JPH03196138A - Silver halide emulsion and silver halide photographic sensitive material using this emulsion - Google Patents

Abstract

PURPOSE:To improve a sensitivity/fogging ratio and the preservable stability in preservation after exposing by adding at least one kind of oxidizing agents to silver after 50% of a water soluble silver salt to be used for particle formation is added and before chemical sensitization is executed. CONSTITUTION:At least one kind of the oxidizing agents to silver are added to the silver halide emulsion after 50% of the water soluble silver salt to be used for particle formation is added to the emulsion and before the emulsion is subjected to the chemical sensitization. The oxidizing agents to silver refer to the compds. having the effect of converting metal silver to silver ions by acting on the metal silver. The formed silver ions may form silver salts hardly soluble in water, such as silver halide, silver sulfide and silver selenide and may form silver salts easily soluble in water, such as silver nitrate. The high sensitivity and the low fogging are obtd. in this way and the preservable stability in the preservation after exposing is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material having an excellent sensitivity/capri ratio and improved storage stability after exposure.

(Prior Art) Recent technological trends in silver halide photographic materials include, for example, in the field of color photographic materials, (1) In response to needs that place emphasis on sensitivity; We use photosensitive materials that have graininess, sharpness, and color reproducibility that can satisfy even ultra-high-sensitivity photosensitive materials and photosensitive materials used for shooting with small format cameras such as the 110 size system and disk size system. This is the direction we will pursue.

Technology to increase the sensitivity of silver halide emulsions is also a major source of grain improvement in that it is possible to achieve the same sensitivity with smaller grains.

Conventional chemical sensitization methods for increasing the sensitivity of silver halide photographic emulsions include sulfur sensitization, selenium sensitization, noble metal sensitization, reduction sensitization, and hydrogen sensitization. The methods have been used alone or in various combinations. These sensitization methods are described in the book by T. H.
theory of the PhotographicP
rocess ) 4th edition (Macmillan Co,
1977) pp. 149-160 and 164-165
stated on the page.

Furthermore, in addition to these sensitization methods, various emulsion manufacturing methods using silver halide solvents or so-called stabilizers have been proposed as techniques for increasing sensitivity.

In addition to this sensitization method, the higher the sensitivity of the photographic material, the larger the grain size of the emulsion is used, and especially in the case of a photosensitive material with an ISO sensitivity of 1600 or higher, the emulsion must be modified to achieve higher sensitivity. Increase particle size (~1.4μ
The current situation is that we have no choice but to rely on the above).

High sensitivity of emulsions can be achieved by the above-mentioned means, but when increasing photosensitivity by devising sensitization methods, the grain size of the emulsion is increased to increase the number of photons absorbed by one grain. In all cases, increasing photosensitivity is accompanied by: 1) an increase in fog;

2) Sensitivity increases due to storage after exposure (hereinafter, this phenomenon will be referred to as "latent image sensitization").

There were two problems.

Conventionally, general formulas (1) to (Ill
) has been proposed in US Pat. No. 3,047,595 for silver iodobromide emulsions, and in JP-A-65-504253 for high-temperature silver emulsions. However, in these proposals, general formulas (1) to (
The detailed usage position (time of addition) of the compound represented by 11) in the emulsion manufacturing process is not stated;
Furthermore, the above-mentioned problem 2) is not mentioned at all.

Problem 2) is that in color photography, the storage stability after exposure is poor, which causes variations in the color balance and gradation balance of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer, resulting in deterioration of photographic performance. It means change.

(Object of the Invention) An object of the present invention is to provide a silver halide emulsion with high sensitivity, low fog, and improved storage stability after exposure. Another object is to provide a silver halide photographic material using the above emulsion that has high sensitivity, low fog, and excellent storage stability after exposure.

(Means for Solving the Problems) The objects of the present invention are as follows: (1) In a silver halide emulsion containing photosensitive silver halide grains in a binder, a water-soluble silver salt used for grain formation of the silver halide emulsion. 1. A silver halide emulsion characterized in that at least one oxidizing agent for silver is added after the addition of sag and before chemical sensitization.

(2) The oxidizing agent for silver has the general formula (1), (
The silver halide emulsion according to claim 1, which is at least one compound represented by II) or (III).

(1) R-8O@B-M (II) R-80 warehouse 8-Rl (f[) R-13018-Ll! l-8801-R
"In the formula, R, R1% R1 may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, m is 0 or 1.

The compounds of general formulas (1) to (III) may be polymers containing divalent groups derived from the structures shown by (1) to (III) as repeating units.

Furthermore, when possible, R, R2, R1, and l may be combined with each other to form a ring.

and (3) having at least one silver halide emulsion layer on the support, the emulsion layer containing at least one silver halide emulsion according to claim (1) or (2). Characteristic silver halide photographic materials.

achieved by

The present invention will be explained in detail below.

The oxidizing agent for silver in the present invention refers to a compound that acts on metallic silver to convert it into silver ions. Particularly effective are compounds that convert extremely minute silver atoms produced by-product in the process of forming silver halide grains into silver ions. The silver ions generated here may form @ salts that are sparingly soluble in water, such as silver halide, silver sulfide, and silver selenide.
Further, a water-easily soluble silver salt such as silver nitrate may be formed.

The oxidizing agent for silver may be inorganic or organic. Inorganic oxidizing agents include ozone, hydrogen peroxide and their adducts (for example, Nl!LBO!"H!
O! "3H20,2NaCO1" 3T1zO2,
Na4F107 * 2T120z, 2 Na, So
, 6EI, O, @ 2H, O), peroxylate (
For example, X2 days t 08, K10! 0m, K2P,
O, ), beoxy complex compounds (e.g., K, (Ti
(0ri0.04) -3H,014x,5o4-T1(
o,) oa-so4@2H! o, 1ia3CVO(Ox
XCtO4)x 6HzO), permanganate (e.g. KMnO4), chromate (e.g. KsOr*O
Oxygen acid salts such as y), halogen elements such as Tendou and bromine,
These include perhalates (eg, potassium periodate), salts of high valence metals (eg, potassium hexacyanoferric acid), and thiosulfonates.

In addition, examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (e.g., N-bromsuccinimide, chloramine T1, clohumin B). is given as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonic acid salts, and organic oxidizing agents such as quinones.

A more preferred oxidizing agent is a thiosulfonate, which can be selected from compounds represented by formula [I] or In). The most preferred among these are the compounds represented by formula (1), which have the effect of converting silver into silver sulfide.

To explain in more detail the thiosulfonic acid compounds of general formulas (I), (It) and (III), when R, R1 and R1 are aliphatic groups, saturated or unsaturated, linear, branched or cyclic is an aliphatic hydrocarbon group, preferably a group having 1 to 22 carbon atoms, in the following formula, 8% R1, R
1 may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compound of general formula (1) or i[) is a divalent group or 1 derived from the structure represented by (1) or In).
It may also be a polymer containing a divalent group derived from the structure shown in m) as a repeating unit.

Further, when possible, R, R', R" and L may be combined with each other to form a ring.

2-ethyμhexVIV, decyl, dodecyl, hexadecyl, octadecyl, cyclohexy~, isopropyl, t
-Buchi μ can be mentioned.

Examples of the alkenyl group include ari〃 and putenylμ.

Examples of the alkini μ group include propargyl, petitiny
can be given.

The aromatic group represented by 8% R1 and R1 includes a monocyclic or condensed ring aromatic group, preferably one having 6 to 20 carbon atoms, such as Fe2μ and Naphthi. These may be substituted.

The heterocyclic group of R, R'' and R1 includes nitrogen, oxygen,
3 having at least one element selected from sulfur, selenium, Te/I/lv and at least one carbon atom
to 15-membered rings, preferably 3- to 6-membered rings, such as pyrrolidine, piperidine, pyridine,
Tetrahydrofufun, thiophene, oxazo-, thiazo-μ, imidazole, benzothiazo-〃, benzoxazo-μ, benzimidazo-μ, selenazole, benzoselenazole, tetrazole, triacyl, benzotriazole, tetrazole, oxadiazole, thiadeacyl ring can be given.

Examples of substituents for R, R'' and R1 include alkyl groups (e.g., methyl, ethyl, hexyfV), alkoxy groups (e.g., methoxy, ethoxy, octyloxy),
Aryl group (e.g. phenyl, naphthyl, triA/)
, hydroxyl group, halogen atom (e.g. fluorine, chlorine,
bromine, iodine), aryloxy groups (e.g. phenoxy)
, alkylthio groups (e.g. methylthio, butylthio)
, arylthio group (e.g. phenylthio), VA/
groups (e.g., acetyl, propionyl, butyryl, parelli/I/), sulfonyl groups (e.g., methylsulfonyl)
, phenylsulfonyl IV), acymu amino group (e.g.
acetylamino, pencil yvami/), stv*=
rv amino group (e.g., methanesulfonylamino, benzenesulfonylamino), acyloquine group (e.g., acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, -802M group, (M is 1 -80, R1 group indicating a valent cation.

The divalent linking group represented by B is C,N.

An atom or atomic group containing at least one selected from S and O. Specifically, alkylene group, alkenylene group, arylene group, arylene group, -O--El--N
It consists of H--00--8O,-, etc. alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include -+CH2)
(n=1 to 12), Examples of the repeating unit include the following.

It will be done.

00□CHf0 horse 00H20H! So, 8MM is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Table (1-1) CH380! 8 Na (1-1s) C! H2= OHOH2802S Na (1-2) CIH5SO2SNa (I-16) (I-5) (!11H13SO2SN& (I-17) 0, H .

(1-20) (I-26) (1-23) (1-24) (1-29) xsso, (aH,), so, sx Amount of oxidizing agent added to silver 1 mo/I/ of the present invention is 10-
1 to 10-1-! It is desirable to choose from the range l:1y, Na5SO2(Cut)4801sna(1-11) NaSElo, (01(2)4El(C!H,)4So
2SNa(1-32) Ru.

The timing of adding the oxidizing agent of the present invention will be explained.

The manufacturing process of silver halide emulsions is broadly divided into steps such as grain formation, desalting, chemical sensitization, and coating. Particle formation is nucleation
It is divided into maturity, growth, etc. This (1-3!l) 802 B Na The timing of addition of the oxidizing agent of the present invention is more preferably 50 minutes of the water-soluble silver salt used for forming grains of the emulsion. If it is added during the desalting process, it can be added at any time during the process as described above, and adding it before chemical sensitization refers to sensitizers such as gold sensitizers, sulfur sensitizers, selenium sensitizers, etc. It means to add it before adding the agent. Furthermore, when a sensitizing dye is added prior to chemical sensitization, it is preferably added before the sensitizing dye.

In order to add the oxidizing agents represented by the general formulas (1) to [■] during the manufacturing process, methods commonly used for adding additives to photographic emulsions can be applied. For example, water-soluble compounds should be prepared as aqueous solutions with appropriate concentrations, and compounds that are insoluble or poorly soluble in water should be prepared in suitable organic solvents that are miscible with water, such as alcohols, glycols, ketones, esters, etc.
Among amides and the like, it can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution.

The average silver halide composition of the entire grain of the silver halide grains of the present invention is silver iodobromide or silver iodochlorobromide containing 1 to 30 mo/I/4 silver iodide. It preferably contains 7 to 20 mol of silver iodide, and may contain 10 mo/I/4 or less of silver chloride.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes; Select from single twins containing one crystal plane, parallel multiple twins containing two or more parallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, etc. depending on the purpose. be able to.

In the case of a normal crystal, a cube consisting of (10()) planes, (1
11) Octahedral particles consisting of planes, dodecahedral particles consisting of (110) planes disclosed in Japanese Patent Publication No. 55-42737 and Japanese Patent Application Laid-Open No. 60-222842 can be used.

In addition, Journal of Engineering Magin”g 5ci
ence Vol. 30, Page 247 As reported in 1986, (211) is the representative (hl) surface number, (331) is the representative (hhl) surface number, (210)
The (hko) plane number representing the ) plane and the (hkl) plane number representing the (321) plane require some ingenuity in the preparation method, but they can be selected and used depending on the purpose. A tetradecahedral particle in which (100) and (111) planes coexist in one particle, (
Particles with coexisting (100) and (110) planes or (1
11) Particles in which two or many surfaces coexist, such as particles in which a plane and a (110) plane coexist, can also be selected and used depending on the purpose.

The grain size of the silver halide grains of the present invention may be fine grains of 11 microns or less, or large grains with a projected area diameter of up to 10 microns.

Although the effects of the present invention can be achieved with both monodispersed emulsions and polydispersed emulsions, monodispersed emulsions are more preferred.

Here, monodispersity is defined by at least one of the coefficient of variation of the projected area area equivalent diameter of the particles or the sphere equivalent diameter of the particle volume being 20 or less. More preferably, it is 15 or less.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Gufufkide, published by Bo-Montel (p.

Glafkides, Ohimie et Phys
ique PhotographiclueFauIM
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffin,
Photog-raphic EmR1sion Ch
emistry (Focal Press, 196
6), “Manufacture and Coating of Photographic Emulsions” by Zelilcman et al., published by Focal 1 Fufu (V, I4 Zelilcman)
et am, Making and Coating
Photographic EhnR1sion, Fo
calFrees, 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 halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. 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 one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling 1) Ag and pH during grain formation. For more information, see Photographic Sand Science and Engineering.
8science and Ifingineerin
B) Volume 6, pp. 159-165 (1962); Jhana/L/ψop-huo F.
our-nal of Photographic 8
science), vol. 12, pp. 242-251 (I
964), US Pat. No. 4,655,394 and British Patent No. 1.415,748.

Further, tabular grains having an aspect ratio of 3 or more are preferable for the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by C1ove, Photogra-p
hy Theory and Practice (I
930)), p. 131;
utoff, PhotoHra-phic Etci
ence and Engineering),
Volume 14.

pp. 248-257 (1970); U.S. Patent No. 4°43
4,226, 4.414.510, 4.435048, 4.459.520 and British Patent No. 2
, 112, 157, and the like. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, and the above-cited US Pat. No. 4.434.226
It is detailed in the issue.

Tabular grains are preferable as the emulsion of the present invention, and tabular grains whose total projected area is 604 or more and have an aspect ratio of 3 or more are more preferable. Particularly preferred are tabular grains having an aspect ratio of '5 to 1°, accounting for a factor of 60 or more of the total projected area. In the case of tabular grains as well, the grain size distribution is preferably monodisperse. It is preferable that the coefficient of variation of the circle equivalent diameter of the projected area or the sphere equivalent diameter of the volume is 25 or less, and more preferably 20
The width is preferably 1 or less, particularly 15 or less.

In the silver halide emulsion used in the present invention, the crystal structure of the silver halide grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure. These emulsion grains are described in British patent no.
No. 021146, U.S. Patent No. 4505,068, U.S. Patent No. 4
, 444,877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides with different compositions may be bonded by epitaxial bonding (
It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

When the silver halide emulsion of the present invention is a silver iodobromide emulsion and has a uniform structure in terms of halogen composition, silver iodobromide with a silver iodide content of 20 mo/L/4 or less is preferred. Further, the preferred silver iodide content varies depending on the purpose.

For example, when an emulsion with fast development progress is required, silver iodide is preferably less than 10 moles, more preferably silver iodide is 5 moles/l/II.
The following are preferred. Further, when an emulsion with a softer gradation is required, an emulsion with a relatively high silver iodide content may be designed, and in this case, it is preferable that the silver iodide content is 5 mo/L/4 or more.

The silver halide emulsion of the present invention can also have a distribution or structure in terms of halogen composition in its grains. Typical examples are JP Publication No. 43-13162 and JP Patent Publication No. 61/1989.
-215540, JP-A-60-222845, JP-A-6
These are core-shell type or double-structured particles in which the interior and surface layers of the particles have different halogen compositions, such as those disclosed in Japanese Patent No. 1-75337. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. Further, although the core portion is a clearly regular particle, the shape of the shelled particle may be slightly distorted or irregular. Moreover, instead of a simple double structure, a triple structure as disclosed in JP-A No. 60-222844 or a more multi-layer structure,
Silver halides having different compositions can be thinly applied to the surface of the core-shell double-structured grains.

In order to give a structure to the inside of a particle, it is possible to create a particle having not only the above-mentioned enveloping structure but also a so-called bonding structure. These examples are disclosed in Japanese Patent Application Laid-Open No. 59-13354.
0, Japanese Patent Publication No. 58-108526 KP199290A
2. Japanese Patent Publication No. 58-24772, Japanese Patent Publication No. 59-16254
etc. are disclosed. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

In the case of a bonded structure, a combination of silver halides is naturally possible, but a bonded structure can be obtained by combining a silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, non-silver salt compounds such as p'bo may also be used if a bonded structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, or conversely, the core part has a low silver iodide content. The particles may have a low silveride content and a high shell portion.

Even in the case of grains having a structure with such a silver iodide content, the preferred silver iodide content on the grain surface differs depending on the purpose. For example, when an emulsion with fast development progress is required, the silver iodide content near the grain surface is preferably less than 10 moles/L/l of silver iodide, more preferably less than 5 mos/+/11 moles of silver iodide. Furthermore, when an emulsion with a softer gradation is required, an emulsion with a relatively high silver iodide content near the grain surface may be designed, and in that case, it is preferable that the silver iodide content is 57 or more. .

In order to adjust the silver iodide content near the grain surface to the desired content, the silver iodide content in the shell portion itself may be set to the desired content, or silver halide of the desired composition may be thinly applied to the grain surface. .

Similarly, grains having a bonded structure may be grains in which the host crystal has a high silver iodide content and the bonded crystal has a relatively low silver iodide content, or vice versa.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is 1! IP-On96
727Ef, 1! : Processing to round particles as disclosed in P-0064412B1 etc., or DB-230644702, JP-A-60-221520
Surface modifications such as those disclosed in .

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion can also be used by selecting the developer or development conditions, as disclosed in JP-A-59-133542. can. A shallow internal latent image type emulsion covered with a thin film may also be used depending on the purpose.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

The silver halide grains of the present invention are subjected to at least one of sulfur sensitization, gold sensitization, or noble metal sensitization at any stage of the silver halide emulsion manufacturing process, typically grain formation. These chemical sensitization methods differ depending on the composition, structure, and shape of the emulsion grains, as well as the intended use of the emulsion, but when chemical sensitization nuclei are embedded inside the grains, they are embedded shallowly from the grain surface. In some cases, chemical sensitization nuclei may be created on the surface. Although the effects of the present invention are effective in any case, it is particularly preferable to create chemically sensitized nuclei near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Preferred chemical sensitization in the present invention (hereinafter also simply referred to as chemical sensitization) is gold sensitization, sulfur sensitization, or noble metal sensitization, either alone or in combination.
Mes), The Photographic Process, 4th edition, McMion Publishing L1977, (T, H, James
s, The Theory of the Pho
to-graphic Process, 4th
ad, Macmillan.

It can be carried out using activated gelatin as described in 1977) 6, p. 76, or Research Disclosure, Vol. 120, April 1974, 12008;
Research Disclosure Volume 34, 1975 6
13452, U.S. Patent Nos. 2,642,361, 4297.446, 772,051, 3,8
No. 57,711, No. 901, 714, No. 4,266
．． No. 018, and No. 1904.415, and PAg5 as described in British Patent No. 1.31 to No. 755.
~10, pT 15-8 and temperature 30-80°C sulfur, selenium, di/L/A/, gold, platinum, badge rum,
It can be iridium or a combination of multiple of these sensitizers. These chemical sensitizations are most preferably carried out in the presence of gold compounds and thiocyanate compounds and in the presence of sulfur-containing sensitizers as described in U.S. Pat. It is carried out in the presence of a sulfur-containing compound such as a compound or hypo, a thiourea compound, or a rhodanine compound. Chemical sensitization can also be carried out in the presence of so-called chemical sensitization aids. Useful chemical sensitization aids include compounds known to suppress capri and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Patent No. 4131.
0! No. 18, No. 5,411,914, No. 554, 7
No. 57, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention shows favorable effects even when gold sensitization is used in combination. The preferred amount of the gold sensitizer is from 1 x 101 to I x 10''-' mol of silver halide, more preferably from f x 10'' to 5 x 10-' 7 µm.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1X10-' to 1 per mole of silver halide.
0i7μ, more preferably 1×10−s~5
X10-' mole.

In gold/sulfur sensitization, it is preferable to use the above conditions in combination.

It is preferable to subject the silver halide grains of the present invention to reduction sensitization during grain formation, or after grain formation, before chemical sensitization, or during or after chemical sensitization.

Here, reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, and a low pAg of 1 to 7 is called silver ripening.
Method of growing or aging in Ag atmosphere, high p
Either a method of growing in a high pH atmosphere of pH 8 to 11 called H ripening or a method of aging can be selected. Moreover, two or more methods can also be used together.

The method of adding a reduction sensitizer is a preferred method since the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrofuzine derivatives, formamidine sulfinic acid, kufun compounds, bofun compounds, and the like are known.

For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can also be used in combination. Preferred compounds as reduction sensitizers include g-i chloride, thiourea dioxide, dimethylamine bofun, ascorbic acid and its derivatives. Since the amount of reduction sensitizer added depends on the emulsion manufacturing conditions, it is necessary to specify the amount added, but it is 1) 1a-7 to I C+- per mole of silver halide.
1-11: tvtD range 1zE4 equivalent.

Reduction sensitizers include water, alcohols, glycols,
It is dissolved in a solvent such as ketones, esters, and amides and added during particle growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle growth. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to precipitate silver halide grains. It is also a preferable method to add the solution of the reduction sensitizer in several portions or continuously over a long period of time as the particles grow.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azo/L/s, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazo-ys, chlorobenzimidazo-Ms,
Bromobenzimidazo-IV, mercaptothiazo-M
mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazo-μs, aminotriazoles, benzotriazoles, diF-lobenzoF-lyases, me-kabutotetofuso tvm<especially 1
-Fueni A/-5-Mercaptotetofuzo A/) etc.-
mercaptopyrimidines; memucaptoY lyazines; thioketo compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (L 3.3a
, 7) tetraazaindenes), pentaazaindenes, etc., many compounds known as anti-capri agents or stabilizers can be added. For example, those described in U.S. Pat. No. 954.474, U.S. Pat.

The photographic emulsion used in the present invention is preferably spectrally sensitized with methane dyes or the like in order to achieve the effects of the present invention. Dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobotucyanine dyes, hemicuanine dyes, styryl dyes, and hemioxono dyes.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a pigment belonging to complex merocyanine pigments.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazoline nucleus, thiozoline nucleus, billow μ nucleus, oxazo-〃 nucleus, thiazole nucleus, selenazole nucleus, imidazo-μ nucleus, tetrazole nucleus, pyridine nucleus, etc.; alicyclic hydrocarbon ring is fused to these nuclei. and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indo-μ nucleus,
A benzoxadole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenacyl nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Typical examples are U.S. Patent Nos. 2.68 & 545 and 2.97.
Su No. 229, same No. 397.060, same! %522゜0
No. 52, No. 527.641, No. 617.295, No. 4628,964, No. 666.480, No. 672,898, No. 679.428, No. 70 &
No. 577, same! W 769.501, same to 814, 6
No. 09, No. 857.862, No. 4,026,70
7, British Patent No. 1.34.4.281, British Patent No. 1.507
No. 803, Special Publication No. 45-4936, No. 53-12.
No. 575, No. 618 to JP-A No. 52-11, No. 52-10
9.925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The sensitizing dye may be added to the emulsion at any stage of emulsion preparation known to be useful. Although it is usually carried out after chemical sensitization is completed and before application, it can be carried out at the same time as chemical sensitization, as described in U.S. Pat. Spectral sensitization can be carried out at the same time as chemical sensitization, or it can be carried out prior to chemical sensitization as described in JP-A-58-11 & 928.
It is also possible to start spectral sensitization by adding it before the completion of silver halide grain precipitation. Furthermore, U.S. Patent No. 4.2
It is also possible to add these said compounds separately as taught in No. 25.666, i.e. some of these compounds are added before chemical sensitization and the rest after chemical sensitization. Possible and U.S. Patent No. 4.184756
at any time during the formation of silver halide grains including the method taught in No.

However, the preferable timing for adding the dye in the present invention is as mentioned above, and the addition is before chemical sensitization, or the amount of halogen added is 4 x 10 → ~ 13 However, in the case of a more preferable silver halide grain size α2 to 1.2 μm, it is approximately 5×10−
8-2 X 10-''-E: A/Kayori is effective.

The various additives mentioned above are used in the photosensitive material related to the present technology, but other various additives can also be used depending on the purpose.

These additives are described in detail in Research Disclosure Etθm 17643 (December 1978).
and Gakko tem 18716 (November 1979), and the relevant parts are summarized in the table below.

In addition, the spectral sensitizing dye used in the present invention is disclosed in Japanese Patent Application Laid-Open No. 62-89
It can be used in combination with a nitrogen-containing heterocyclic compound described in No. 952 and represented by the following general formula.

General formula (wherein R1 represents at least one 1000M or 1808M aliphatic group, aromatic group or heterocyclic group, M is a hydrogen atom, alkali additive type RD 17643 RI) 18716 1 Chemical sensitizer 2 Sensitivity increasing agent Page 23 Page 648 Right column Same as above The amount used is per mole of silver halide, 1×4 brightener Page 24 Various color couplers can be used in the present invention. A specific example of this can be found in the aforementioned Research Disclosure (
RD) ffil 7643, ■-c~G.

As a yellow coupler, for example, U.S. Patent No. 934
No. 501, No. 4,022,620, No. 4.32 to 024, No. 4.401.752, Special Publication No. 1987-1
0739, British Patent No. 1,425,020, British Patent No. 1
．． 47 & 760 are preferred.

As magenta couplers, 5-pizzolone and bifuzoloazole M compounds are preferred, for example, US Pat.
, 31 (No. 1,619, No. 4.351.897, European Patent No. 74656, US Patent No. 4061, 432, US Patent No. 472 to 067, Research Disclosure P&I 24220 (June 1984), Special 1986-
No. 55552, Research Disclosure Na24
230 (June 1984), JP 60-45659, U.S. Patent No. 4,500.650, 4.54 to 6
Particularly preferred is the one described in No. 54 No. 0.

As cyan couplers, pheno-p type and naphtho-μ
For example, U.S. Patent No. 4.05 Otsu 2
No. 12, No. 4.14 & 596, No. 4.22 &
No. 233, No. 4.29 to No. 200, No. 2.369.
No. 929, No. 2,801,171, No. 2,772
, No. 162, No. 2,895,826, No. F 7Z
OO2, same No. 75 a308, same No. 4,334,
No. 011, No. 4.327.173, West German Patent Publication No. 4529.729, European Patent No. 121,365 A, US Patent No. ! No. 4444622, No. 4.33 &
No. 999, No. 4.451.559, No. 4.427
．． 767, EP 161,626A are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available, for example, from Research Disclosure Nl117.
Section ■-G of 643, U.S. Patent No. 416 to 670, Japanese Patent Publication No. 57-59415, U.S. Patent No. 4.004.929
No. 4.13 & 258, British Patent No. 1,146.
! The one described in No. 168 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include, for example, U.S. Patent No. 4,566.257, British Patent No. 2,
Preference is given to those described in German Patent No. 125,570, European Patent No. 96,570 and German Patent Publication No. i 234.533.

Typical examples of polymerized pigment-forming Kabutsu are U.S. Pat. No. 4,451.820, U.S. Pat.
It is stated in No. 3, etc.

Couplers that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR cadets that release development inhibitors include the aforementioned RD17645,
■ - Nine patents listed in Section F, JP-A-57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 4Q 97.14.
No. 0, No. 2,131,188, JP-A-59-157
Those described in No. 658 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include Competitive Deaf described in U.S. Pat. No. 4.13 (1,427), U.S. Pat. .53 a393, same no. 4,310゜618
Multi-equivalent Kadewo described in No. 1, etc., JP-A-60-18595
0, DIR redox compound described in JP-A No. 62-24252, etc. or I) IR Kabutu-emitting force Bufu or D
IR Capfu emission power output def- or V-dox, a coupler that releases a dye that recolors after separation, described in European Patent No. 171502A, R, I), II41111449, I24241, JP-A-61-201247, etc. and the ligand-releasing couplers described in U.S. Pat.

The couplers used in the present invention can be incorporated into the g-light material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (e.g., dipty-μ phthalate, synchrohexyl phthalate, di-2-ethylhexyμ-phthalate V- ), decyl phthalate, bis(2゜4-di-t-amiμpheniA/
) Lid v-t, screw (2,4-di-t-ami~fenif)
v) Isophthalate, bis(1,1-diethylpropy/
I/) phthalate)), esters of phosphoric acid or phosphonic acid (e.g. Eva) Lihueni μ phosphate, Frecci i
V pho7 phosphate, 2-ethy μhexy μ diphenyl phosphate, tricyclohex VILI phosphate, )! J
-2-z-hexy phosphate, tritide VIV phosphate, triptoxyethyl phosphate),)! J
Chloropropyl phosphate, di-2-ethylhexylphene (μphosphonate)), benzoic acid esters (e.g. 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexylp-hydroxybenzoate), amides (e.g. N, N -diethyldodecaneamide, N,N-diethyllaurylamide, N-tetofudecyμ
pyrrolidone), alcohol μ or pheno-/'l] (
For example, isonuteari M alco-tv, za-ter.
t-amiMpueno fv), aliphatic acid esters [lIt is bis(2-ethylhexy/I/)sepacate, dioctyl azelate, glycero-μ triptylate F, isostearyl fuctate, trioctyl citrate], Aniline derivatives (e.g. N, N-dipty/l/-
2-butoxy-5-tert-octylaniline), hydrocarbons (for example, puffin, dodecylbenzene, diisopropylnaphthalene), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of the process, effects, and ftex of the impregnated layer of the latex dispersion method include U.S. Pat. It is described in.

The silver halide of the present invention can be applied to various color photosensitive materials. Color negative film for general use or motion pictures, color reversal film for film or television
Typical examples include cuff-vapor, cuff-positive film, and cuff-inverted vapor.

When the present invention is used for cuff photographic materials, it can be applied to photosensitive materials of various configurations and photosensitive materials that combine layer configurations and special color materials.

A typical example is illustrated below. JP 47-49031, JP 49-5843, JP 50-21248, JP 59-58147, JP 59-60457,
JP 60-227256, JP 61-4045, JP 61-43743, JP 61-42657
A combination of the coupling speed and diffusivity of the cuff-coupler and the layer structure, as in No. Tokuko Sho 49-154
No. 95, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 55-3701
No. 7, Special Publication No. 53-37018, Japanese Patent Publication No. 51-490
No. 27, JP-A-52-143016, JP-A-53-9
No. 7424, JP-A-53-97831, JP-A-62-
200550 and JP-A-59-177551, which stipulate the arrangement of a "high-sensitivity layer" and a low-sensitivity layer, and the arrangement of layers with different color sensitivities.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, 28 pages of 1lk17643 and art book 18716
It is described from the right column on page 647 to the left column on page 648.

The color photographic light-sensitive material according to the present invention includes the above-mentioned RD, L
17643, pages 28-29, and N18716, 6
51. Development processing can be carried out by the usual methods described in the left column to right column.

The color developing 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. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methy/L'-4-amino-N, N-jethyμ aniline. , 3-methy/L'-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl'-N-β-methanesulfonamidoethylaniline, 3-methyl Examples thereof include /L/-4-amino-N-ethyl A/-N-β-methoxyaniline and their sulfates, hydrochlorides, and p-)A/enesulfonates. These compounds are used depending on the purpose2
It can also be used in combination with more than one building.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazo-s or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethyl hydroxylamine, sulfite m, hydrazines, phenyl-semicarbazides, triethanolamine, catechol sulfonic acid 1i, )
Liethylenediamine (1,4-diazabicyclo[2゜2
．． 2] Various preservatives such as octane), solvents such as ethylene glycol-μ and diethylene glycol, development accelerators such as benzyl alcohol, polyethison glycol, quaternary ammonium salts, and amines, dye-forming couplers, Competitive capacitors such as Kabufu sodium boron hydride, auxiliary developing agents such as 1-Fe=A/-3-bifuzolidone, viscosity-imparting agents, amitobolic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonic acid, etc. Various chelating agents represented by bonic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitriloacetic acid, etc. -N, N,
N-trimethylenephosphonic acid, ethylenediamine-N,
N, N'.

Typical examples include N'-tetofumethylenephosphonic acid, ethylene diamine di(0-hydroxyphenyl acetic acid #), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-PhenyA/-5-
Known black and white developing agents such as 3-virazolidones such as bifuzolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

These color developing solutions and black and white developing solutions generally have a pH of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but generally it is less than 3 times per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 times. −
You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (1m), cobalt (I),
Compounds of polyvalent metals such as ff), chromium (■), and copper i), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (ill) or copal (fil), such as ethylenediaminetetraacetic acid, diethyltriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glyco-
〃Amicibolic acid such as ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (II) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid fil complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but it is also possible to process at a lower pH to speed up the processing. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 4,894,858, German Patent No. 1.2.
No. 90.812, No. 2.059.988, Japanese Unexamined Patent Publication No. 1973
-32,736, 53-51831, 55-3
No. 418, No. 53-74623, No. 53-95, 6
No. 50, No. 53-9 to No. 631, No. 5!1-104,2
No. 32, No. 53-124, 424, No. 53-141.
623, No. 53-211426, Research Disclosure Na [7゜129 (July 1978), etc. Compounds having a mercapto group or disulfide group; Thiazolisones described in JP-A-50-140,129 Derivatives: Japanese Patent Publication No. 1983-A506, Japanese Patent Publication No. 1982-
2G, No. 852, No. 53-32,735, thiourea derivatives described in U.S. Pat. No. 4,706,561;
Iodide salt described in No. 964410, West German Patent No. 2
．． Polyoxyethylene compounds described in No. 74 &430; polyamine compounds described in Japanese Patent Publication No. 45-8856;
Other genitals No. 49-42, 434, No. 49-59.6
No. 44, No. 53-94, 927, No. 54-5 727
Compounds described in No. 1, No. 55-24506, and No. 58-164940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred in US Pat. No. 4,894.
No. 858, West German Patent No. 1,290,812, JP-A-5
The compounds described in No. 3-95.630 are preferred. Furthermore,
Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material.

These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixatives include thiosulfates, thiocyanates, thiether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonidibisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after deoxidation treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as Kapfu), the application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
ur-nal of the 5ociety of
Motion Picture andTe1θvis
ion Engineers Volume 64, P, 24B-
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing the amount of μsium ions and magnesium ions described in Japanese Patent Application No. 61-151, 632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendaseals, and chlorinated sodium isocyanurate described in Japanese Patent Application Laid-open No. 57-542, and other chlorine-based disinfectants such as benzotriacy N, "Bacterial and fungicidal agents" written by Hiroshi Horiguchi, It is also possible to use disinfectants described in "Chemistry", "Sanitation Technology Lifeline", "Sterilization, Disinfection, and Antifungal Technology of Microorganisms", and "Dictionary of Antibacterial and Antifungal Agents" of the Japanese Society of Antibacterial and Antifungal Agents.

The pH of the washing water in processing the photosensitive material of the present invention is 4-9.
and preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 25
A range of 30 seconds to 5 minutes at -40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-IL543, 58-14, 83
All known methods described in No. 4, No. 60-22 to No. 345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various fungicides and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. Since K is incorporated, it is preferable to use various precursors of color developing agents. For example, U.S. Patent No. 4342.597
Indoaniline compounds described in No. 434Z599
No., Research Society Disclosure No. 14,850 and Ship base type compounds described in No. 1 to No. 159, No. 1 & 92 of the same.
Adole compound described in No. 4, US Patent No. 5.719.
Metal salt complex described in No. 492, JP-A-53-13 & 628
Examples include the urethane compounds described in No.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 1-Phenyl A/- for the purpose of promoting color development.
3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-144,547.
No. 58-115゜438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, and conversely, lower temperatures can improve image quality and stability of the processing solution. be able to. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 674,499 may be carried out.

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500.626, JP-A-133449, No. 5
It can also be applied to heat-developable photosensitive materials such as those described in European Patent No. 9-218443, European Patent No. 61-238056, and European Patent No. 21 to No. 66OA2.

When the photosensitive material of the present invention is used in the form of a roll, it is preferably stored in a cartridge. The most common cartridge is the current 135 format cartridge. In addition, cartridges proposed in the following patents can also be used.

Utility Model Publication No. 58-67529, Japanese Patent Application Publication No. 58-181035
No., Japanese Patent Application Publication No. 58-1B2654, Japanese Patent Publication No. 58-1B-195
No. 236, U.S. Patent No. 4,221,479, Patent Application No. 1983-5
No. 7785, Japanese Patent Application No. 183344 (1983), Special Application No. 183344 (1988)
-525658, Japanese Patent Application No. 1-21862, Japanese Patent Application No. 1
-25562, Japanese Patent Application No. 1-50246, Japanese Patent Application No. 1-
No. 20222, Japanese Patent Application No. 1-21865, Japanese Patent Application No. 1-3
No. 7181, Japanese Patent Application No. 1-33108, Japanese Patent Application No. 1-85
No. 195, Japanese Patent Application No. 1-172595, Japanese Patent Application No. 1-17
No. 2594, Japanese Patent Application No. 1-172595, U.S. Patent No. 48
No. 46418, U.S. Patent No. 4,848,695, U.S. Patent No. 4
No. 832275.

(51! Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1) Example 1 shows an example of tabular grains.

Preparation of Emulsion A A solution of 21 f of inert gelatin, 7, Of of potassium bromide in 1.4 t of distilled water was stirred at 50°C, and added to the solution 12. 70 cc of an aqueous solution of silver nitrate and 70 cc of an aqueous solution containing potassium bromide aor and potassium iodide α5f were simultaneously added at a constant flow rate for 45 seconds using the dab/l/jet method (first stage addition). After adding 2,201 g of an inert gelatin solution to this, the temperature was raised to 65°C. 50 minutes after the temperature reaches 65°C, an aqueous solution 43 containing 150 tons of silver nitrate
4 steps were added in 35 minutes, during which time 200f of potassium bromide was added.
, and an aqueous solution containing 4.3 t of potassium iodide to maintain the pBr at 2.5 (second stage addition)
.

After the second stage addition was completed, 45 cc of potassium thiocyanate 1N solution was added. After 2 minutes, silver nitrate 95? Aqueous solution 51 of
7 CC was added over 20 minutes, during which time 200 CC of potassium bromide was added.
pBr was maintained at 2.5 using an aqueous solution containing 1 and 43 tons of potassium iodide (fifth stage addition).

The desalting process was started 10 minutes later, and after the desalting process was completed, the mixture was redispersed and optimally sensitized with gold and ions at 60°C.

After completion of chemical sensitization, at 40 DEG C., 6.times.10@-4 mo.mu. of the dye described later was added per mole of silver nitrate.

Goton and Dan! In cup emulsion A, 10 minutes after the start of the second addition,
-5) thiosulfonic acid compound was added at 1×1 (+'7) per mole of silver nitrate for grain formation.

Other than that, it was made in the same manner as Emulsion A.

Preparation of Emulsion C In emulsion BIC, the timing of addition of the thiosulfonic acid compound was changed to 22 minutes after the start of the second addition.

Other than that, it was made in the same manner as Emulsion B.

Preparation of emulsion In emulsion B, the timing of addition of the thiosulfonic acid compound was changed to coincide with the start of addition in the third stage.

Other than that, Emulsion 9 is made in the same manner as Emulsion B.

Preparation of Emulsion E In Emulsion B, the timing of addition of the thiosulfonic acid compound was changed to 15 minutes after the start of the third addition.

Other than that, it was made in the same manner as Emulsion B.

Preparation of Emulsion F In Emulsion B, the timing of addition of the thiosulfonic acid compound was changed to 10 seconds after the completion of the third addition.

Other than that, it was made in the same manner as Emulsion B.

Preparation of Emulsion G In Emulsion B, the same number of moles of hydrogen peroxide was added instead of the thiosulfonic acid compound.

Other than that, it was made in the same manner as Emulsion B.

Preparation of Emulsion H In Emulsion E, the same number of moles of hydrogen peroxide was added instead of the thiosulfonic acid compound.

Other than that, it was made in the same manner as Emulsion E.

Preparation of Emulsion B-2 In Emulsion B, after the desalting step was completed, the following chemical sensitization was carried out. That is, dye A was added at 60°C per mole of silver nitrate.
X 10''-'7μ was added, and 20 minutes later, gold and sulfur sensitization was optimally carried out at 60°C.

emulsion? In prepared emulsion A of -2, after the desalting step was completed, the following chemical sensitization was performed. That is, dye A was added at 60°C per mo μ of silver nitrate.
Gold and sulfur sensitization was optimally carried out at 60° C. 20 minutes after adding 10 −4 μg of X.

The above emulsions A-1'I, B-2, and IF-2 all have an average equivalent circle diameter of 11.6μ and an average aspect ratio of 5.
．． It was a tabular grain with a coefficient of variation of equivalent circle diameter of 194.

Samples 101 to IQ8 coated with emulsions A-H and emulsions B-2, ? Sample 109°110 coated with -2 was prepared as follows.9.

Preparation of Sample 101 The emulsion layer and protective layer shown below were coated on a triacetyl cellulose film support provided with an undercoat layer.

・Emulsion layer ・Silver halide grains of emulsion A Silver - Coating amount 18 f / m "Kapfuu" 1,527m” 110.

Samples 101 to 110 were coated with Sensitometry Kawagiri/Trickrezi Phosphate) 1.1027 m"/Zefthi:y 2.5027 m"0 protective layer - 4-dichlorotriazine-6-hydroxy-8-triazine sodium salt (o, osr/m") ・Gelatin (1,8027m")
) Preparation of Samples 102 to 108 Samples 102 to 10 were obtained by changing the emulsion of Sample 101 to Emulsion B-III, and Emulsions B-2, ?
Sample 1o9° (1/100
), and one set was left at 30° C. and relative humidity 60° C. for one month. Another set was left at 40° C. and relative humidity 604 for 2 weeks. Thereafter, these samples were also subjected to the color development process described below, and the density of the processed samples was measured using a green filter. The results are shown in Table 1.

Among the above photographic performance results, sample 10
The sensitivity of 1 (fog plus optical density [sensitivity of 1, 2)] is 1
It is expressed as relative sensitivity when set to 00.

Processing method Color development processing was carried out at 38°C according to the following processing steps.

Color development 2 minutes 45 seconds Bleaching 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 5 minutes 15 seconds Safe, stable, 1 minute, 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0 fl-
Hydroxyethylidene-1,1-diphosphonic acid 2. Of Sodium Bisulfite 4. OF potassium carbonate 3[10F potassium bromide
1.4F potassium iodide
1.31119 Hydroxy μ amine sulfate 2.42 4-(N-ethyl/l/-N-β-hydroxyethyl amine/)-2-methylaniline sulfate 4.51 Add water and H Bleach solution Ethylenediaminetetraacetic acid Add ferric ammonium salt ethylenediaminetetraacetic acid disodium salt ammonium bromide ammonium nitrate aqueous solution (H) Fixer ethylenediaminetetraacetate disodium mound Sodium sulfite ammonium thiosulfate aqueous solution (Part 70) Add sodium bisulfite water and H Stabilizer <Table 1 〉 1, Ot 1 α 0 10 αOf 1 α0f 15Q, Of 1 αOf 1, Ot &0 1, Of 4, Of 175.0st/ 4.62 1, Ot &6 Table 1. It can be seen that the emulsion of the present invention has an excellent fog/sensitivity ratio (low fog υ) due to the oxidizing agent for silver, and is stable without sensitization in terms of storage when moist heat is applied after exposure.

Dye A This emulsion I was redispersed at 40° C. through a normal desalting and washing process.

Emulsion I was then optimally gold and sulfur sensitized at 60°C. After completion of this chemical sensitization, emulsion I was prepared by growing the dye A described in Example 1 at 40 DEG C. at 2.times.10@-' molar mass per 1 m3' of silver nitrate until it had a thickness of 1.4 .mu.m.

<Table 2> Furthermore, the chemical sensitization of Emulsion J was changed as shown below. The number indicates whether the oxidizing agent was added.

・Silver halide grains of emulsion A Silver coating amount Kabufu 1.8 f/nt" 11 97 m" at -tricresyl phosphate 1.10? /? PIff
i・ze'l f:/ 2.3
017m”0 protective layer・2.4-47 chlorotriazine-6-hydroxy-S
-) Lyazine sodium salt ([1L08t/W?) e Zeftin (t80f/m'') Preparation of samples 202 to 208 Samples 202 to 208 were obtained by changing the emulsion of sample 201 to emulsion JP, respectively. Emulsion J-2, N-2
The sample was changed to 209°210.

Sensitometry (1/1
oo') and left at 40° C. and relative humidity 604 for one month. Thereafter, this sample was also subjected to the same color development process as in Example 1, and the density of the processed sample was measured using a green filter. The results are shown in Table 3.

Among the above photographic performance results, sample 10
It is expressed as a relative sensitivity when the sensitivity of 1 (sensitivity of fog density α2) is set as 100.

From Table 5, it can be seen that the octahedral emulsion also has low fog due to the oxidizing agent for silver, and is stable without sensitization during storage when moist heat is applied after exposure.

Table 3. 〉 Example 3) It was prepared as follows.

<Table 4> Emulsion R-2 was prepared by changing the chemical sensitization of Emulsion R as shown below. That is, the amount of water-soluble silver salt (silver nitrate) used for particle formation, including the spectroscopically enriched seed crystals after redispersion, was added and the oxidizing agent for silver was shown in numbers.

The results of the photographic performance obtained are shown in Table 3.

Separately, one set of samples 301 to 308 was prepared, and these samples were exposed to light for sensitometry (1/1oo').
was given and left for one month at 40° C. and relative humidity 604°C (see Table 5). After this, the chemical sensitization of the emulsion Q-X prepared in Example 3 was completed for this sample as well.
5 ■ ■ Dye group 1 (red-sensitive dye) Dye group 2 (green-sensitive dye) Emulsion R-2°σ -2 ■ V-2 prepared in Example 3 is Emulsion R2 U.

Emulsions R-4, 17-4, and V-4 were prepared in which the dye added in the direction of dye group 2 to V was changed to dye group 3.

A multilayer color light-sensitive material was prepared by coating each layer having the composition shown below on a cellulose triacetate film support which had been undercoated with these emulsions.

(Composition of photosensitive soda) The coating amount is f/ for silver halide and colloidal silver.
- the amount of silver expressed in units, and for coupler additives and ceftin in units of t/-, and for sensitizing dyes - the amount of silver per moA/silver halide in the same layer. It was shown in

1st layer: antihalation layer black colloidal silver Silver coating amount 11.2 Zeftin 2.204-1
[L1σV-2CL2 Cpd-1104 0pd-2 (LO2 8o1v-1[1,!10 801v-2001 2nd layer: Intermediate layer fine grain silver iodobromide (AgI1.0mo/I/4 sphere equivalent diameter α0
7 pm) Silver coating amount Q, 15 gelatin 1.0BxC-4G
, 03 C! p(t-51:L2 sFa: 1st red-sensitive emulsion layer silver iodobromide emulsion (Ag process SO mo/%/4, surface height Ag,
Type, equivalent sphere diameter 119 μm, coefficient of variation of one sphere equivalent diameter 214,
Tabular grains, diameter/thickness ratio 7, s)
Silver coating amount [L42 silver iodobromide emulsion (AgI 4.
Omo/I/4, internal high AEI type, equivalent ball diameter 14μm1
Coefficient of variation of equivalent sphere diameter: 18, tetradecahedral particles) Silver coating amount: 0.40 Gelatin: 1.0E
El -14,5X10"'e/L'1!i X El
-21,5X10"?/%/α4X10-'Mole Q, 50 0.11 [LOO9 α 023 α 24 xB-5 4th layer: 2nd red emulsion layer silver iodobromide emulsion (AgIa 5 mo/%/regret, internal high jugI
Type, equivalent sphere diameter 1.0 μm, coefficient of variation of one sphere equivalent diameter 254,
Plate-shaped particles, diameter/thickness (Changing 〇) Gelatin X8-I L3X10-'7〃 (Llo [LO5 025 α 1a 511: Third red-sensitive emulsion layer Silver iodobromide emulsion I Silver coating amount Ceftin'HxO-2 xC-4 xC3-5 oxv-1 olv-2 6th layer : Intermediate layer gelatin pa-4 olv-1 7th layer: First glaucoma emulsion layer Silver iodobromide emulsion (AgI 5.0 moA/4, surface height AgI type, equivalent sphere diameter α9 μm 1 sphere equivalent diameter coefficient of variation 21 Unfortunately, tabular grains, diameter/thickness ratio "10) 1 1.0 1.50 6 α 08 α 01 Q, 06 (L12 12 α 1 Silver coating amount (L2B Silver iodobromide emulsion (AgI 4.0 7) , internal high AgI type,
Equivalent sphere diameter α4 μm1 Decadecahedron α 16 1.2 5×10−4 mo, ν 2×10−4 mole l×10−’ mole [L 50 (Llo Q, 05 L2 α 03 particle Coefficient of variation of sphere equivalent diameter 18 mm) Silver coating amount Gelatin a5 mo/L/4, internal high iodine type, equivalent ball diameter 1.0 μm%, coefficient of variation of equivalent ball diameter 25,
Plate-shaped particles, diameter/thickness treatment〇) Silver coating amount [LSI Gelatin [L55ExS-
555X10-4 mole Bx day-61,4X10-'7 118x day-7 XM-1 1! : xM-2 F, xM-3 olv-1 01v-4 9th layer: Intermediate layer gelatin 017-1 10th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion■ Silver coating amount Gelatin 1! :xM-4 04 n,oos [LOl 101 α 2 105 α 5 E? olv-1α 1 12th layer: Intermediate layer gelatin (L5Cpcl-
30,1 #c13 layer: 1st blue emulsion layer Silver iodobromide emulsion (Ag process 2Mo/I/4, uniform iodine type, equivalent sphere diameter [1L55μm Coefficient of variation of 1 sphere equivalent diameter 25#I
Tabular grain diameter/thickness ratio y, o) Silver coating amount α2 Gelatin 1.0KXB-8
3X10-'mol ExY-1 (L6 WxY-2α02 8o1v-1α15 14th layer: second blue emulsion layer silver iodobromide emulsion (Ag process 19.0 moA/4, internal high AgI
Type, equivalent sphere diameter 1.0 μm, coefficient of variation of one sphere equivalent diameter 164,
Octahedral grains) Silver coating amount α19 Gelatin xB-8
Equivalent sphere diameter cL 13 μm) Silver coating amount α2 α 36 α 3 2X10-47〃 α 22 (LQ7 Gelatin No. 16W: Third blue emulsion layer Silver iodobromide emulsion I Silver coating amount Gelatin WxY-1 o1v-1 No. 17N1 : 1st protective layer gelatin V-1 4-2 o1v-1 oxv-2 1°55 (L5 (L2 α07 1.8 11 (L2 α01 (1,01) 18M: 2nd protective layer fine grain silver chloride (equivalent to sphere) 0.07 μm in diameter) Silver coating amount L56 UV-1: Polymethyl methacrylate particles (1.5 μm in diameter) L2 0 aooax.

C! p d -71,0 In addition to the above, each layer includes B-1 (total α2097 m"),
1.2-benzisothiazolin-3-one (about 200 ppm on average relative to zeftin), n-butyl, p-hydroxybenzoate (about 1.000 ppm relative to zeftin),
and 2-phenoxyethano-A/(approximately 1α000pp
m) was added.

UV-2: Wx C-1 x/y=7/3 (tfl ratio) (1) C! , Horse QC! NH ODD NxM-2 ExM-3 ExM-6 ExM-1 t t ExM-4 t ExM-5 XY-2 0p(1-1 pd-2 0pcl-3 Qpd-4 8H13 [C!pd-5 H -1 1olv - olv- Bo 1v-4 Qpd-6 Qpd-7 -1 -1 OH!=C!ESO!OH!0ONH-(3H!0 H
2=O'HBO20 HorseC0NH-CIIIffixS- xB-2 XS-3 (oHρ, 80.HN (C, Tω3Ex Day-5 KX8-9 (amρ, So, H-N (0,)

XS- xEJ-8 xS- ((Hρ4 5O8e ! (CHD4 EIO3H-N(0,H5)3 5th layer, 109th layer. Silver iodobromide emulsion I in the 16th layer.

(2) and (2) gold in emulsion Q-X prepared in Example 4;

Multilayer color photographic materials 401 to 408, which incorporate emulsions that have been spectrally sensitized with dye groups 1 to 3, are shown in the table below. Prepared as shown.

In addition, emulsions R-2, R-5, R-4, U-2, U-3, to which dye groups 1 to 3 were added prior to gold and sulfur sensitization,
Multilayer color photographic materials 409 to 411 incorporating U-4 and V-2, V-3, and V-4 were prepared as shown in the table below.

These samples 401 to 411 were exposed to light for sensitometry (1/1oo') and subjected to the following color development process.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter.

Separately, a set of samples 401 to 411 was prepared, and these samples were exposed to light for sensitometry (1/1oo') and left at 40° C. and relative humidity 604 for one month. After this, this sample was also subjected to the following color development process.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter.

Processing method Color development processing was carried out at 38°C according to the following processing steps.

Color development 5 minutes 15 seconds Bleaching 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water washing 3 minutes 15 seconds Safe, stable, 1 minute, 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Soethylenetriaminepentaacetic acid 1.0f1-Hydroxyethylidene-1,1-cyttcsyt<:yeZ□ Sodium bisulfite 4. Ofpotassium carbonate
3αOf potassium bromide
1.42 potassium iodide
1.3 Misaki Hydroxyamine Sulfate
2.4f4-(N-ethyμ-N-β-hydroxyethylamino)-2-methylaniline sulfate * Add tsy water f, o t'9Hj(
LO Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 1oαOf Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Add water H Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Ammonium thiosulfate aqueous solution (704) Add sodium bisulfite water H Stabilizing liquid formalin (401) Polyoxyethylene-p-7nononi A/Phenyate (Average degree of polymerization 10) 1 αOf 5CLQf 1 (LOP 1, Ot 6, Oj, Qfp 4.0? 175.0m 4 .6 t 1, Ot 6.6 2.0- α3 f Addition of water 1.O6 The results obtained correspond to those obtained in Example 5, and emulsions T, tT, V and It was found that a stable photosensitive material with low fog and no sensitization during storage when moist heat was applied after exposure was obtained in the multilayer cuff photosensitive material using X.

In particular, when an emulsion was used in which a spectral sensitizing dye was present prior to gold and sulfur sensitization during chemical sensitization, the results corresponded to those of Example 3, and particularly good results were obtained.

Example 5) Using samples 401 to 408 of the present invention and comparative examples, the same experiment as in Example 4 was conducted except for the treatment method shown below. The color development process was carried out using an automatic developing machine according to the method described below.

Processing method Process Processing time Color development 3 minutes 15 seconds Bleach White 1 minute 00 seconds Bleach fixing 3 minutes 15 seconds Washing with water (1) a O seconds Washing with water (2) 1 minute oo seconds Stability 40 seconds Drying 1 minute 15 seconds Next, the composition of the treatment liquid will be described.

(color developer) diethylenetriaminepentaacetic acid 1-hydroxyethylidene- 1,1-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate Processing temperature 38℃ 38℃ 38℃ 35℃ 35℃ 38℃ 55℃ (unit?) 1.0 Fifty 4.0 3[10 1,4 1,5q 2.4 4-[N-ethyl-N-(β- Hydroxyech lv) Amino] -2-methyμ aniline sulfate add water H (bleach solution) Ethylenediaminetetraacid number: Iron ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt ammonium bromide ammonium nitrate bleach accelerator Ammonia water (27’l) add water H (bleach-fix solution) 4.5 1.Ot. 1 α05 (unit?) 12 [L.

1Q, 0 IQ[LO 110 α005Mo μ m-〇- 1.Ot. & 5 (unit?) Ethylenediaminetetraacetic acid 2nd Iron ammonium dihydrate sn.

Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (704) 24α〇-Ammonia water (274) 6: Add Od water
1.04 pH 7,2 (washing liquid) A mixed bed type in which tap water was filled with an H-type strongly acidic cation exchange resin (Amperfitoe R-120B, manufactured by Rohm and Haas) and an oH-type anion exchange resin (Amperfitoe R-400, manufactured by Rohm and Haas). Water was passed through the column to adjust the concentration of μsium and magnesium ions to sxq/, followed by the addition of 2 oq/l of sodium isocyanurate dichloride and tsr/IJ of sodium sulfate. The pH of this solution is &5-
It is in the range of 7.5.

(Stabilizer) (Unit: t) Formalin (37 tons) 2. Low polyoxyethyl V-p-monononylphenyther (average degree of polymerization 10) a3 Ethylenediaminetetraacetic acid disodium salt α05 Add water 1.0tp) (s, o-a.

Similar to Example 4, good results of the present invention were obtained by this treatment.

Example 6) Samples 401 to 408 of the present invention and comparative examples were subjected to the same experiment as in Example 4, and processed using an automatic processor in the manner described below.

Processing method step Processing time Processing temperature Color development
2 minutes 30 seconds 40°C bleach-fixing 3 minutes 00 seconds 40°C water washing (1) 20 seconds washing (2) 20 seconds stability 20 seconds drying 50 seconds Next, the composition of the processing solution is described.

(Color developer) Diethylenetriaminepentaacetic acid 1-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxyμ amine sulfate 4-[N-ethy μmN-(β- HydroxyVethy/I /) Amino] Add -2-methylaniline sulfate and pH 35°C 35°C 35°C 65°C (Unit: f) 2.0 50 4.0 3 α 0 1.4 1, 539 2.4 4.5 1, Ot IQ, 05 (bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution (704) Acetic acid (984) Bleach accelerator (unit f) 5 [LO 5 ,0 12,0 26[LOd -〇- Add 0.01 mol water 1.04 pH & 0 (Washing liquid) Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas), Water was passed through a mixed bed column filled with 011 type anion exchange resin (Amperlite R-400) to adjust the calcium and magnesium ion concentration to sg/, followed by sodium chloride isocyanuric acid 2owp/ 1 and 15 t/l of sodium sulfate α were added.

The pH of this solution is in the range of &5-7.5.

(Stabilizing liquid) (Unit f) Formalin (374) zo-polyoxyethylene-p-monononiphenyl ether (average degree of polymerization 10) α3 Disodium ethylenediaminetetraacetic acid #L α05 Add water 1.0tpHHaO-110 Invention It was confirmed that the same effect as in Example 4 can be obtained by this treatment.

Claims (3)

[Claims] (1) In a silver halide emulsion containing photosensitive silver halide grains in a binder, chemical sensitization is performed after 50% of the water-soluble silver salt used for grain formation of the silver halide emulsion has been added. 1. A silver halide emulsion, characterized in that at least one oxidizing agent for silver is added before the silver halide is processed. (2) The oxidizing agent for silver has the general formula (I), (II)
The silver halide emulsion according to claim 1, which is at least one compound represented by ) or (III). (I) R-SO_2S-M (II) R-SO_2S-R^1 (III) R-SO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different. Often represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of general formulas (I) to (III) may be polymers containing divalent groups derived from the structures represented by (I) to (III) as repeating units. Furthermore, when possible, R, R^1, R^2, and L may be bonded to each other to form a ring. (3) The support has at least one silver halide emulsion layer, and the emulsion layer contains at least one silver halide emulsion according to claim (1) or (2). A silver halide photographic light-sensitive material.