JPH01113745A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enlarge a specific surface area, to facilitate a spectral sensitization and to improve the development property of the title material by incorporating a silver halide particle which as a protrusion on the prescribed surface of a base particle, in said material. CONSTITUTION:The silver halide photographic sensitive material contains particle constituted of deposited protrusions (A) of the silver halide having different halogen composition from that of the base particles on each crystal faces (111) of a silver halide tetradecahedron or octahedron particles which have >=30% the surface area ratio of a crystal faces (111). And, the protrusions (A) having <=0.15mum mean projecting area diameter are formed on the crystal faces (111) of the base particles in an amount of 10-1,000 numbers/mum<2>. And, in the positions here the protrusions one not deposited, for example, the crystal faces (100) of the tetradecahedron particles and the top or the edge of the octahedron particles, a chemically sensitized nucleus are preferably formed with a sulfur sensitizer, etc.

Description

Detailed Description of the Invention (Technical Field) The present invention relates to a silver halide photographic light-sensitive material, and particularly silver halide tetradecahedral grains or silver halide octadecahedral grains having a {111} face ratio of 30% or more. This invention relates to a silver halide photographic material which is preferred by spectral sensitization rather than by increasing the specific surface area of the faceted grains.

(Prior art) The spectral sensitization technology of /No silver genide photographic emulsion is a photosensitive material with high sensitivity and excellent color reproducibility 't-15! This is an extremely important and essential technology for building. In order to provide photosensitive materials with high W&D, a large number of spectral sensitizers have been developed, and many technical developments have been made regarding their use, such as supersensitization methods and addition methods. The spectral sensitizer absorbs light in the long wavelength range, which silver halide photographic emulsions do not substantially absorb light, and has the effect of transmitting the light absorption electrons and /f or light absorption energy to the silver halide. Therefore, increasing the amount of light captured by a spectral sensitizer is advantageous for increasing photographic sensitivity.For this reason, not only attempts to develop spectral sensitizers with high light absorption coefficients but also efforts to develop silver halide emulsions have been made. Attempts have also been made to increase the amount of light captured by increasing the amount of addition.

(Problems to be Solved by the Invention) For this reason, attempts have been made to improve and develop methods of adding spectral sensitizers that can increase the amount of spectral sensitizers added, and to develop and improve methods for producing silver halide grain emulsions.

For example, Thomas L+P
Enner), P, He, Kilman, Sixnia (P, B, Gilman Jr.) 7 Otographic
Science and Engineering (Photo8c
i, Em), 20C3), and 27-1O6 (176), depending on the appropriate potential relationship! Attempts have been made to adsorb a large amount of a spectral sensitizer on a silver halide crystal in a layered manner to increase the amount of light captured by the spectral sensitizer and to suppress the decrease in light intensity caused by the addition of a large amount of the spectral sensitizer. Attempts have also been made to improve the silver halide grains themselves. One method is to use tabular silver halide with a large specific surface area.
13ri No. 27, 3g-//3ri No. 26, j1-//
3ri No. 30, same j♂-//3ri 31I-, same jza-/
//ri3≠ issue, same jzaita j337, same 3g-101
32g issue, 3g-IO? ! This is disclosed in Publication No. 26 and the like.

On the other hand, Sea A/+1 Berry (C, kL, Berry
) and D.C. Skillman (D, C05k 1man)
) by J, AppA, Phys, 33.2/63
-276 (l 6≠) and JP-A-39-1999 by J.E. Maskasky (J.E. Maskasky) kC.
/333≠Q shows a grain in which chloride was epitaxially grown on the surface of a silver bromide grain.

Although these examples are not originally intended to increase the specific surface area, they are one method of increasing the specific surface area.

However, for any of the grains shown in these figures, the protrusions epitaxially grown on the grain surface are large in size and/or the number per unit area is small, so it is difficult to compare the protrusions with the same size particles without protrusions. It cannot be expected to increase the specific surface area sufficiently.

Therefore, from the viewpoint of increasing the specific surface area, as a technique to create smaller protrusions and make them stably present during the subsequent process, especially during chemical sensitization, stabilization is performed using a particle formation stopper prior to chemical sensitization. An attempt was made to
However, prior to chemical sensitization, a mercapto compound (particularly l-7 er-j-mercaptotetrazole) is added as a particle formation stopper, and in the subsequent process chemical sensitization. Disadvantages such as extremely slow speed and increased fog occurred, and disadvantages also occurred in the spectral sensitization process such as inhibition of dye adsorption and formation of aggregates.

Therefore, in the patent application No. 1986/-300 HiroIO.

In order not to adversely affect the spectral sensitization process, it is stated that it is preferable to use a dye that has both the purpose of stopping particle formation and spectral sensitization.

However, the optimum dye that acts as a particle formation stopper and the optimum dye that acts as a spectral sensitizer do not necessarily match, and the degree of freedom of the dye for spectral sensitization is considerably narrowed, and the color sensitivity etc. photographic characteristics must often be sacrificed.

Therefore, by creating the protrusions after chemically sensitizing silver halide grains, the process of chemical sensitization, which is the most unstable environment for the protrusions, can be avoided, and a grain formation stopper can be used. Although a method can be considered in which the protrusions can be omitted, if the silver halide grains after chemical sensitization are simply covered with the protrusions, the developability will deteriorate.

In addition, in the Special Publication No. 31-211-772, the tetradecahedron mh
A method for producing a hybrid silver halide crystal in which a second silver halide is preferentially added to the (/ / / ) surface of the (/ / / ) surface is described. By preferentially adding the second silver halide, there is no intention to increase the specific product in terms of ultimately creating cubic crystals.

For this reason, a silver halide photographic emulsion that is suitable for spectral sensitization by depositing silver halide protrusions to increase the specific surface area and also has good developability has been awaited.

(Object of the invention) The object of the invention is to provide a silver halide photographic light-sensitive material,
By increasing the specific surface area of silver halide tetradecahedral grains or silver halide octahedral grains with a {111} face ratio of 30% or more, it is suitable for spectral sensitization and has good developability. It is an object of the present invention to provide a silver halide photographic material having the following properties.

(Disclosure of the Invention) An object of the present invention is to selectively remove halogen only from {111} of silver halide tetradecahedral matrix grains or silver halide octahedral matrix grains having a {111} plane ratio of 30% or more. The halogen composition of the protrusions is different from the halogen composition of the base grain, and the average projected area diameter of the protrusions is 0°/Jμm or less, and the number is 1O~1.
0,000 particles/μm2 was achieved by a silver halide photographic W& optical material containing silver halide grains present in {111} host grains. Furthermore, even better results were obtained by providing chemical sensitizing nuclei at positions where the silver halide protrusions were not present.

(Specific structure of the invention) Hereinafter, a specific configuration of the present invention will be explained in detail.

The structure of the silver halide grains of the present invention is based on host grains (hereinafter referred to as (
lll) Silver halide tetradecahedral matrix grains or silver halide octahedral matrix grains with a surface ratio of 30% or more are collectively referred to as "matrix grains") S fraction and the {111
} consists of silver halide protrusions selectively formed only on the surface.

The silver halide emulsion of the present invention can be prepared by selecting and combining various methods known in the field of silver halide photographic materials.

By adjusting the pAg of the base particles at the time of particle formation,
Can be easily formed.

It is preferable that the base particle has a flat {111} face ratio (///face ratio of 3096 or more, preferably ≠O
% or more, more preferably 30% or more.

The surface ratio can be directly observed from electron micrographs of silver halide emulsion grains taken by the carbon fiber method, and more precisely, it rots. ri μ
The method described on page 2 can be used. That is, the reflection spectra of thick liquid emulsion layers to which various amounts of a dye (anhydro-3,3'-bis-(sulfobutyl)-termethylthiacarbocyanine hydroxide pyridinium salt) were added were measured, and it was found that the dye was (100) On the surface and {11
By focusing on the fact that it gives significantly different spectra on the plane {1} and treating it with Kubelker-Munk's equation, we can obtain (1
The ratio between the 001 plane and the (llll) plane can be determined.

In the present invention, in the process of base particle formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, an O diwam salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The silver halide grains of the present invention are chemically sensitized before or after selectively forming protrusions on the (lll) plane of the base grain. However, in order to ultimately maintain the shape of the protrusions, chemical sensitization is preferably performed before the protrusions are formed.

For chemical sensitization, for example H, FriesermDie
Grundlagen der Photogr
ahhischenProzesse mit 8i1
berhalogeniden (Akrdemisch
e Verlagsgesellschaft.

/6g) The method described on pages 673-7341c can be used.

In other words, sulfur sensitization using sulfur-containing compounds that can react with active gelatin or silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines), selenium sensitization, reducing substances (e.g. reduction sensitization using noble metal compounds (e.g., soot salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds);
In addition to known total complex salts such as chloroauric acid, a noble metal aggravation method using complex salts of metals in group (I) of the periodic table such as Pt and Ir%Pd can be used alone or in combination.

Specific examples of these include U.S. Patent No. 1 for sulfur sensitization.
．． 3717. Rihiro≠ issue, same issue i, ttio.

No. 6, No. 2,271. ri ψ7, same No. 2゜72g
, T, TG No. 3, 1,36.733, etc., and U.S. Patent No. 1. j7 hiro.

ri≠≠No., same/, l, 02. J Octopus, same/, 623.
It is described in the 4t Tata issue. Regarding the increased return N & method, U.S. Patent No. 2. 13. l, No. 0, No. 2゜Il, l
ri, Tough No., same No. ≠, 03 Hiro, ≠jg etc.

, US Patent Nos. 2 and 3 regarding the noble metal sensitization method.

No. 013, same No. 2. LtGr, ozO, British Patent No. 1. /1,07zI, etc., and is described in books such as fIlll.

Also, a method of chemical sensitization in the presence of an inhibitor such as human axy/, 3.3a, 7-chitraazaindene (Japanese Patent Application Laid-Open No.
Especially when using methods such as the method of slowing down the addition rate of the sensitizer and selectively chemically sensitizing specific parts of the particles (Japanese Patent Application Laid-open No. 1983/1983; Hirohiro No. 7 '3), etc. Favorable results may be obtained.

Among these chemical sensitization methods, one particularly preferably used in the present invention is sulfur sensitization and gold sensitization.

The sulfur sensitizers used in the present invention include sodium thiosulfate and organic chemical sensitizers such as thioureas, rhodanines, oxazolidines, polysulfides, and selenoureas. Particularly preferred are organic chemical sensitizers.

In the present invention, it is desirable that the chemical sensitizing nuclei exist at positions where no protrusions are present. By separating the positions of the protrusions from the positions of the chemical sensitizing nuclei, the progress of development was accelerated, and it was also possible to prevent a decrease in sensitivity in the inherent sensitivity range due to the addition of a large amount of sensitizing dye.

In this manner, in order to separate the protrusions and chemically sensitized nuclei, when the base particle is a tetradecahedron, it is preferable to chemically sensitize its (100) face. Further, it is known that the vertices and edges of octahedral particles are composed of index planes other than {111} planes. Therefore, when the base particle is an octahedron, it is preferable to chemically sensitize its vertices and edges.

Particularly preferred sulfur-sensitized compounds in the present invention are specifically shown below.

8-/S-≠S CH3CONH-C-N)12 -J S-J'S-ta2H5 S-//C2)i5 8-/, 2 There are no particular restrictions on the conditions for chemical sensitization in the present invention. However, the pAg is 6 to 1/, preferably 6 to 1O1
More preferably 6-ri! and the temperature is 33~
The temperature is preferably 3J-31 DEG C. The addition f of the chemical sensitizer is 1ONIO mol per silver mol, preferably 10 to 10-4 mol.

The determination of the a-image forming position in the present invention is performed in the following manner.

A photosensitive material coated with the target silver halide emulsion on a support was exposed to light for 1 second, and developed with a Kodak formulation MAA-/developer at 20°C for 70 minutes. Exposure is performed at an exposure amount corresponding to (maximum density - minimum density) XI/X or up to 7000 times that amount. Next, it is developed with the following suppressing developer at 0° C. for 70 minutes. However, depending on the particle size and halogen composition, the development time and pH of the developer may vary.
By changing the amount of surface active agent and surfactant, a micro-
Adjust so that it can be easily observed.

(Suppressing developer) For example, if the natural content is high or the development is strongly inhibited by the sensitizing dye used, the pH may be slightly raised with caustic soda or the development time may be extended.

Further, the surfactant in the suppressing developer makes the developed silver, which tends to spread into filaments, into a lump, making it easier to determine the formation position of the developed silver.

After developing like this! Stop development with a glacial acetic acid aqueous solution, recover silver halide particles by enzymatic decomposition with pronase without fixing, place a small amount on a micromesh for electron microscope, and carbon evaporate to prevent print act silver from forming. After that.

It is fixed with a fixing solution to create a carbon replica, and the position of the remaining developed silver, that is, the position of latent image formation, is observed using a 15-photon microscope.

The halogen composition of the base particles of the present invention is as follows.

Although AgBr and AgBrI (I content of 110 molt or less) are used, in order to selectively form protrusions on the {111} planes of the base particles, it is better that the AgI content near the surface of the base particles is small. The AgI content near the surface is 10 molts or less, preferably j molts or less, more preferably 2 molts or less.

The AgI content near the surface can be measured with E8CA.

When it is desired to increase the total AgI content of the base particles, it is possible to reduce the AgI content near the surface by using double structure or multilayer structure particles.

Regarding double structure particles, JP-A-60-/≠333/I
IC is disclosed. Further, regarding multi-structure particles, it is disclosed in Japanese Patent Application Laid-Open No. 1312-1987.Next, a protrusion which is selectively deposited only on {111} of the base particle will be described. This protrusion is connected to the base particle (t
(it) Since the specific surface area of the silver halide grains is increased by the deposition, it is very advantageous for spectral sensitization. In order to increase the specific surface area by the protrusions, the smaller the size of the protrusions, the better (and the larger the number of protrusions per unit area).

The halogen composition of the protrusions of the present invention is different from the halogen composition near the second surface of the base particle, and is Agα or AgclB.
r, preferably Agα or AgαBr having an α content of 3 folds or more, and particularly preferred is Agα.

E in the protrusions may be contained in a trace amount that does not substantially affect photographic properties (particularly developability).

When depositing the protrusions, it is desirable to deposit the protrusions so that the base particles and the protrusions do not mix with each other.

The specific method for the deposition is preferably carried out by superimposing a water-soluble silver salt and a water-soluble halide salt corresponding to the composition of the silver halide protrusions. The addition rate of water-soluble silver at this time is preferably as fast as possible without causing re-nucleation.

In order to deposit halide protrusions, the silver potential at the time of deposition is It is often desirable to produce 'A' at a high silver potential.

The silver potential is +100 mV or more, preferably +I10 mV or more, more preferably +t2 omV or more. However, the potential value is expressed in terms of pair 5-C-E.

The temperature during the preparation of the protrusions is preferably lower than 0°C, preferably 70°C, although this will vary depending on other conditions during the preparation.
The temperature is preferably 63°C or lower, more preferably 63°C or lower.

As described above, by setting the rate of addition of water-soluble silver, the silver potential at the time of depositing the protrusions, and the temperature during the preparation of the protrusions to the above-mentioned preferable conditions, the average projected area diameter of the protrusions becomes smaller.
Moreover, the number of pieces per unit area also increases.

Although the presence of an additive that serves as a silver halide solvent during the preparation of protrusions is not preferred, it may be used as long as the base grains and protrusions do not mix with each other more than necessary.

As a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers,
Although gelatin is advantageously used, other hydrophilic colloids can also be used.

Examples include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, etc.; sugar derivatives such as sodium alginate and dextran; polyvinyl alcohol, poly-N-
A multi-base hydrophilic polymer i such as a single or copolymer of vinylpyrrolidone, polyacrylic/l' acid, polyacrylamide, polyvinylimidazole, etc. can be used.

In addition to lime-processed gelatin, gelatin includes #I-processed gela f7, klull, Soc, Sci, and Phot.

Japan, y16/lp, P2O</91. ,b
Enzyme-treated gelatin as described in ) may be used, and gelatin hydrolysates and enzyme dispersions may also be used.

The photographic emulsion of the present invention preferably contains silver halide grains having the above structure in an amount of 30% by weight or more, particularly 30% by weight or more of the total grains in the emulsion.

Such a structure of the emulsion of the present invention can be confirmed by examining the halogen composition and quantitative relationship of the base grains and protrusions using analytical means such as X-ray analysis.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles, such as penzothiazoliwam salts, nidroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles. , aminotriazoles, benzotriazoles, nitrobenzotriacy/I/M, mercaptotetrazoles (% l-phenyl-j-mercaptotetrazole), etc.: Mercaptopyrimidines; Mercaptotriazines: For example, oxadorintheone Thioto compounds; azaindenes, such as triazaindenes, tetraazaindenes@(≠-hydroxy-substituted (/, j, ja, 7) tetraazaindene), pentaazaindene, etc.; benzene Many compounds known as antifoggants or stabilizers can be added, such as thiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like. For example, US Patent 3. rij≠, ≠7≠ issue, same 3.
9g No. ≠ No. 7 1% Those described in Kosho 32-, 2g, No. 660 can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as nityl, ester, and amine, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent J, 1500
, No. 332, 2. ≠23,3μri issue, times, l, 7/
ls, No. 062, same! , is/7, 2gθ issue, is/7, 3,7
No. 72゜0.21, No. 101.003, British Patent/.

<zr♂, No. 721 can be used.

In order to better exhibit the effects of the present invention, it is desirable that the particles of the present invention be spectrally sensitized.

Examples of documents describing methine dyes preferably used in the present invention include F., M. Hamer [The Chemistry Off", Terocycle Link,
Pawans (The Chemistry of He)
terocyclic compounds),
Volume 1 The Cyanine D
Yes and Re1ated Compounds
)j (A, WeisSber
ger@, Interscience, New York/9614), l).

M. Star? - (8turmer) "The Cyanine Dyes and Related Humpounds, Volume 30"
dRelated Compounds)J (A+
Weissberger, E.C., Taylor (ed., John Wiley Co., New York, 1977), Research Disclosure (RESEARCH DISCLO8URE) / 7A
roll.

4/7A≠3, p, 23~λ≠ (7g), German Patent No. 2'Z, No. 010, US Patent: 2,23/.

AjJ', 21≠23.74CF, 2,303
．． No. 77A, same λ, J/ri, 00/, same co.

rilλ, 32nd number, same j, 4j6. Rijri issue, same, 3,
672. ♂ri No.7, 3.6ri≠, λ17, Dohiro, 0
23.3 ≠ issue, same ≠, Q Hirois,! ;72, UK 1%
Allowance l1.2≠2. Jgg issue, Tokuko Sho≠17hiro 030, 32-2t1tI≠≠ issue, British patent 3g Hiro, 60ri issue, same/, /77, ≠λri issue, JP Shoμg-gjf/3
No. 0, same lI-tatata 6λθ, same hirotar l/≠ hiro2
No. Q, No. 32-i32-1O, U.S. Patent No. 27≠,
7F, No. 2, same λ.

j33. ≠No. 72, -λ, ri36. ．． No. 17, same 3,
/4CI, /za7, same 3. /77.07g issue, 3I
λ417, 127, 3.3≠O9zag7, 3.
37J, No. 70≠, No. 3, No. 633.203, No. 3.
77g, ≠ No. 72, same≠, 07/.

Examples include No. 3/2, Yoko, 070, JJ, No. 2, etc.

These spectral sensitizers may be used alone or in combination (combinations of 1-minute sensitizers are often used especially for the purpose of supersensitization).

Along with the spectral sensitizer, the emulsion may contain a substance exhibiting supersensitization, such as a dye having no spectral sensitizing effect or a substance that does not substantially absorb visible light. For example, aminostilbene compounds substituted with fluorine-containing heterocyclic groups (for example, U.S. Pat.
No. 33,721), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3,7 H. No. 3,310
(described in the above issue), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3,613゜6/3,
Same 3. ls/3. ls≠1, 3,617.2, 5, 3. The combinations described in A3J, No. 72/ are particularly useful.

Next, typical compounds of dyes used as spectral sensitizers in the present invention are shown below.

- D-/D-2 dU3K M (J3 D-Hiro-s 5U a IN a b ()3L)-
f D-tar-l0 D-/ / D-/2 O3 D-/3 1)-/ ≠ D-/3 D-/6 D-/7 D-i ♂ D-/RiD-,2/ C21 "5 D-, 2 Co D-, 23 D-Nohiro D-, 2J The silver halide emulsion of the present invention is suitable for use in black and white silver halide photography g
Optical materials (for example, X-ray sensitive materials, black and white negative film, etc.), color photographic A-sensitive materials (for example, color negative film, color reversal film, color paper, heat development described in European Patent No. 1 IOTZ6OH, etc.) photosensitive materials, etc.). On the other hand, more favorable effects can be obtained as a tube-sensitive emulsion.

In addition, an emulsion washing method for the emulsion of the present invention, a dispersion medium, a hardening agent,
For example, research on dimensional stability improvers, antistatic agents, coating aids, dyes, color couplers, anti-adhesion agents, photographic property improvers (e.g. development acceleration, contrast enhancement, sensitization), and their uses.・Disclosure magazine, /7 & volume,
777g, December issue (item/76≠3), same/♂
Volume 7, 1/97 issue (item 716), Tokukai Show JLF-//3 2 Otsu issue, 31-/3 λ7 issue, 3 G-//3 2 G issue You can refer to the description of the same Jter 20♂≠λ.

Below is a list of relevant sections of Research Disclosure magazine.

l Chemical sensitizer page 23 6≠g page right column Sensitivity increasing agent Same as above 3 Spectral sensitizer, 23~λhiro page 6 μza page right column ~ super sensitizer 6≠ page right column≠ Brightening agent
λ≠Teij Anti-fogging agent Pages 2-2J Page 6 Right column and stabilizer 6 Light absorber, fiber Page 26 Right column on page 611 ~ Luther dye ultraviolet tSO Page left column Line absorber 7 Preventing staining Agent page 2J right column bso page left to right column ♂ Dye image stabilizer page 23 ta Hardener page 26 43/page left column I
Q Binder 26 pages Same as above//
Plasticizer, lubricant Page 27 6jO page right column/2
Coating aid, surface page 26-27 Same as above Activator 13 Static inhibitor page 27 Same as above I Hiro Color coupler 2g page 6≠7-6
Hirog page Yellow couplers that can be used in the present invention include:
A typical example is a hydrophobic acylacetamide coupler having a ballast group. A specific example is US Patent No. 2. ≠No. 07,210, same@co.

No. 74.037 and No. 3 of the same. ．． 26! , No. 306, etc. The use of two-equivalent yellow couplers is preferred for the present invention, and US Pat. Octopus G, No. 3. 33.3
No. 01 and No. ≠, No. 022゜6.20, etc., or Japanese Patent Publication No. 3G-1073, U.S. License No. Hiroshi, Hiroshi 0/, 732
No. ≠, 324, No. 021I-, RIDlza0;
3 (Hirotsuki, 2007), British Patent Nos. 1 and 4 (λj,
No. 020, West German Application Publication No. 2. λ/Ri, Ri No. 77, same No. 2. ．． 2A/, No. 361, No. 2, 32, Jza No. 7? and the same No. 2゜≠33. A representative example of this is the nitrogen atom dissociative yellow coupler described in No. 2, No. 2, etc. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include:

Examples include hydrophobic indacylon- or cyanoacetyl-based couplers having a ballast group, preferably j-pyrazolone- and pyrazoloazole-based couplers. J-pyrazolone couplers are preferably those in which the 3-position is directly substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye. No. 2, No. 2,3≠3.703, No. 2,600.7fg, No. 2,70g, j73
No. 3.01. ,! , No. 633, same No. 3. /3λ,
Zari No. 6 and No. 3. 36.0/3, etc. As the leaving group for the two-equivalent j-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat.
The IJ-ruthio group described in No. 7 is particularly preferred. Furthermore, the j-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides high color density. Examples of pyrazoloazole couplers include the virazolobenzimidazoles described in U.S. Pat. c] (l.

λ, ≠] Triazoles, Research Disclosure λHiroshi 220C/RIGHiroshi June 2013) and JP-A-60-3
Pyrazolotetrazoles described in No. 333.2 and Research Disclosure Co.
Examples include pyrazolopyrazoles described in JP-A No. 10-10-1A31s3 and JP-A No. 10-1031-3. U.S. Pat.
The imidazo(/,,2-b)pyrazoles described in U.S. Pat.
Pyrano C1 (/, j-b) (/, 2. Hiroshi) described in the issue
Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant 7-tall and phenolic couplers. ≠7 Hiroshi.

273, preferably the naphthol couplers described in U.S. Patent No. 4c, 032, . 2/J issue, same No. 1 Hiroshi.

Typical examples include two-equivalent naphthol/l/system couplers of the oxygen atom separation type described in 1tA 6.376, 1tA ≠, 22g, 233, and 1tA Kota Is, 200. Further, specific examples of phenolic couplers include US Pat. Za0/, 17
No. 1, No. 2,772,162, No. 2,193. It is written in Za No. 26, etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic cyan coupler having an alkyl group, U.S. Patent No. 2,77λ, /&, No. 2, No. 3.7! ;r.

No. 301, No. ≠, /jA, No. 3, No. 6, No. 3.

33≠, 0// issue, same @≠, J, 27. /73, West German Patent Publication No. 3,327,722 and European Patent Tube 1λ
2,3-diacylamino-substituted phenolic couplers described in U.S. Pat. 't<
Having a phenylureido group at the λ-position described in Yumi, No. 6ii, No. ≠, No. 333゜Tatata, No. ≠, Kosi, No. ssri and No. 4!27, 7A7, etc. and!
A phenolic coupler having a 7-syl amino group at the -position,
and j-aminonaphthol couplers described in European Patent No. 1 &/, A, 26A.

In order to correct unnecessary absorption of color pigments, it is preferable to perform masking by using a colored coupler in combination with a color photosensitive material for photographing. U.S.%=F≠, 1lp3,670 and Japanese Patent Publication No. 7-32 G13, etc., yellow colored magenta coupler or U.S. patent cylinder μ, OO≠, λ
No. 1, No. 13g1.2jg and British Patent No. 1. Typical examples include the magenta-colored cyan coupler described in I-Hiro No. 6.36g. Other colored couplers are described in the above-mentioned RD/764cj, items ① to G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Specific examples of magenta couplers are found in US Patent No. 11,361s, 237 and British Patent No. Specific examples of yellow, magenta or cyan couplers are described.

Dye-forming couplers and special couplers listed above.

A dimer or higher polymer may also be formed. Typical examples of polymerized dye-forming couplers are U.S. Pat.
3/, No. 120 and the same No. G, OzaQ.

, No. 2//. Specific examples of polymerized magenta couplers are described in British Patent No. 1, i02.173 and US Patent No. ≠, 367.2g2.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler that releases the development inhibitor is the above-mentioned RD/7A≠3.1.
The patented couplers described in paragraphs 1 to 2 are useful.

Preferable combinations with the present invention include JP-A-37-
/! Developer deactivation type represented by /ri≠≠; timing type represented by U.S. Patent No.≠, λ Hiroza, No. 762 and JP-A-Sho, 57-/J Ko2ri≠; JP-A-Sho 1sO-/I≠
, 244f, and a particularly preferred one is JP-A-47-/! /9μμ issue, same jg-λ17
No. 232, JP-A No. 1 po-iiztau, same bo-,
These are the developer-deactivated DIR couplers described in Japanese Patent Application No. 32633 and the like, and the reactive L) IR couplers described in Japanese Patent Application No. 32633 and the like.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent No. 2. Qri 7゜/Hiro θ No. 2, 1
3/, /Zaza issue. Particularly preferred are couplers that release a nucleating agent that has an adsorption effect on silver halide;
1, 31 and 39-/701≠O.

In the photosensitive material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the back layer. Examples are chromium salts, aldehydes (formaldehyde).

glutaraldehyde, etc.), N-methylol compounds (
(dimethylol urea, etc.) are given as specific examples. Active halogen compounds (such as λ,≠-dichloro-6-hydroxy-1,3,3-triazine) and active vinyl compounds (l,3-bisvinylsulfonyl-1-propanol, /, 2-bisvinylsulfonylacetamidoethane) Alternatively, a vinyl polymer having a vinyl sulfonyl group in its side chain is preferable because it quickly hardens hydrophilic colloids such as gelatin and provides stable photographic properties.

N-carbamoylpyridinium salts and haloamidinium salts are also excellent in their fast curing speed.

As an antistatic agent, perfluorooctanesulfonic acid, salt%N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly(n=j)oxyethylenebutanesulfonic acid Na salt, heperfluorooctanesulfonyl-N', N', N'-trimethyl, ammoniodiaminopropane chloride, N
-Perfluorodecanoylaminopropyl-N'N'
Fluorine-containing surfactants such as -dimethyl-he'-carboxybetaine, JP-A-60-1983-1, Or Hiroza No., Mukai 61-//
λl≠G, patent application No. 6/-1337g, same 1s/-/
1s031. Nonionic surfactants, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides obtained by doping these with antimony or the like can be preferably used.

The developing solution used in the present invention includes all developing solutions.

The development processing temperature of the photosensitive material in the present invention is normal/I”C
, to 30°C, but the temperature may be lower than 11°C or higher than 30°C.

The development time is preferably 10 seconds to 30 minutes.

For example, developers used in black-and-white photographic processing can include known developing agents.

As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-
phenyl-3-pyrazolidone), aminophenols (
For example, hemomethyl-p-aminophenol) can be used alone or in combination.

The color-forming visual solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing crude drugs, but p-7
22-diamine-based compounds are preferably used, typical examples of which are 3-methyl-Hiro-amino-N, N-diethylaniline, 3-methyl-≠-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-guamino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-μmamino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or anti-capri agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as l-phenyl-3-pyrazolidone. , viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids; An antioxidant or the like may be added to the color developing solution.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (1),
Compounds of polyvalent metals such as cobalt (1), chromium (VI), and copper (II), peracids, quinones, nitrone compounds, and the like are used. Ferricyanide as a typical bleaching agent;
Dichromate; organic complex salt of iron(1) or cobalt(1) 1 For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid wI! , nitrilotriacetic acid, aminopolycarboxylic acids such as l,3-diamino-2-propatoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates: manganates; nitroso-7 ale, etc. Can be used. Among these, ethylenediaminetetraacetic acid iron (1) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Additionally, iron ethylenediaminetetraacetate (1>m salt) is useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

The present invention will be further explained below with reference to Examples.

Example 1 O0Oλ weight containing 0.001 AM potassium bromide
* Gelatin solution/1. was maintained at 60°C and mixed with 0.3OM silver nitrate solution using the double jet method while stirring.
, soM potassium bromide solution and gold were added at ≠Qcc, respectively. After the addition is complete, ammonium nitrate with a JO'4 concentration of 1
scc and 2j% ammonia water6. Added dabuki. Thereafter, 1 ft of 2M silver nitrate solution was added over 30 minutes. A 1.3M potassium bromide solution was added simultaneously so that the pAg was maintained at g,l during this addition.

After this, the emulsion was cooled to 33"C.1, washed by the conventional 70° curation method, and at .mu.O.degree. C. to pH 6.3, p.
After preparing Ag♂ to 7, the temperature was further increased by 60'GK to 6
Sulfur sensitization was carried out using an optimal amount of compound-1 for 0 minutes.

Compound I S Emulsion A prepared here consists of monodispersed tetradecahedral grains (coefficient of variation 13%), and its average projected rfJ area diameter is 0.
1 gμm, calculated from Kubelker-Munk's formula {1
11} The amount ratio was 63%.

(Preparation of emulsion-l) Add water to emulsion A♂ (7p (corresponding to AgNO3309) and maintain at JO'C, aqueous silver nitrate solution (AgNOai
, oy) and sodium chloride aqueous solution at silver potential +
It was added by the double jet method while maintaining the voltage at 190 mV. Immediately before the end of the addition, add 1.3X10” of dye D-t3.
Emulsion-1 was prepared by adding 'mole/mole of silver. The grains contained in this emulsion-7 are (l//
) Microscopic protrusions were deposited only on the surface.

(Preparation of Emulsion-λ) Emulsion-C was prepared under the same conditions as in the preparation of Emulsion-11&: except that the silver potential was set to +≠OmV. This emulsion-
The particles included in λ are {111} of the parent dodecahedral particles.
Silver chloride was deposited only on the surface, but no microprotrusions were formed.

(+15 Preparation of fabric sample!!I) Triacetylcellulose film support with undercoat layer Coated each emulsion/~λ and protective layer with coating amounts as shown in Table 1, and coated sample l~ I made λ.

Table 1 (1) Emulsion layer ○ Emulsion Each emulsion / -, 2 scissors j P/1riO dodecylbenzenesulfonic acid sodium salt 0, / "l/rr
? O poly-p-styrene sulfonic acid potassium salt /llP/lt?
○Gelatin 4', , r f
/rr? (2) Protective layer 0 gelatin 0.79/ioN-oleoyl-N-methyltaurine sodium salt Oo, 2■/-〇 polymethyl methacrylate fine particles (average particle size 3 pm) 0. /3q/rr? (Sensitometry) Sample 1-2 was subjected to wedge exposure in the spectral sensitization region through a sharp cut filter 8C-30 manufactured by Fuji Photo Film@.

These samples were developed with the following developer at 20''C for 20 minutes, fixed, washed with water, dried, and the density of the processed samples was measured.

(Developer) Metol! , jri L-ascorbine r! J! 10f Nuvox (sodium metaborate) 3jtfKB
r /P Add water /I.

Table 2 Note that the spectral sensitivity (8o, 2) is expressed as the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2.
In Table 2, the spectral sensitivities of emulsions made of sulfur-sensitized dodecahedral matrix grains and spectrally sensitized by adding dye D-13 in an optimal amount are expressed as lOO. expressed.

As is clear from Table 2, the present invention was found to be much more sensitive than the comparative example.

The average projected area diameter of the example co-base particles is 1. An emulsion containing monodisperse silver bromide octahedral grains (coefficient of variation: //H) of 0 .mu.m was prepared, and this emulsion was optimally sulfur-sensitized with Compound-1 used in Example 1. This is called emulsion B.

Water was added to this emulsion Bt7sC)l (AgN (corresponding to J3309), and the temperature was kept at ≠j℃.
gNO3JP) and a sodium chloride aqueous solution were heated by a double jet method while maintaining the silver potential at +160 mV. Immediately after finishing the addition, add dye D-/J,
θ-4 mol/kg mol was added to give 4 g of emulsion-3tWt.

The grains contained in Emulsion-3 had minute protrusions deposited on the surface of the octahedral matrix grains.

Emulsion Hiroshi was prepared under the same conditions as in preparing Emulsion-3, except that the silver potential was set to 7 mV.
Unlike Emulsion-3, no microprojections were formed in the grains contained in Emulsion-3.

Coating sample-3, ≠ was prepared under the same conditions as in Example-1, except that Emulsion-7,2 in Example-7 was changed to Emulsion-3,4c. Further, the sample was exposed, developed, fixed, washed with water, and dried under the same conditions as in Example 1, and the density of the processed sample was measured. The results are shown in Table 3.

Table 3 Spectral sensitivity (8o, 2) Vis fog value +0°2
In Table 3, the optimum amount of Dye-73 is added to each emulsion consisting of sulfur-sensitized octahedral matrix grains. The spectral sensitivity of the emulsion spectrally sensitized was expressed as 100.

As is clear from Table 3, it was found that the non-inventive sample had a much higher sensitivity than the comparative example.

In addition, in order to observe the wrinkle formation position of the latent image on Sample-3, Sample-3 was exposed for 1 second at an appropriate exposure amount, and then developed with the above-mentioned suppressing developer at 20°C for 10 minutes. I observed the particles in -3 using an electron microscope.

As a result, most of the microscopic silver indicating the development start point was observed at the apex of the octahedral host particle (point where microprojections were not present).

Example 3 A 0.02% gelatin solution/L containing 0.001/-M potassium bromide was kept at 60°C, and potassium bromide and potassium iodide were dissolved while stirring the entire solution. The solution and the IR silver bath were added to each other by a double jet method while maintaining an appropriate transfer potential.

After the completion of the heating, the temperature was lowered to 3 J'G, and soluble salts were removed by the sedimentation method, and then the temperature was raised to ≠0°C again, and gelatin jOP was added and dissolved, and adjusted to p)ill, , and r to form a mother particle emulsion. made. The obtained base particles are monodisperse dodecahedral particles (coefficient of variation lμ%>, and the average projected area diameter is 002
3 μm, calculated from Kubelker-Munk's formula {11
1} What is the surface ratio? It is a male, and the AgI charge near the surface is .

By measuring E8CA, 1. It was zamoruchi.

The temperature of this base grain emulsion was raised to tl-60°C, and the following compound
and chemical sensitization using chloroauric acid for ≠j minutes to prepare emulsion-j.

Further, the above parent grain emulsion was chemically sensitized at 60°C using compound -■ and chloroauric acid for ≠j minutes, and then the temperature was lowered to 60°C, and a slight aqueous solution of nitric acid and a 1-17 um aqueous solution to be dammed were added. Emulsion-6 was prepared by adding microprotrusions selectively only on the {111} planes of the tetradecahedral matrix grains by adding them by the double jet method while maintaining the potential at +/lsOmV.

Samples j and 6, which are multilayer color light-sensitive materials each having the composition shown below, were prepared on a cellulose triacetate film support that had been undercoated with emulsion j and emulsion 6.

(Composition of the optical layer) The coating amount is expressed in units of silver paste/I for silver halide and colloidal silver, and P/r? for couplers, additives and gelatin. 'jt expressed in units and, for sensitizing dyes, expressed in m/l/mole per mole of halogenation in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.2 Gelatin 7.3 Colored coupler 〇-/ ,,, 0.01s UV absorber LI
V-10, / Same as above LIV-,! ...Ol, 2 dispersion oil 0il-/ ...0. O/same as above
0i1-. 2... o, oi second layer (intermediate #
) Fine grain silver bromide (average particle size 0.07 μ)... o, is gelatin
/, O colored coupler〇-,2... 0.02 minute oil 0il-/
0. /Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 molar ratio, average grain size 0.3μ)... Silver O0μ gelatin
... 0.6 sensitizing dye +
---/, (7X/(7'sensitizing dye B...j, OX/0-'sensitizing dye 1.../X/0-5 coupler C-3...0.06 coupler C -Hiroshi... 0.06 Coupler C-za... 0.0≠Coupler C-2・
... 0.03 Dispersion oil 0il-/ ... 0.03 Same as above
0i1-3 ... 0.0/2nd high layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide molar coefficient average grain size 0.3 μ) ... 0.7 sensitizing dye l
...1xio-'sensitizing dye■
...3x10' sensitizing dye■ ...
/Xl0-5 Coupler C-3... 0.2≠ Kapfu C-≠... 0.2≠Coupler C-g... 0.0≠Coupler C-2・
... 0.0μ Dispersion oil 0il-/ ... o, ij Yokami
0i1-j ... 0.02 3rd JdC 3rd
Red-sensitive emulsion layer) Emulsion-3... Silver i.

Gelatin... /, Ofu* I
+& color 21 ---
ixig-'Shukukan Ikisaku■...
3X/0''-'sensitizing dye 1...
・ /XIO' Coupler C-6... O0θj Coupler C-7... 0. / Dispersion oil 0il-/ ... 0. O7 same as above
Oil -, 2... 0.03 6th layer (middle layer) Gelatin... /, O compound C
pd-A...0.03 dispersion oil 0i
l-/...O,OS 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (iodide-≠molar ratio, average grain size 0.3μ)...0.30 sensitizing dye ■
... 5xio 'sensitizing dye■
...0.3×10' sensitizing dye V
... 2xio-'gelatin
... 7.0 coupler C-ta...
・0.2 coupler C-j...0
．． 03 coupler C-t...0.03
Pardon oil 0il-/...0.3 g
Layer (Mu green-sensitive emulsion layer) Silver iodobromide emulsion (OS mole iodide, average grain size 0.3μ)... Q, ≠ Sensitizing dye■
... j X / 0"-'sensitizing dye V ... ko
...0,3 X/0-'Coupler C-ta...0. ．． 2J coupler C-
i...0.03 coupler C-10・
・・ 0.0/! Coupler C-s...0.0/minute oil 0il-/0.2nd layer (3rd
Green-sensitive emulsion 1-) Emulsion-j...Silver o, rs gelatin...1.0 sensitized color gW
---3, txlo-4 sensitizing dye V
.../, ≠X70-4 coupler C-//
...0.0/Coupler C-/λ...
・0.03 coupler C-t3...0.
．． 20 coupler U-/...0.02
Cobra-C-/j... @ 0.0.2 fractional oil Co11-/... o,, 2゜ Same as above (Jil -, 2... 0.Ojth i0j wound C yellow filter no) gelatin
... 1.2 Yellow colloidal silver ...
0.0g compound cpa-B...0.
/Dispersion oil 0il-/ ... 0.3 1st
/layer (12th IIA emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide Hiromorchi, average grain size 0.3
μ) ... Trowel O1≠gelatin
・・・ 1.0 Exacerbation pigment ■ ・・・
Co×io-'Coupler C-/u...
o, 5F coupler C-j...0.07
Dispersion oil 0il-/...00.2 1st
2 layers (second blue-sensitive emulsion layer) Emulsion-3... Silver 0.3 Gelatin... 0.6 Sensitizing dye ■.../X/0''-'Cabra-C-/Hiroshi... 0.2j dispersion oil 0
il-/... 0.07 13th layer (first protective layer) Gelatin... O3 UV absorber TJV-t... 0. / Same as above U
V-, 2... 00.2 Dispersion oil 0il-/
... 0.0/Dispersion oil 0il-2...
o,oi@/l? ii (Second Fam) Fine grain silver bromide (average particle size 0.07 μ) ・ ・ ・ 0, j Gelatin ・ 0. ≠j polymethyl methacrylate particles (diameter/, jμ) ... 00.2 hardener)
1-t...O0 Hiroformaldehyde scavenger 8-/...0.3 Formaldehyde scavenger 8-λ...0.
3. In addition to the above-mentioned components, a surfactant was added to each J- as a coating aid.

Next, the chemical structural formula or chemical name of the compound used in the present invention is shown below: UV-/I X/Y=773 (weight ratio) C-4 H2O-C-CH3 CH2 C(CH3)3 C- Tamol. wt,, about 2. o. oo.

C-tt -tr C-t Hiro C-/J H3 CpdA CpdB Sensitizing dye 1 Sensitizing dye■ Sensitizing dye amount Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye v1 Sensitization Dye ■ -t In sample j, the amount of sensitizing dye in each layer containing emulsion j is
This is the optimum amount for spectral sensitization of emulsion j.

Sample 6 was prepared in the same manner as sample j, except that the emulsion used in sample j was changed to emulsion jt-emulsion 6, and the amount of dye in each layer containing the emulsion was increased by 7.6 times.

This photographic element was exposed to JJCM8 using a tungsten light source and the color temperature was widened and adjusted to QO°KK with a filter, and developed at 3♂nC according to the processing steps below.

Color development 3 minutes lJ seconds Bleached white 6 minutes 30 seconds Water Wash λ minutes io seconds Fixed arrival time μ minutes 20 seconds Water Wash 3 minutes ij seconds Safe, stable, 1 minute 03 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, Op/-Hydroxyethylidene- /, /-diphosphonic acid J, θ-sodium sulfite, θ-potassium carbonate
30. Ofpotassium bromide
/,≠potassium iodide
/, J dahyde a xylamine sulfur [Ji
J, ≠1≠-(N-ethylhe-β-humanmixiethylamino) 1! -Methylaniline sulfate 4. Add water i, oxpHlOo
o Bleach solution ethylenediaminetetraacetic acid ferric ammonium salt 100.0 taethylenediaminetetraacetic acid disodium salt / 0, 09 ammonium bromide ijo, op ammonium nitrate / 0, 09 add water
/, o2pal,,.

Fixer Ethylenediaminetetraacetic acid disodium salt I, op sodium sulfite Hiroshi, op thio[acid ammonium aqueous solution (70%) /7j, Ox6 sodium bisulfite Hiroshi, 6P Add water
i, obph, g, + stabilized formalin (≠Ochi) 2. Otd polyoxyethylene-p-mol nonylphenyl ether (average degree of polymerization 10), Q, 3 with addition of water /, Q2 Trial #+6 using Emulsion-6 of the present invention was compared with Comparative Emulsion-j. It was confirmed that the sample j used had high sensitivity. This example shows that the present invention is extremely effective even in multilayer color photosensitive materials.

A preferred embodiment of the present invention is the photosensitive material according to claim 1, wherein the base particles are AgBr or AgBr1 (I" content≠θ mole or less).

2. The A g I content near the surface of the base particle is lo-F:
The photosensitive material of the above 1, which is less than /I/H.

3. The above /σ)+5-element material in which the amount of Agl1 near the surface of the base particle is less than j morti.

≠, the above-mentioned photosensitive material in which the AgI content near the surface of the base particle is λ morti or less.

j, protrusions are AgCJ or AgαBr ((J” content 30
The photosensitive material according to item 1 above, which is (Mole or more).

1. The photosensitive material j above, in which chemical sensitizing nuclei are selectively present on a surface other than the i//1 surface.

7. After forming silver halide tetradecahedral grains or octahedral grains with a {111} facet ratio of 30% or more, chemical sensitization is performed, and further halogens different from the grains are selectively applied to the {111} facets. A method for producing a silver halide emulsion, characterized by forming silver halide protrusions of the composition, ♂, the average projected area diameter of the protrusions is 0.13 μm or less, and the number is 10 to 10,000 pieces/μm ! The manufacturing method according to 7 above.

The dodecahedral particles and octahedral particles are AgBr or AgH.
rl (1e content 1/-0% or less) and the protrusions are Ag (J or AgctBr).

10. 8-/~8-/ unwritten as a chemical sensitizer
2. The above manufacturing method.

ii. The above production method, wherein the surface AgI content of the dodecahedral particles and octahedral particles is 2 molt or less.

/2. flk potential 10 toomV or more (vs. -8-e-E)
The above-mentioned manufacturing method in which protrusions are formed with.

/3. The above manufacturing method in which protrusions are formed at a silver potential of 1/j (7 mV or more (vs. 8-C-E)).

Claims (1)

[Claims] 1) Silver halide tetradecahedral matrix grains or silver halide octahedral matrix grains with a {111} facet ratio of 30% or more.
111} selectively having silver halide protrusions only on the plane,
The halogen composition of the protrusions is different from that of the base particle, and the average projected area diameter of the protrusions is 0.15μ.
m or less, and the number is 10 to 10,000 pieces/μm^
A silver halide photographic light-sensitive material characterized in that 2 contains silver halide grains present on the {111} plane of a base grain. 2. The silver halide photographic light-sensitive material according to claim 1, wherein chemical sensitizing nuclei are present at positions where no silver halide protrusions are present.