It is also difficult to achieve sufficient effect.

Therefore, it is desirable that the layer itself is resistant to stress.

By the way, for example, if silver nitrate is added to a solution containing gelatin, potassium bromide, and potassium iodide, the resulting emulsion will have a marked decrease in photosensitivity when pressure is applied, which is extremely inconvenient in practice. The characteristic of desensitizing to light when such stress is applied is created by adding pure silver bromide or a solution of silver nitrate and/or chlorides using the double jet method to prevent re-nucleation. This property is improved in completely uniform silver iodobromide grains. However,
On the other hand, the particles tend to easily bulge under stress, which is not desirable in practice.

On the other hand, it was reported in JP-A-53-2240 that development activity could be increased and sensitivity could be increased by using laminated type silver halide grains in which multiple shells were attached to the outside of an inner core.
Publication No. 8, Special Publication No. 13162/1984, Journal of Photography, Inc. Science (J, Ph.
oto, Sci, ) +24.196 (1976
) etc.

However, silver halide grains obtained for these purposes do not necessarily improve stress properties, and problems such as stress-induced desensitization and capri occur. For example, JP-A-53-2
Publication No. 2408 describes pure silver bromide (inner core)/silver iodobromide (
Laminated type silver halide grains consisting of pure silver bromide (iodine content 1 mol %)/pure silver bromide have been described, but fogging due to pressure occurs strongly, and from the viewpoint of pressure characteristics, it is different from the conventional completely uniform iodine odor. There are problems similar to those of silver oxide emulsions.

Silver halide grains in which a coating layer is provided on the outermost layer of silver halide grains by halogen substitution are disclosed in West German Patent No. 293265.
No. 0, Japanese Unexamined Patent Publication No. 51-2417, No. 51-1743
Although these silver halide grains can speed up the fixing speed, they actually inhibit development, making it impossible to obtain sufficient sensitivity. It is not practical as a film-type emulsion.

Further, monodi-type (internal latent image type) silver halide grains having a plurality of coating layers on the outside of the inner core by halogen substitution are known, as described in U.S. Pat. No. 2,592,250, Specification No. 4,075,020, JP-A-55-12754
It is described in detail in Publication No. 9, etc. These silver halide grains are often used in internal latent image type direct positive light-sensitive materials such as those for diffusion transfer, and because of their high internal density, they cannot be used in the negative emulsion that is the object of the present invention. It is not used at all.

Sensitization of this type of silver halide grain surface is also described in German Patent No. 2,932,650, but the use of such silver halide emulsions does not improve stress properties at all.

For example, in the specification of JP-A-5S-X27SA9,
A silver halide emulsion is described in which almost 100% of the inner core is converted to silver iodide by converting chlorine to bromine and bromine to iodine in the inner core, and then the inner core is coated with silver iodobromide. However, it is not used because pressure desensitization occurs strongly.

Even if the surface of the particles were subjected to sensitization treatment and turned into a negative type, pressure desensitization would still occur strongly, making it impractical.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide emulsion free from such problems, and thereby a silver halide hole photographic light-sensitive material which has little change in sensitivity due to stress and has improved stress characteristics, that is, pressure sensitization and pressure fog. Our goal is to provide the following.

[Structure of the invention]

It has been found that the above object can be achieved by using the silver halide emulsions described in JP-A-59-178447 and JP-A-60-35726 as shown below. That is, the above purpose is to provide an inner core made of silver bromide or silver iodobromide, a first coating layer made of silver iodide or silver iodobromide on the outside of the inner core, and a further substantial layer on the outside of the first N layer. and a second coating layer made of silver iodobromide having a low iodine content, which is silver bromide, or a second coating layer made of silver iodobromide having a different halogen composition from the first coating layer, and the ratio of the projected area diameter to the thickness is In silver halide grains having a particle diameter of less than 5, 11 the iodine content of the first coating layer is 10 mol% or more higher than the iodine content of the internal core, and (2) the ratio of silver in the first coating layer to the entire grain. (3) a negative silver halide emulsion layer containing grains, in which the iodine content of the second coating layer is 0.001 to 10 mol %; This is achieved by a silver halide photographic light-sensitive material comprising a hydrophilic colloid outer layer containing a 77 agent having an average grain size of 2.0 μm or more.

In the present invention, negative type has a meaning commonly used in the art, and refers to one whose surface sensitivity is equal to or higher than the internal sensitivity (preferably twice or more).

The size of the silver halide grains of the present invention is expressed by the projected area diameter, where the projected area diameter refers to the diameter of a circle of area equal to the projected area of the grain.

The size of the silver halide grains of the present invention is 0.3 to 5.
．． 0 μ is preferable, and 0.4 to 3.0 μ is more preferable.

Further, the ratio of the projected area to the thickness is less than 5, and the thickness here refers to the shortest length of the diameter passing through the center of gravity of the particle.

When the inner core of the present invention is made of silver iodobromide, it is preferably a homogeneous solid solution phase. Homogeneous here means 95 mol% of silver halide in the inner core in the distribution of silver iodide content.
is within 40% of the average silver iodide content.

As for the halogen composition of the internal core, the average content of iodine is preferably 10 moles or less, more preferably O~
5 mol %, particularly preferably 0 to 3 mol % 1.

The proportion of silver in the inner core relative to the silver in the entire particle is preferably 5 moltf or more, more preferably 10 to 95 moltf.

The silver iodide content of the first coating layer is 10 or more moles higher than the silver iodide content of the inner core, preferably 20 moles or more, particularly preferably 40 moles or more.

The silver iodide content of the first coated eyebrow is 100 moltyl, 10 molt, preferably 200 moltyl, 10 molt.
molti, more preferably 40 mol % to 100 mol %.

The ratio of silver in the first coating layer to the total silver of the particles is preferably 0.02 to 20 molt, more preferably 0.
．． 0.02 to 15 mole, particularly preferably 0.05 to 10 mole.

When the second coating layer consists of silver iodobromide, it does not necessarily have to be homogeneous, but it is more preferably a homogeneous silver iodobromide.

Further, the second coating layer needs to sufficiently cover the first coating layer, and for this purpose, the average thickness of the second coating layer is preferably 0.02μ or more, more preferably 0.04μ or more. be.

The silver iodide content of the second coating layer is preferably from 0.001 to
The amount is preferably 10 mol, more preferably 0.01 to 5 mol, particularly preferably 0.05 to 3 mol.

Further, the silver iodide content of the second coating layer is preferably lower than that of the first coating layer.

The ratio of the scissors of the second coating layer to the total silver of the particles is preferably 3 to 90 mol.

Although the size distribution of the silver halide grains of the present invention is arbitrary, monodispersity is more preferable. Here, monodisperse means a dispersion system in which 95% of the particles are within ±60 inches, preferably within ±40 inches of the number average particle diameter. Here, the number average particle diameter is the number average diameter of the projected area diameter of particles.

The proportion of silver halide grains in the emulsion layer containing the silver halide grains of the present invention may be arbitrarily selected, but is preferably 40% or more in terms of silver amount based on all silver halide grains. , particularly preferably 90% or more.

Next, a method for producing the silver halide emulsion of the present invention will be described. That is, generally silver bromide or silver iodobromide (iodine content of 10 molt or less)
After forming a core (inner core) consisting of, a first coating layer consisting of silver iodobromide or silver iodide is formed on the nucleus by a halogen substitution method or a coating method, and further on the first coating layer,
What is the first coating layer? In the method for producing three-layer structure silver halide grains in which a second coating layer consisting of silver iodobromide or silver bromide having a different halogen composition is provided, the iodide of the first coating layer is The silver halide grains are produced so that the silver content is 10 molti or more larger than the inner core, and the amount of silver in the first coating layer is 0.001 to 30 molti of the entire silver halide grain.

Details are described below.

First, the inner core of the silver halide grains of the present invention is described in Chimie Photographic by Glafkides, P.
etPhysigue Photography
) (Paul Mante 1, 1967),
・Photographic Emulsion Chemistry (Ph.D.) by G.F. Duffin
otographic Emulsion Chemi
(Published by The Focal Press, 1
966), Gui el Zelikman et al.
Making collating photographic emulsion collection (Makin) by Likman at al.
g and coating photography
c Emulsion) (The Focal Pr.
ess, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble silver salt is the one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As a form of simultaneous mixing method, silver halogenide is produced in the liquid phase? It is also possible to use a method of keeping pAg constant, that is, the chondral double jet method.
Wear. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

When preparing the inner core of silver halide grains, it is preferable that the inner core has a uniform halogen composition. When the inner core is silver iodobromide, it is preferable to use the double jet method or the controlled double jet method. Also,
When the inner core is silver bromide, the one-sided mixing method is preferred.

The PAg used when preparing the inner core varies depending on the reaction temperature and the type of silver halide solvent, but is preferably 7 to 11 degrees. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, commonly known silver halide solvents such as ammonia and thioether can be used.

The shape of the internal core is plate-like, spherical, and twinned. It may also be an octahedron, a cube, a tetradecahedron, or they may coexist.

The first coating layer of the silver halide grains of the present invention may be formed by a conventional halogen substitution method, a method of coating with silver halide, etc. after the formed inner core is subjected to a desalting step. There is one thing you can set up.

The halogen substitution method can be carried out, for example, by adding an aqueous solution consisting mainly of an iodo compound (preferably potassium iodo), preferably at a concentration of 10% or less, after the internal core is formed. At this time, 0.0 based on the number of moles of silver in the entire finished particle.
Add 1 to 30 moles of iodine compound. Further, at this time, PAg is preferably 5 to 12. For details, see U.S. Pat. No. 2,592,250, 4,07
This can be carried out by the methods described in JP-A No. 5,020, JP-A-55-127549, and the like.

At this time, in order to reduce the difference in iodine distribution between particles in the first coating layer, it is desirable that the concentration of the iodine compound aqueous solution be 10@-2 molti or less and the addition over 10 minutes.

A mixed system etc. can be used.

Furthermore, the inner core may be polydisperse (1) or monodisperse, but monodisperse is more preferable. Here, "monodisperse" has the same meaning as described later.

In addition, to make the particle size uniform, British patent 1, s
No. 35,016, Special Publication No. 4B-36890, 52-1
There is a method of changing the addition rate of K, silver nitrate, or alkali halide aqueous solution depending on the grain growth rate, as described in US Pat. It is preferable to use a method of changing the concentration of the aqueous solution as described above to grow quickly within a range that does not exceed the critical supersaturation degree. These methods do not cause re-nucleation and each silver halide grain is coated uniformly, and therefore are preferably used when introducing the first and second coating layers described below.

In the process of forming internal nuclei of silver halide grains or physically ripening, cadmium salts, zinc salts, lead salts, thallium salts,
As a method for newly coating the inner core with iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, etc., silver chloride aqueous solution and silver nitrate aqueous solution are used. This can be carried out by adding the two at the same time, by the simultaneous mixing method, or by the controlled double quenot method. For details, see JP-A-53-
Publication No. 22408, Japanese Patent Publication No. 13162/1973, Journal of Photographic Science (J
, Photo, Sci, ) + 24.198 (1
976), etc.

At this time, 0 for the number of moles of silver in the entire completed particle.
．． 0.1 to 30 mole of silver nitrate, an equal mole or more (approximately double the amount or more) of an iodide compound, and if necessary silver bromide are added to the aqueous solution of a rogendide.

The pAg when forming the first coating layer varies depending on the reaction temperature and the type and amount of the silver halide solvent, but preferably the one described above is similarly used.

As a method for forming the first coating layer, a simultaneous mixing method or a controlled double jet method is more preferable.

The second coating layer of the silver halide grains of the present invention is provided on the outer side of the inner core having the first coating layer on the surface thereof, and
- It can be provided by a method in which silver halide having a different halogen composition from the halogen composition is coated by a simultaneous mixing method or a controlled double jet method.

Regarding these methods, the method of providing the first coating layer described above is similarly used.

When introducing the second coating layer, since the halogen composition of the second coating layer is different from that of the first coating layer, the second coating layer is difficult to precipitate on the surface of the first coating layer. Therefore, it is necessary to consider changes in the critical supersaturation degree. Further, it is preferable to increase the number of moles added per unit time as the total surface area of the particles increases.

When the second coating layer is silver bromide, a method (one-sided mixing method) in which an aqueous silver nitrate solution is added in the presence of an inner core having bromide and the first coating layer in advance can also be used.

It is preferable that the second coating layer has a uniform chlorine composition, and for this purpose, it is preferably formed by a simultaneous mixing method or a controlled double-layer method.

Regarding the iodine content of the first coating layer of the silver halide grains of the present invention, for example, J.L. Goldstein (Gol.
dstein), D. E. Williams (Wi]
The method described in "X-ray analysis in TEM/ATEM" Scanning Electron Microscope (1977), Volume 1 (IrT Research Institute), Page 651 (March 1977) It can also be found by

In preparing the Rogge/silver oxide grains of the present invention, the emulsion can be extracted from the emulsion after precipitation of the second broken layer or after physical ripening, or if necessary, from the emulsion after internal nucleation or after the formation of the first coating layer. To remove salts, the Tardel water washing method, which is performed by gelatinization, may be used, but it is still possible to remove inorganic salts, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. unionized A sedimentation method (flocculation) using gelatin, carbamoylated gelatin, etc.) may also be used.

The grain surfaces of silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, Burr-Friesel (H,
Fr1eser ) ed.
er Photography Prose
ss mit Silberhaloge-niden
) Akademisehe Verlagsges
ellschaft.

1968, pages 675-734 can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a substance with an original reference, a noble metal sensitization method using gold or other noble metal compounds, etc., may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thianols, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat. No. 1,574,944,
No. 2,410,689, No. 2,278,947, 2,7
No. 28,668, No. 3,656,955, No. 4,032,
No. 928, No. 4,067.740. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat.
No. 87,850, No. 2,419,974, No. 2,518,
No. 698, No. 2,983,609, No. 2,983,610
No. 2,694,637, No. 3,930,867, 4
, No. 054,458. For noble metal sensitization, in addition to total complex salts, complex salts of metals in the synchronized group II, such as platinum, iridium, elephant, and crumb, can be used.
Specific examples are U.S. Pat. Nos. 2,399,083 and 2,44
No. 8,060, British Patent No. 618,061, etc.

For the silver salt particles of the present invention, a combination of two or more of these chemical sensitization methods can be used.

Examples of inorganic matting agents for the matting agent according to the present invention include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, norium sulfate, calcium carbonate, and glass. Examples of organic matting agents include starch, cellulose esters (e.g. cellulose acetate propionate),
Examples include cellulose ethers (eg, ethyl cellulose), synthetic resins such as polymeric esters of acrylic acid and methacrylic acid (eg, polymethyl methacrylate), polyvinyl resins (eg, polyvinyl acetate), polycarbonates, polymers and copolymers of styrene, and the like. Others listed in υ5P-2731347 and patent application 1984-
117138, 59-135884, 59-141
092, 59-141093, and fluorine-containing organic matting agents. In addition, the above mark/
) agent exhibits a remarkable effect on abrasion resistance when used in combination with the silver halide grains according to the present invention. In this case, the average grain size of the matting agent is preferably from 2.0 μm to 10 μm.

Here, the average particle diameter is expressed by the following formula.

In the formula, 6 is the average particle diameter, Di is the individual particle diameter, and n is the number of particles.

When the above-mentioned capping agent is used in combination with silver halide grains other than the silver halide grains according to the present invention, it has no or almost no effect on improving the resistance to frictional force, and when the above-mentioned matting agent is used in combination with the silver halide grains according to the present invention, When used in combination, there is little change in sensitivity due to stress, and stress characteristics, that is, pressure increase/decrease sensitivity and pressure force blur, are all improved, and overall pressure resistance is improved.

The capping agents used in accordance with the present invention include the inorganic and organic types exemplified above. Also, a combination of at least two different matting agents is used, for example a combination of matting agents that differ from each other in hardness, for example one relatively soft such as polymethyl methacrylate and the other relatively hard such as silicon dioxide. You can also do that.

The cloak agent used in accordance with the present invention includes a hydrophilic colloid coating in the outer coating layer. ! L&I compositions, particularly in protective coatings applied over photographic silver halide emulsion layers. Any method that achieves a uniform dispersion of particles in Fuchu may be used for this.

The amount of capping agent can be varied within a very wide range. Generally, the matting agent is used in an amount of about 10 mg to 10 mg per side of the support.
It can be used for total coverage in the range of about 100+ng/rd. However, larger amounts can also be used. The average particle size of the matting agent is about 2. Preferably, at least 50 particles of the matting agent have a diameter of 2-6μ.

The coating amount of silver in the silver halide photosensitive material applied to the present invention is arbitrary, but preferably 1000 mg/m2 or more15
000m97m2 or less, more preferably 200m2 or less
0m 7m2 or more and 10000m97m2 or less.

Additionally, photosensitive layers containing the particles may be present on both sides of the support.

As the binder and protective colloid for the photographic emulsion of the invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxyl methyl cellulose, cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Alcohol 4 IJ Vinyl alcohol partial acetal, Bo'J-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Various types of synthetic hydrophilic polymers such as single or copolymers Substances can be used.

Enzyme-treated gelatin as described on page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatino. The product obtained by the reaction is used.

The photographic emulsion of the present invention may contain various compounds for the purpose of preventing capri or stabilizing photographic performance during the manufacturing process, storage or photographic processing of the light-sensitive material. i.e. azoles such as benzothiazolium salts, nitroinda! -ols, nitrobenzimidazoles, chlorobenzimidanols, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothia diazoles, aminotriazoles,
Benzotriazoles, nitrobenzotriazoles,
Mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc.; mercazotobiliminones: mercadettriacunes; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes. (especially 4-
Hydroxy-substituted (1,3,3a,7)tetraazaindenes), tetraazaindenes, etc. Known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds can be added.

In addition, in order to prevent image quality deterioration when using a roll conveyance type automatic developing machine that operates at high temperatures for a short period of time, such as X-ray film, special
3, 57-144832, 58-109947, 58-42778, 57-84960. 57-14
2055, 57-144833 can be added.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the photographic emulsion of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsion dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast Various surfactants may be included for various purposes such as sensitization, sensitization), etc.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol 1.IIJ
Ethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol ester KR1-t-') ethylene glycol sorbitan ester fL4+) alkylene glycol alkylamine or amide, silicone polyethylene nonionic surfactants such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carbates, alkyl sulfones acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, Anionic surfactants containing acidic groups such as calxoxy group, sulfo group, phospho group, sulfate ester group, phosphate ester group, such as polyoxyethylene alkyl phosphate esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl Amphoteric surfactants such as sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts 1. Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium, imidazoliu, mu, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are available from Research Disclosure (Re
5earch Disclosure) Volume 176 1
7643 (published in December 1978), page 23, item 5, ■.

A photographic light-sensitive material using the photographic emulsion of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer and other hydrophilic colloid layers. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (tumethylol urea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3- hydroxydioxane, etc.), active vinyl compounds (1゜3.5-triacryloyl-hexahydro-8-)riazine, 1,3-vinylsulfonyl-2-promisole, etc.), active halogen compounds (2,4-dichloro-6 −
Hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucovinoxychloroic acid, etc.), etc. can be used alone or in combination.

A photographic light-sensitive material using the photographic emulsion of the present invention may contain a dispersion of a water-insoluble or poorly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. . For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrynaute, (meth)acrylamide,
Vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β
-Unsaturated cucarzenic acid, hydroxyalkyl (meth)
The monomer component is a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. d IJ mom - can be used.

The photographic emulsion layer of the photographic light-sensitive material using the photographic emulsion of the present invention contains a color-forming coupler, that is, an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) during color development treatment. It may also contain a compound that can develop a color by oxidative camping. For example, magenta couplers include 5-♂ lazolone couplers, vilazolobenzimidazole couplers, cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, etc.; yellow couplers include acylacetamide couplers (e.g. penzoylamotoanilides, biazolobenzimidazole couplers, Examples of cyan couplers include naphthol couplers and phenol couplers.

These couplers are preferably non-diffusive and have a hydrophobic group called a .zeta.last group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

When carrying out the present invention, the following anti-fading agents can also be used together, and examples include non-derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols used in the present invention. .

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an oryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and ultraviolet absorbing 1f IJ moms can be used. . These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.

Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The light-sensitive material of the present invention uses hydroquinone derivatives, aminephenol derivatives, gallic acid derivatives,
It may also contain ascorbic acid derivatives. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer can be formed by a Tinob coating method, a roller coating method, a curtain coating method, an extrusion coating method, or the like. US Patent 2,68
No. 1,294, No. 2,761,791, No. 3,526
, 528 is an advantageous method. The support is preferably a cellulose ester film such as a cellulose triacetate film, a polyester film such as a polyethylene terephthalate film, or paper coated with an α-olefin polymer.

The silver halide emulsion of the present invention can be directly or indirectly
It can be used not only for black and white photosensitive materials such as photosensitive materials, lithographic photosensitive materials, and photosensitive materials for black and white photography, but also for color photosensitive materials such as color negative photosensitive materials, color reversal photosensitive materials, and color pages.

For photographic processing of the light-sensitive material of the present invention, for example, Lisa Chidiskloji? -(Re5earch Disclo
(sure) solution can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually selected between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (Tatoeba Hydroquinone), 3-
Pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p
-aminophenol) etc. may be used alone or in combination. The developing solution generally contains other known preservatives, alkaline agents, buffering agents, anti-capri agents, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like.

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

When forming a dye image, conventional methods can be applied.

For example, the negative-positive method (e.g. "Journal of the Society of Photographic and Television Engineers")
f the 5ociety of Motion P
ictureand Te1evision Engi
neers) + vol. 61 (1953), 667~
(described on page 701); developed with one developer containing a black and white developing agent to form a negative silver image, followed by at least one uniform exposure or other suitable fog treatment, followed by color development. What to do - Color reversal method to obtain a positive image The photographic emulsion layer containing the two dyes is exposed and developed to form a silver image.A silver dye bleaching method is used in which the dye is bleached using this as a bleaching catalyst. It will be done.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-7 minol). N
-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino/-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, Photographic Gloss Seeding Chemistry by F. A. Mason
icProcessing Cheistsy *F
ocal Press, 1966), 226-22.
9 pages, U.S. Patent No. 2,193,015, U.S. Patent No. 2,592,
364, JP-A No. 48-64933, etc. may be used.

The color developer may also contain a buffer, a development inhibitor or an anti-capri agent, and the like. Also, if necessary,
Contains no water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, anti-fogging agents, fogging agents, auxiliary developers, viscosity imparting agents, polycarzene acid chelating agents, antioxidants, etc. .

After color development, the photographic emulsion layer is usually bleached. Bleaching may be carried out simultaneously with the fixing process or may be carried out separately. Bleaching agents such as iron (III), copper (IV), chromium (Vl), and copper (II) can be used. Compounds of valent metals, peracids, quinones, nitroso compounds, etc. are used.

For bleach or bleach-fix solutions, see U.S. Patent No. 3,042,52.
No. 0, No. 3,241,966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thiol compound described in JP-A No. 53-65732, various additives may also be added. [Examples of the Invention] The present invention will be further explained below with reference to Examples.

It goes without saying that the present invention is not limited to the examples.

Example 1 (1) Preparation of Comparative Sample 1-1 ■ Preparation of silver iodobromide grains for physiognomy (inner core) In 1 liter of water, 25 g of gelatin, potassium bromide - 8,9,0,1% 3.4
- Add 80 cc of a methanol solution of dimethyl-4-thiazoline-2-thione into a container kept at 75°C, and add 1 s of an aqueous solution containing 250 g of silver nitrate per liter (solution A) while stirring.
o o mt and 780 d of an aqueous solution (liquid B) containing 5 g of potassium iodide and 206 g of potassium bromide per liter to pB
They were added simultaneously by double jet method over 60 minutes while maintaining r 1.42.

The thus obtained silver halide grains are octahedral silver iodobromide grains having a projected area diameter of 0.95 μm in a defined size (hereinafter the same) and containing 2 mot % of silver iodide.

■ Growth of phase C (coating layer) 34g of silver and 790c of water were added to the phase A emulsion described in ■ above.
c, gelatin 15g, 0.1% 3,4-trimethyl-4-
Mix 80 cc of a methanol solution of thiazoline-2-thione and add 0.65 ml of thiazoline-2-thione while stirring to a container kept at 75°C.
650 cc of N AgNO3 solution and 1. IN's KI3c
c and 1. Mix 647 cc of KBr solution in pBr
While maintaining the temperature at 1.41, the mixture was added at the same time by the double jet method over 50 minutes. The silver halide grains thus obtained are monodisperse octahedral grains with an average diameter of 1.50 μm, and structurally have a core-shell structure consisting of a human phase and a C phase. This was called particle A.

The thus obtained particles A contained 10-' mol of chloroauric acid I and 2.5 x 10-' mol of sodium thiosulfate per 1 mol of silver.
After adding 5 mol and chemically ripening at 58°C for 65 minutes, 4-hydroxy-6-methyl-1,3,3a,
adding 3 X 10-3 moles of 7-chitrazaindene;
It was designated as emulsion A.

In addition, 50 g of gelatin, 5% aqueous solution of sodium dodecylbenzenesulfonate, an antistatic agent and coating aid, 3
0 cc and a hardening agent were added to water 11 to create a liquid (■), and to this R liquid, 1 g and 2 g of polymethyl methacrylate particles with an average particle size of 3.2 μm were further added to create a liquid (■) and a liquid (■). These were used as a gelatin protective layer solution.

Then, the emulsion layer was coated on a polyethylene terephthalate (PET) base using a slide hopper coater so that the silver content of the emulsion was 5jj/m2, and the protective layer was coated with protective layer liquid 11755 A2! Dry the cloth and
Comparative samples Cup 1, Cup 2, and A3 shown in the table were created.

[2] The preparation method of silver iodobromide in which the B phase (first coating layer) was introduced by the substitution method with iodide ions is the same as that of comparative sample 1-1, but the A phase is grown before moving on to the growth of the C phase. To 34 g of silver in the emulsion, 100 cc of Kl aqueous solution was added over 10 minutes at 75°C with sufficient stirring to introduce phase B, and then C of silver iodobromide containing 0.5 mol of iodine was added. A phase (second coating layer) was provided to obtain monodispersed octahedral particles of 1.48 μm. The amounts of KI used were 0.29, 0.3 I, 0.4 & 1.0 g per 100 grams of aqueous solution for emulsions B and C, respectively.

D and E were created. However, the process conditions after chemical ripening are the same as in Example 1-■.

Emulsions B, C, D, and E prepared as described above.

Protective layer liquid used for comparison sample preparation 1. An emulsion layer and a protective layer were formed in the same manner as in the comparative sample by combining n, I[[, and samples &4 to 15 in Table 1 were prepared.

[3] Method for evaluating the scratch resistance properties of the above samples The 15 types of sample films obtained as described above were heated at 23°C and 35% R.
The humidity was conditioned for 5 hours under H.H., and these humidity control sample films were placed on a CRH-type laboratory bench manufactured by Yamato Scientific Co., Ltd. with the emulsion coated side facing down. A heavy film of .6 cm2 and weighing 1 kg was placed on the film, and the film was pulled at 45 crn at a speed of 0.1 m/sec, and these films were subjected to XD-90 development using a Q-1200 automatic processor manufactured by Konishiroku Photo Industry Co., Ltd. The film was developed with a solution for 90 seconds, and the density difference ΔFog value between the average density of the area where scratches were generated and the fog was determined.

[4] Characteristic measurement results Table 1 shows the fog measurement results. It should be noted that the smaller the ΔFog value is, the fewer the scratch failures are and the better the results. From Table 1, samples of the present invention A 5 , A 6 , Boiled 8 , A
9. Ni-11, A12, Ni-14, and A15 have good scratch resistance, and by using the silver halide particles of the present invention in combination with a matting agent, the scratch resistance can be greatly improved. Understood.

Table 1 (Note) A phase AgBrI (I = 2 mot %)
, B phase Ag4, C phase AgBr1, silver molar ratio of A phase/C phase = 1/3 Example 2 While controlling at 60°C, pAg = 8, pH = 2.0, the average grain was A monodisperse cubic emulsion of silver iodobromide emulsion containing 2.0 mol of silver iodide and having a diameter of 0.3 μm was obtained. An electron micrograph of this emulsion showed that the incidence of twin grains was less than 11% in number.

After desalting the particles, add silver nitrate solution and heat at 60°C.
Silver ripening was performed for 70 minutes at Ag = 3, -26.

Of this emulsion, an amount corresponding to 2 moles of all the silver halogenide used for growth was used as a seed crystal to grow as follows.

That is, the seed crystals were dissolved in a solution 8.51 containing protected gelatin and ammonia kept at 40°C, and further mixed with glacial acetic acid.

Using this reed as a mother liquor, add a 3.2 N ammoniacal silver ion aqueous solution and a Noride aqueous solution to the double jet method f1 at a flow rate as shown in Fig. 1,
Stirring and mixing were performed.

In this case, as shown in Table 2, by changing the ammonia concentration, P', and PAg of this mother liquor, a second
Silver iodide was localized at various concentrations as indicated in the table.

Next, while keeping pAg constant at 9.0, - was changed from 9 to 8 in proportion to the amount of ammoniacal silver ion added.
A shell of pure silver bromide with gI = 0.6 mot% AgBrI was formed.

In this way, eight types of monodispersed emulsions shown in Table 2 were prepared (A2+-1 to 2-8). Emulsions other than Emulsion Shop 2-1 and &2-6 were ripened at pAg of 11.5 for 3 minutes at the end of grain growth, and the grains were rounded. In each emulsion, the total ratio of silver iodide to total silver halide was 2 molti.

In addition, the AgI mold of the localized part of silver iodide is as shown in Table 2, and the shell thickness is O15~0.8μ.
m, and the average particle diameter was 1.21 to 1.23 μm.

Excess water-soluble salts were removed from each emulsion obtained by a coagulation precipitation method, and ammonium thionate, chloroauric acid, and hypo were added to perform gold-sulfur sensitization. Then, 4-hydroquine-6-methyl-1゜3.3a,7-chitrazaindene was added, and further gelatin 100 g/1 m
ol...Common photographic additives such as silver halide grains, spreading agents, thickeners, hardeners, etc. were also added.

For the protective layer solution, the following compound (a) was added to the protective layer solution I used in Example 1, as shown in Table 3, Protective layer overnight boiling ■.
5F/V, with the following compound (b) added at 0.8 g/l, the following compound (c) added at 0.31/l, and a hardening agent also added, protective layer liquid boiled in Table 3. As shown in Figure 0, the protective layer P2i, the average particle size of 1.0 to 50 μm
of polymethyl methacrylate or average particle size 1.2-4
．． A material to which a 5 μm silicon dioxide matting agent was added was used.

Table 3 Compound (a) C2H5 CH2C00CH2CH"4H9 Na03S CHC00CH2CHC4H92H5 Compound (b) Compound (C) CH2-C00CH2 (CF2CF2) , HNa03
S -CH-C00CH, (CF, CF2)3H and the emulsion layer of the emulsion in Table 2 each has a silver content of 697 m
2, the protective layer was coated on the slide coater coated PET base so that each of the 11 types of protective layer liquids shown in Table 3 was Il/45 m'' and dried.
Samples/L16 to &50 shown in Table 4 were prepared.

The scratch resistance of the thus obtained sample was evaluated in the same manner as in Example 1, and the ΔFog value was determined.

In addition, each sample was subjected to 3.20 MSr wedge exposure, and developed using XD-90 processing solution for 190 seconds using a QX-1200 automatic processor manufactured by Konishi Roku Photo Industry Co., Ltd. to determine the sensitivity of each sample. . Sensitivity is determined by calculating the reciprocal of the amount of light necessary for the blackening density to increase by 1.0 due to exposure, and is expressed as a relative value 1, with sample boiling 1 set as 100.

Table 4 shows the measurement results. As is clear from this table,
Even particles grown under cubic growth conditions can be
2, A36, Boiled 37, Boiled 38, Boiled 41.442 and A
No. 44 obtained good results.

Further, emulsion A2-8, in which the shell is pure silver bromide, does not produce any effect even when combined with a matting agent having a diameter of 2 μm or more.

Example 3 A two-layer color photosensitive material sample having the composition shown below was prepared on a triacetyl cellulose triacetate support.

1st layer: red-sensitive emulsion layer sensitizing dye ■・・・・・・・・・・・・・・・・・・
...6 x 10 moles of sensitizing dye per mole of silver
・・・・・・1.5×10 molar coupler EX-1 for 1 mole of silver・・・・・・・・・4.0×10 molar coupler EX-2 for 1 mole of silver・・・・・・3.0×10 mol per mole of silver Coupler EX-3・・・・・・・・・6.0×10 mol per mol of silver 2nd layer, protective layer trimethyl methacrylate Particle average diameter approximately 1.1μ,
Four types of gelatin layers including 1.8μ, 2.1μ, and 2.8μ were coated with trimethyl methacrylate at 20μ/m2 and gelatin at 197m2. In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

The compounds used to prepare the samples were as follows: 0 X-2 X-3 Na Development processing step 1, color development
...3 minutes 15 seconds 2, bleaching...
・・・・・・・・・・・・・・・6 minutes 30 seconds 3, Wednesday
Washing・・・・・・・・・・・・・・・・・・・・・
・3 minutes 15 seconds 4, established...
・・・・・・・・・6 minutes 30 seconds 5, wash with water...
・・・・・・・・・・・・・・・・・・・・・3 minutes 15
Second 6, stable・・・・・・・・・・・・・・・
...3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer sodium nitrilotriacetate 1. OI Sodium Sulfite 4.0g Sodium Carbonate
30.0p potassium bromide
1.4g Hydroxylamine sulfate salt2.
4 g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5 g Add water 11 Bleach solution Ammonium bromide 160.0 g Aqueous ammonia (28 t) 25.0 cc Ethylene diamine - Sodium iron tetraacetate 130.0. i9
Add 14.0 cc of glacial acetic acid water 11 Fixer Tetra+IR Sodium nophosphate 2.0 g
Sodium sulfite 4.0 g Ammonium thiosulfate (70 t) 175.0 cc Sodium bisulfite 4.611 Add water
11 Stabilizing liquid formalin Add 8.0 cc of water 11 The samples used in the experiment include the type of emulsion in the red-sensitive emulsion layer, the presence or absence of a matting agent in the protective layer, and the grains of the matting agent if a matting agent is present. If we distinguish them based on their diameters, there were a total of 16 types of samples, 47 to A62 in Table 5. In addition, emulsion A was prepared using the same preparation method f as for grain A in Example 1, in which the coating layer (C phase) of the inner core (physiology) was made of pure silver bromide.
' was used for comparison, and a total of three types of samples A63 to A65 in Table 5 were also prepared.

Table 5 (Notes) A: No scratches at all, Mouth: Slightly scratches, C: Slightly more scratches, 22 scratches frequently. After cutting to a width of 35 mm, perforations were made and the film was transported and rewound for 30 minutes using an FT-1 eye reflex camera made by Konishi Roku Photo Industry in a dark room at 5°C and 30% RH. The degree of scratches was visually evaluated using a 10x magnifying glass.

As shown in Table 5, it can be seen that the samples of the present invention have excellent scratch resistance. Furthermore, it can be seen that the effect of the matting agent is effectively exhibited when the second coating layer is made of silver iodobromide rather than pure silver bromide.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide photographic material which has few scratch failures, little change in sensitivity due to stress, and good stress characteristics.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the supply flow rate profile of silver ions and halide ions during the growth of halogen particles of each sample in Examples. Figure 1 8 + Time (minutes) Procedure Written by Principal Ho Masaru (self-motivated) January 20, 1985 Commissioner of the Patent Office Kuro 1) Mr. Akio 1, Indication of the case 1986 Patent application No. 027913 2, Invention Name: Silver halide photographic light-sensitive material 3, relationship with the person making the amendment Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4. Contents of the amendment in column 6 of “Detailed Description of the Invention” in the agent’s specification As shown in the attached sheet (1) Lines 9 to 12 of page 8 of the specification "Substantially consisting of..." is corrected to "consisting of a second coating layer consisting of silver iodobromide having a different halogen composition from that of the first coating layer." (2) On page 9, line 10 of the same book, "equal to" is amended to "equal to". (3) "Second coating layer----" on page 10, line 20 of the same book
--- Correct "It is" to "The silver iodobromide of the second coating layer is." (4) "Sono" in line 10 of page 29 of the same book is amended to "it". that's all

Claims (1)

[Scope of Claims] An inner core made of silver bromide or silver iodobromide, a first coating layer made of silver iodide or silver iodobromide on the outside of the inner core, and further coated on the outside of the first coating layer. The first coating layer is composed of a second coating layer made of silver iodobromide having a different halogen composition,
In silver halide grains having a ratio of projected area diameter to thickness of less than 5, (1) the iodine content of the first coating layer is 10 mol% or more higher than the iodine content of the internal core, and (2) the iodine content of the entire grain is On the other hand, the proportion of silver in the first coating layer is 0.01 to 30 mol%, and (3) the iodine content of the second coating layer is 0.001 to 10 mol%. A silver halide photographic material comprising a silver halide emulsion layer and a hydrophilic colloid outer layer containing at least one matting agent having an average grain size of 2.0 μm or more.