JPH03237453A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure high sensitivity and to reduce fog by incorporating a silver halide emulsion subjected to reduction sensitization in the presence of a specified compd. and further incorporating at least one of specified sensitizing dyes. CONSTITUTION:A silver halide emulsion layer contg. a silver halide emulsion subjected to reduction sensitization in the presence of at least one of compds. represented by formula I and further contg. at least one of sensitizing dyes represented by formulae II-IV is formed. In the formula I, each of R, R<1> and R<2> is an aliphatic, arom. or heterocyclic group, M is a cation, L is a divalent combining group and m is 0 or 1. In the formulae II-IV, each of R<3> and R<4> is alkyl, R<5> is H, alkyl or aryl, X<-> is an anion, n is a number for regulating electric charges in the entire molecule, and in the case where an inner salt is formed, n is 0. Fog can be inhibited.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a spectrally sensitized silver halide photographic material with high sensitivity.

[Conventional technology]

The basic properties required of silver halide emulsions for photography are high sensitivity, low fog, and fine grain.

In order to increase the sensitivity of an emulsion, it is necessary to (1) increase the number of photons absorbed by a single grain, and (2) increase the efficiency with which photoelectrons generated by light absorption are converted into silver clusters (latent images). (3) In order to effectively utilize the formed latent image, it is necessary to increase the development activity.

Increasing the size increases the number of photons absorbed by one particle, but
Decrease image quality. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel development such as color development, graininess generally deteriorates. In order to increase sensitivity without causing deterioration of graininess, it is most preferable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity. In order to increase quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible. It is known that reduction sensitization, which creates small silver nuclei with no development activity inside or on the surface of silver halide, is effective in preventing recombination.

Attempts at reduction sensitization have been considered for a long time.

Carroll, U.S. Patent No. 2,487,
850, polyamine compounds in Lowe et al. No. 2,512,925, and Fallens et al. in British Patent No. 78.
No. 9, No. 823 disclosed that thiourea dioxide-based compounds are useful as reduction sensitizers. Furthermore, Co
11ier (Korea) is Photographic
5science and Engineering 23
Volume 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She employed dimethylamine borane, stannous chloride, hydrazine, high pH aging, and low pAg aging methods. The reduction sensitization method is further described in U.S. Pat. Nos. 2,518,698 and 3.
, No. 201,254, No. 3,411,917, No. 3,779,777, and No. 3,930,867. Regarding not only the selection of reduction sensitizers but also the improvement of reduction sensitization methods, Japanese Patent Publication Nos. 57-33572 and 58
-1410. Among these, conventionally known reduction sensitizers are listed, and ascorbic acid is mentioned among them. However, compounds such as thiourea dioxide are preferred, and those shown in the Examples are thiourea dioxide, silver chloride, and hydrazine. Therefore, favorable properties of ascorbic acid compounds as reduction sensitizers have not been found. Further improvements are disclosed in Japanese Patent Application Laid-Open No. 179835/1983.

However, in order to put reduction sensitization into practical use, it is necessary to overcome the problem of the shelf life of light-sensitive materials. Regarding the technology for improving the storage stability of reduction-sensitized emulsions, Japanese Patent Application Laid-Open No. 57-8283
No. 1 and No. 60-178445, but it has not yet reached a sufficient level of improvement.Despite many studies, the hydrogen enhancement process in which photosensitive materials are treated with hydrogen gas under vacuum has not yet reached a sufficient level of improvement. The increase in sensitivity was insufficient compared to the sensitivity. This is a Journal of fading
5ctence, Vol. 29, p. 233 (1985), Motsar et al. At the same time, improvements in the pressure characteristics of photosensitive materials containing reduction-sensitized emulsions have been awaited.

Generally, various pressures are applied to photographic materials coated with silver halide emulsions. For example, general photographic negative film is folded or pulled for frame advance when it is wound into a cartridge or loaded into a camera.

On the other hand, sheet films such as photosensitive materials for printing and X-ray photosensitive materials for direct medical use are frequently handled by humans, so they often break or bend.

Furthermore, all types of sensitive materials are subjected to great pressure during cutting and processing.

As described above, when various pressures are applied to a photographic material, pressure is applied to the silver halide grains using gelatin, which is a holder (binder) for the silver halide grains, and a plastic film, which is a support, as a medium.

It is known that when pressure is applied to silver halide grains, changes occur in the photographic properties of photographic materials.
Mather, J., Opt., Soc., Ag., 38.
1054 (1948).

P, Faelens and P, de 5set, S
ci, et Ind, Phot,, 5.178 on 25
(1954), P., Faelens, J., Phot, S.
ci, 2, 105 (1954), etc.

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

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

For example, British Patent No. 738,618 describes heterocyclic compounds, British Patent No. 738,637 describes alkyl phthalates, British Patent No. 738,639 describes alkyl esters, and U.S. Patent No. 2,960,404 describes polyhydric compounds. Alcohol, 3.1
No. 21,060 contains carboxyalkyl cellulose,
Japanese Patent Publication No. 49-5017 discloses a method using paraffin and a carboxylic acid salt, and Japanese Patent Publication No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

However, the method of adding a plasticizer reduces the mechanical strength of the emulsion layer, so there is a limit to its usage. However, it is difficult to achieve sufficient effect.

Regarding naphthoxazolocarbocyanine, Japanese Patent Publication No. 61-80237, Japanese Patent Publication No. 60-108838,
61-8023, 63-291057, 61-3
2841, 60-225146, 60-1284
33, 60-128432, 59-185330,
59-149346, 59-116646, 59
-78338, 63-214145, Special Publication 1977-
34609 etc.

However, naphthoxazolocarbocyanine of general formula [A] or (B) or (C) and -a formula CI) or (
It is not disclosed or even suggested that the effects of the present invention described below can be achieved by combining II) or (I[I] with a silver halide emulsion reduction-sensitized in the presence of thiosulfonic acid. do not have.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic material with high sensitivity and little fog.

Another object of the present invention is to provide a silver halide photographic material with improved pressure resistance.

(Means for Solving the Problems) As a result of intensive research, the present inventors have obtained a silver halide photographic material with high sensitivity and low fog, as well as improved properties against pressure, by the configuration shown below. I found out that it can be done. That is, (1) in a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer is formed by the following general formula CI), (II), or (II[)
It contains a silver halide emulsion that has been reduction sensitized in the presence of at least one compound selected from the compounds represented by the formula [A], [B] or (C), and further contains a sensitizing dye represented by the general formula [A], [B] or (C). Silver halide photographic material containing at least one of: [I] R-3O,SM [1) R-3o,5-Rl (II[)R5OzS Lm SS○ R1 (in the formula , R, R', and R'' 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, and m is 0 or l.

The compounds of general formulas [I] to [III] may be polymers containing divalent groups derived from the structures shown in (1) to 1) as repeating units. ) (In the formula, R3 and R4 represent an alkyl group.

RS represents a hydrogen atom, an alkyl group or an aryl group. XO represents an anion, n represents a numerical value to adjust the charge of the entire molecule, and when forming an inner salt, n
=0. ) and (2) the silver halide photographic material according to the above (1), which contains a silver halide emulsion reduction-sensitized in the presence of ascorbic acid or an ascorbic acid derivative; .

The present invention will be explained in detail below.

The manufacturing process of silver halide emulsions can be broadly divided into steps such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly; the order of the steps may be reversed, or the steps may be repeated.

The term "reduction sensitization" being carried out during the production process of the silver halide emulsion basically means that it can be carried out at any step. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to or after chemical sensitization other than reduction sensitization. . When chemical sensitization is carried out in combination with gold sensitization, it is preferable to carry out reduction sensitization prior to chemical sensitization to avoid undesirable fogging.Most preferably, reduction sensitization is carried out during the growth of silver halide grains. It is a way of feeling. Growing is a method in which reduction sensitization is performed while silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. This means that it also includes a method in which reduction sensitization is performed in the same state and then further growth is performed.

The reduction sensitization of the present invention includes a method of adding a known reducing agent to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere of 94g1 to 7, which is called silver ripening,
Either a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH Pr1i 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, atrium salts, polyamic acids, hydrazine derivatives, formamidine sulfinic acids, silane compounds, borane compounds, and the like are known. In the present invention, a compound selected from these known compounds can be used, or two or more kinds of compounds can be used in combination. Preferred compounds as reduction sensitizers are stannous chloride, thiourea dioxide, and dimethylamine borane. The amount of the reduction sensitizer to be added depends on the emulsion manufacturing conditions and must be selected, but it is suitably in the range of 10@-7 to 10" moles per mole of silver halide.

It is particularly preferred to use ascorbic acid and its derivatives as the reduction sensitizer of the present invention.

Specific examples of ascorbic acid and its derivatives (hereinafter referred to as r-ascorbic acid compounds) include the following.

(A-1) L-ascorbic acid (^-2) Sodium L-ascorbate (A-
3) Potassium L-ascorbate (A-4)
D L-ascorbic acid (A-5) D-sodium ascorbate (A-6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-
6-pal-sentate (A-8) L-ascorbic acid-6-penzoate (A-9) L-ascorbic acid-5,6-diacetate (A-10) L-ascorbic acid-5,6-0- Isopropylidene The ascorbic acid compound used in the present invention is desirably used in a larger amount than the amount in which conventional reduction sensitizers are preferably used. For example, Tokuko Sho 57-33572
The issue states, ``The amount of reducing agent is usually 0.75X per gram of silver ion.
1 t per 10-"mm (8 x 10 mol/Ag
molar) is often effective. ” (converted value is by the inventors). US-2,487,
No. 850 states that "the amount of tin compound that can be added as a reduction sensitizer is 1 x 10-' to 44 x 10-'mol". Further, in JP-A-57-179835, the amount of thiourea dioxide added is about Q, 0111 g to about 2 I1 g per mole of silver halide, and the amount of tinnous chloride is about 0.
．． It is stated that it is appropriate to use 01g to about 311g. The ascorbic acid compound used in the present invention depends on the emulsion grain size, halogen composition, emulsion preparation temperature, p.
The preferred amount added depends on factors such as H, p/Ig, etc., but it is 5X10-' mol to 1 mol per mol of silver halide.
It is desirable to select from the range of ×10 moles. More preferably, it is selected from the range of 5×10 −′ mol to 1×10 −z mol. Particular preference is given to selecting from the range of 1 x 10-3 mol I x 10-'' mol.

Reduction sensitizers include water, alcohols, glycols,
Dissolved in solvents such as ketones, esters, and amides,
It can be added during grain formation, before or after chemical sensitization. Although it may be added at any stage of the emulsion manufacturing process, it is particularly preferable to add it during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble root salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. 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 are formed.

To explain the compounds of general formulas [I], [II] and (I[l) in more detail, when R, R' and R2 are aliphatic groups, preferably an alkyl group having 1 to 22 carbon atoms, a carbon number is a 2 to 22 alkenyl group or alkynyl group,
These may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and L-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R, R' and R2 preferably have 6 to 20 carbon atoms, such as phenyl and naphthyl groups. These may be substituted.

The heterocyclic group of R, R' and R2 includes nitrogen, oxygen,
A 3- to 15-membered ring containing at least one element selected from sulfur, selenium, and tellurium, such as pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, and benzothiazole ring. ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, tetrazole ring, triazole ring, benzotriazole ring, tetrazole ring, oxadiazole ring, and thiadeazole ring.

Examples of substituents for R, R' and R2 include alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (
For example, methoxy, ethoxy, octyloxy), aryl groups (phenyl, naphthyl, tolyl), hydroxy groups,
Halogen atoms (e.g. fluorine, chlorine, bromine, iodine), aryloxy groups (e.g. phenoxy), alkylthio groups (
(e.g. methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl, valeryl), sulfonyl! (e.g. methylsulfonyl, phenylsulfonyl), acylamino groups (e.g. acetylamino, benzamino), sulfonylamino groups (e.g. methanesulfonylamino, hensensulfonylamino), acyloxy groups (e.g. acetoxy, benzoxy), carboxyl groups, cyano groups, sulfonylamino groups (e.g. methanesulfonylamino, hensensulfonylamino), carboxyl groups, cyano groups, group, amino group, etc.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include (-CH,
-)-=-(n = 1-12), -CH2-CH=
CH-CH2- -CHtC3CCH.

Examples include xylylene groups. (2) Examples of the divalent aromatic group include phenylene and naphthylene.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Organic cations include ammonium ions (e.g. ammonium, tetramethylammonium, tetrabutylammonium)
, phosphonium ion (tetraphenylphosphonium)
, guanidine group, etc.

Specific examples of compounds represented by formula (1), (n) or ([1) are listed in Table A, but the invention is not limited thereto.

The compound of general formula [I] can be easily synthesized by the method described in JP-A-54-1019 and British Patent No. 972,211.

The compound represented by the general formula (1), (II) or [III] has an amount of 10-7 to 10-1 per mole of silver halide.
Preferably, it is added in moles. Furthermore, 10 to 10-”
Particularly preferred is an amount of 10-s to 10'' 3 mol 1 mol Ag.

The compound represented by the general formula (13 to CI[I) can be added during the manufacturing process by a method commonly used for adding additives to photographic emulsions.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Water-insoluble or N-soluble compounds can be dissolved in a suitable water-miscible organic solvent, such as alcohols, glycols, ketones, esters, amides, etc., that do not adversely affect photographic properties. However, it can be added as a solution.

- The compound of type (I), (II) or (Ill) may be added at any stage during the grain formation of the silver halide emulsion, before or after chemical sensitization. Preferably, reduction is A method in which the compound is added before or during sensitization is performed.Particularly preferred is a method in which the compound is added during grain growth.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation. Alternatively, the compounds of general formulas (1) to [III] 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 form particles. It is also a preferable method to add a solution of the compound of general formulas N) to [III] in several portions or continuously for a long period of time as particles are formed.

Among the compounds represented by formulas (1) to [III], the most preferred compound for the present invention is a compound represented by -form CI).

Next, the sensitizing dyes represented by general formulas (A), CB), and (C) will be further explained.

The optionally substituted alkyl group represented by R and R4 is an alkyl group (unsubstituted alkyl group) having 1 to 8 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups, such as aralkyl groups (
(e.g. benzyl, 2-phenylethyl), hydroxyalkyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl groups (e.g. 2-hydroxypropyl),
carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl groups (e.g. 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl), sulfoalkyl groups (e.g. 2
-Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-(3-sulfopropoxy)
ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl groups (e.g. 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (e.g. 2-(pyrrolidine) -2-one-1yl)ethyl, tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylamineethyl) or an allyl group.

Either R3 or R4 is preferably a sulfoalkyl group or a carboxyalkyl group.

R5 is a hydrogen atom, an optionally substituted alkyl group (
(eg, methyl, ethyl, benzyl), an optionally substituted aryl group (eg, phenyl, p-tolyl). Particularly preferred is ethyl group.

XO is an inorganic or organic anion (e.g. chloride, bromide, ioside, p-toluenesulfonate), p-nitrobenzenesulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate,
1,5-naphthalenedisulfonate).

n represents a numerical value for adjusting the charge of the entire molecule, and is O when forming an inner salt.

The sensitizing dyes represented by the general formula (A), CB) or [C] used in the present invention are F, ? 1. Hamer (F
, M. Hamer), Heterocyclic Compounds, Cyanine Soybeans and Related 3 Combines.
ndsCyanine Dyes and Re1at
ed Compounds)” Chapter 4, Chapter 5, Chapter 6, pp. 86-119, published by John Wiley and Sons (
(1964), D.M., Starmer (D.?I.).

Heterocyclic Conbounds Special Topics in Heterocyclic Chemistry
+poundsSpecial Topics in
Heterocyclic Chea+1try)”
.

It can be easily synthesized based on the method described in Chapter 8, pp. 482-515, published by John Wiley & Sons (1977).

Specific examples of the sensitizing dyes represented by the general formulas [A], [B], and (C) used in the present invention are shown in Table B-1, Table 8-2, and Table 8-1 below, respectively. 3, but the present invention is not limited thereto.

General formulas [A], [B] and (C) used in the present invention
The sensitizing dye represented by the formula may be incorporated in any step of the manufacturing process of the silver halide photographic light-sensitive material.

General formulas (A), [B] and (C) used in the present invention
In order to incorporate the compounds represented by the formula into a silver halide emulsion, they may be directly dispersed in the emulsion, or they may be dispersed alone in a solvent such as water, methanol, ethanol, acetone, methyl cellosolve, or fluorinated alcohol. Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. When added to a silver halide emulsion, it may be added during the demonstration process of silver halide grains, or it may be added afterward to silver halide grains that have been pre-produced. When added during the demonstration process of silver halide grains, immediately before the reaction process between silver and halogen, physical ripening process, chemical ripening (post-ripening) process,
It can be added during or immediately after the chemical ripening process.

Alternatively, these may be dissolved alone or in a substantially water-immiscible solvent such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid directly or using a surfactant, and this dispersion is added to an emulsion. It's okay.

General formulas [A], [B] and (C) used in the present invention
The amount of sensitizing dye added, represented by
X10-'mol-8X10-'mil.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides contain 30 mole % or less (including zero) of silver iodide;
Silver iodobromide is also silver bromide and silver chlorobromide. More preferred is silver iodobromide.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, examples such as those explained in the Photographic Society of Japan, Basic Silver Salt Photography of the Photographic Industry (Corona Publishing), p. 163,
For example, depending on the purpose, there are single twins with one twin plane, parallel multiple twins with two or more parallel twin planes, nonparallel multiple twins with two or more nonparallel twin planes, etc. You can choose and use it. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and Japanese Patent Publication No. 554273.
7, disclosed in Japanese Patent Application Laid-Open No. 60-222842 (1
10) Dodecahedral particles consisting of faces can be used.

Further Journal of Ieaagrng 5c
jence, Vol. 30, Page 247, a (hl) plane particle with (211) as a representative, as reported in 1986.
(hhl) plane particle represented by (331), (210)
Although (hko) plane particles representing the plane and (hkl) plane particles representing the (321) plane require some ingenuity in their preparation methods, they can be selected and used depending on the purpose. (100) plane and (1
11) A tetradecahedral particle in which faces coexist in one particle, (10
Particles in which 0) and (110) planes coexist or (111
Particles in which two planes or a large number of planes 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 may be fine grains of 0.1 micron or less, or large grains with a projected area diameter of up to 10 microns. It may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 80% or more of all grains fall within ±30% of the average grain size in terms of grain number or weight can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Physi
que Photography Paul Mo
Ntel, 1967), "Photographic Emulsion Chemistry" by Duffin
, published by Focal Press (G.F., Duffin, Ph.
otographicEwulsion Chemises
try (Focal Press, 1966), Zelikman et al., "Manufacture and Coating of Photographic Emulsions J," published by Focal Press (V. L., Zelikman et al., Mak
ing and coating photography
ic Esulsion, Focal Press.

(1964) and others. 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 the particles are formatted 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 above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling pAg and pl during grain formation.
and Engineering (Photographic
5science and engineering)
Vol. 6, pp. 159-165 (1962); Journal
On Photographic “Science” (Journa)
l orPhotographic 5science)
+ Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. L413,
It is described in No. 748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in Rieve's Theory and Practice of Photography J (C1eve.

Photography Theory and Pr
actjce (1930)) + 131 pages; by Gadoff,
Photographic Science and Engineering (Gutoff, PhotographicSci
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4,
No. 434.226, No. 4,414,310, No. 4,4
33.048, British Patent No. 4,439.520 and British Patent No. 2.112,157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency with sensitizing dyes, and the above-mentioned U.S. Pat.
It is described in detail in No. 34,226.

Tabular grains are preferred as emulsions of the present invention.

In particular, particles with an aspect ratio of 3 to 8 account for 50% of the total projected area.
Tabular grains occupying the above amount are preferable.

The crystal structure may be similar, the inside and outside may be composed of different types of silver halide, or the crystal structure may be a layered structure. These emulsion grains are described in British Patent No. 1,027.
No. 146, U.S. Patent No. 3.505.068, U.S. Patent No. 4,4
44,877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains.

Typical examples include halogen compositions in which the interior and surface layers of particles are different, as disclosed in Japanese Patent Publications No. 43-13162, No. 61-215540, No. 60-222845, No. 61-75337, etc. These are core-shell type or double-structured particles.

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. Furthermore, although the core portion is a clearly regular particle, the shelled particle may have a distorted shape or an irregular shape.

Moreover, it is not just a double structure, but also
It is possible to form a triple structure or a multilayer structure with more than that as disclosed in , or to apply a thin layer of silver halide having a different composition to the surface of a core-shell double structure grain.

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 EP199290A2
, Japanese Patent Publication No. 58-24772, Japanese Patent Publication No. 59-16254
etc. are disclosed. The crystal to be bonded has a composition different from that of the host crystal, and can be bonded to the edge, corner, or surface of the host crystal to form a single precept.

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 PbO 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. 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 HP~009672
7B1, BP-0064412B1, etc., or DE-
The surface may be modified as disclosed in JP-A-60-221320, No. 2306447C2.

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 shell can also be used depending on the purpose.

It is known that silver halide solvents are useful in promoting ripening. For example, it is known to have an excess of halide 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 P! A ripening agent can be used, and the entire amount of these ripening agents can be blended into the dispersion medium in the reactor before the silver and halide salts are added, and one or more halogen It is also possible to add compound salts, silver salts or peptizers and introduce them into the reactor. 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.

In the present invention, chemical sensitization represented by sulfur sensitization and gold sensitization is preferred, and it is extremely important to carry out these sensitizations.

The location where chemical sensitization is applied varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use of the emulsion. There are cases in which chemical sensitizing nuclei are embedded inside the particles, in cases where they are embedded in shallow positions from the particle surface, or in cases where chemical sensitizing nuclei are created on the surface.6 The effects of the present invention are effective in all cases, but Particularly preferred is the case where chemically sensitized nuclei are created near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Chemical sensitization is described by T. H. James,
The Photographic Process, 4th edition, Macmillan Publishing, 1977, (T, H, James + The
Theory of the Photographic
Process, 4 tb ed, Macmill
an.

1977), pp. 67-76, or as described in Research, Disclosure, Vol. 120, April 1974, 1200.
8; Research Disclosure, Volume 34, 1975
June 13452, U.S. Patent No. 2,642.361
No. 3,297,446, No. 3,772,031, No. 3,857.711, No. 3,901,714,
4,266.018 and 3.904,415
pAg 5-10, p) 15-8 and temperature 3 as described in British Patent No. 1,315.755.
It can be carried out at 0-80°C using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers.

Chemical sensitization is optimally carried out in the presence of gold compounds and thiocyanate compounds, and in the presence of sulfur-containing compounds 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 chemical sensitization aids. Chemical sensitization aids used include azaindene,
Compounds known to suppress fog and increase sensitivity in the process of chemical sensitization are used, such as azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are U.S. Pat.
No. 14, No. 3,554.757, JP-A-58-126
No. 526 and the aforementioned Duffin, “Photographic Emulsion Chemistry,” 1
38-143.

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. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrohencitriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; There are many known antifoggants or stabilizers such as zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc. Compounds can be added. For example, US Patent 3.954
．． No. 474, No. 3,982,947, Special Publication No. 5228
, No. 660 can be used.

The photographic emulsion used in the present invention has the general formula [A],
Spectral sensitization may be performed using methine dyes other than the sensitizing dyes represented by [B] and (C). The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. 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, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. 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, thiobarbinuric acid nucleus, etc. 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 sensitization.

A typical example is U.S. Patent No. 2,688,545, 2.9
No. 77.229, No. 3,397.060, No. 3,52
No. 2.052, No. 3,527,641, No. 3,617
, No. 293, No. 3,628,964, No. 3,666.
No. 480, No. 3,672,898, No. 3.679, 4
No. 28, No. 3,703,377, No. 3,769,30
No. 1, No. 3,814,609, No. 3,837,862
No. 4,026,707, British Patent No. 1,344,2
No. 81, No. 1,507,803, Special Publication No. 43-493
No. 6, No. 53-12.375, JP-A No. 52-110.
No. 618 and No. 52-109,925.

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 dye may be added to the emulsion at any stage of emulsion preparation known to be useful.

Most commonly, this is done after chemical sensitization is complete and before application, but as described in U.S. Pat. No. 3,628,969 and U.S. Pat. The spectral sensitization can be carried out at the same time as the chemical sensitization by adding it at the same time, or it can be carried out before the chemical sensitization as described in JP-A-58-113,928.
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
Adding these said compounds separately as taught in US Pat. Also possible, U.S. Patent No. 4.183.75
Any time during silver halide grain formation including the method taught in No. 6 may be used.

The amount added is 4X10-' to 5 per mole of silver halide.
xio-'' moles can be used, but for the more preferred silver halide grain size of 0.2 to 1.2 .mu.m, about 5.times.10-' to 2.times.10-' moles are more effective.

General formulas rA), (B) and (C) used in the present invention
and other sensitizing dyes may be added to the silver halide grains simultaneously or separately.

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 more detail in Research Disclosure p-Item 17643 (December 1978).
and same Item 18716 (November 1979)
The relevant sections are summarized in the table below.

Additive type RD17643 RD187161 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity enhancer Same as above 4 Brightener Anti-stain agent Dye image stabilizer Hardener Binder Plasticizer, lubricant Page 24 Page 25 Right column 25 Page 26 Page 26, page 27, page 650, left to right column, page 651, left column, same as above, 650, right column. Various color couplers can be used in the present invention.
RD) Shame 17643, described in the patent described in ■-C-C.

As a yellow coupler, for example, U.S. Pat. No. 3,93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401,752, Special Publication No. 5
No. 8-10739, British Patent No. 1,425.020;
1.476.760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4.35L897, European Patent No. 7
3.636, U.S. Patent No. 3,061,432, U.S. Patent No. 3.725,067, Research Disclosure Hiroshi 24220 (June 1984), JP-A-60-33
No. 552, Research Disclosure 24230
(June 1984), JP 60-43659, U.S. Patent No. 4,500,630, U.S. Patent No. 4,540,65
Particularly preferred are those described in No. 4 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4.228.23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2.801, 171, No. 2.772.
No. 162, No. 2,895.826, No. 3.772
, No. 002, No. 3,758,308, No. 4.33
No. 4.011, No. 4,327.173, West German Patent Publication No. 3,329.729, European Patent No. 121,365
A, U.S. Patent No. 3.446.622, U.S. Patent No. 4.33
No. 3.999, No. 4.45L559, No. 4.42
Those described in No. 7,767, European Patent No. 161.626A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Tsui 17643.
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138,258, British Patent No. 1,146,36
The one described in No. 8 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat. No. 4,080,211; U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643 as previously described.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in US Pat. No. 4,248,962.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-179840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-equivalent coupler described in JP-A-60-185950, etc.
DIR redox compound or DIR coupler releasing coupler or DIR coupler releasing coupler or redox described in JP-A-62-24252 etc., European Patent No. 1
73, 302A, a coupler releasing a dye that recovers color after separation, R, D, Hiro 11449, 24241
, the bleach accelerator-releasing coupler described in JP-A No. 61-201247, and the ligand-releasing coupler described in U.S. Pat. No. 4,553,477.

The coupler used in the present invention can be introduced into the light-sensitive 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.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid ester N (e.g. dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2゜4-di-t-amyl phenyl)). Phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(1,l-diethylpropyl)
phthalates), esters of phosphoric or phosphonic acids (
For example, triphenyl phosphate, tricrenyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate), Benzoic H esters (e.g. 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), adands (e.g. N,N-diethyldodecanamide, N,N-diethyllauramide) , N-tetradecylpyrrolidone), alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g. bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g. N,N-dibutyl 2-butoxy-5-tert-octylaniline), hydrocarbons (e.g. paraffin, dodecylbenzene, diisopropylnaphthalene), etc. can be mentioned. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30'C or more, preferably about 50'C or more and about 160°C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. has been done.

The present invention can be applied to various black-and-white and color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

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

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 59-58147, JP 59-60437,
JP 60-227256, JP 61-4043, JP 61-43743, JP 61-42657
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, as shown 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. 53-3701
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-
Examples include those that specify the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities, such as No. 200SSO and JP-A-59-177551.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of k17643, and page 6 of k18716
It is described from the right column on page 47 to the left column on page 648.

The color photographic material according to the present invention is described in the above-mentioned RD, Ko 17643, pages 28-29, and N1118716.
651, 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. Aminophenol compounds are also useful as color developing agents, but P-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, and P-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

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, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, gnitite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (l,4-diazabicyclo(2,2,2)octane) various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol grade ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, foggers such as sodium boron hydride. agent, auxiliary developing agent such as 1-phenyl-3-virapritone, viscosity imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, etc. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-l,■-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine Typical examples include -N,N,N', N'-tetramethylenephosphonic acid, ethylene cyanodi(0-hydroxyphenylacetic 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 known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-virapritone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pi (pi) of these color developing solutions and black and white developing solutions is generally 9 to 12.Also, the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but in general, the pi of the light-sensitive material 1 31 per square meter, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 500 per square meter.
It can also be less than mf. 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 development, 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 (■), Kobal I-(I
Compounds of polyvalent metals such as I[), chromium (Vl), and #14(n), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide dichromate; organic complex salts of iron (II) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and L3-diaminopropane. Aminopolycarboxylic acids such as tetraacetic acid, glycol ether diamine tetraacetic acid, and complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; nitrohenzenes, and the like can be used. Among these, aminopolycarboxylic acid iron (I[I) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (I[[) complex salts] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, the aminopolycarboxylic acid iron(I[[) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron(II[) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. can.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
, No. 290,812, No. 2.059.988, JP-A-53-32, No. 736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72.623, No. 53
-95,630, 53-95,631, 53-
No. 10.4232, No. 53-124,424, No. 53
-141.623, 53-28.426, Research Disclosure N (117,129 (197
Compounds having a mercapto group or disulfide group as described in JP-A No. 1983-140.129; thiazolidine derivatives described in JP-A No. 45-8,506; JP-A-Sho 52-20.832; No. 53-32,735
No., thiourea derivatives described in U.S. Pat. No. 3,706,561;
16.235; West German Patent No. 966.
Polyoxyethylene compounds described in Japanese Patent Publication No. 410, No. 2,748.430; Polyamine compounds described in Japanese Patent Publication No. 45-8836; Others No. 53-94.927, same 5
No. 4-35.727, No. 55-26,506, No. 58
Compounds described in No.-163.940; 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, as described in US Pat. No. 3,893,858 and West German Patent No. L29.
Compounds described in No. 0,812 and JP-A-53-95,630 are preferred. Additionally, U.S. Patent No. 4,552,834
Also preferred are the compounds described in No. 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 fixing agents include thiosulfates, thiocyanates, thioether 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 carbonyl bisulfite 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 desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of 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
Urnalof the 5ociety of Mo
tion Picture and Television
n Engineers Vol. 64, p. 248-253
(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 calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, RL Chemistry of Bacterial and Mildew Preventive Agents J, Hygiene Technology Complete Edition "Sterilization of Microorganisms, It is also possible to use the fungicides described in "Sterilization and Antifungal Techniques" and "Encyclopedia of Mildew and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pi (pi) of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to io minutes at 15-45°C is selected, preferably 30 seconds to 5 minutes at 25-40°C.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such a stabilization process, Japanese Patent Application Laid-open No. 57-. No. 8,543, 58-
All known methods described in No. 14.834 and No. 60-220.345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed, and as an example, the bath is used as a final bath for color photographic materials. Mention may be made of stabilizing baths containing formalin and surfactants.

It is also possible to add various botanical agents and antifungal agents 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. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
No. 15,159, aldol compounds described in No. 13,924, U.S. Patent No. 1
Metal salt complex described in No. 3.719.492, JP-A-53-
Examples include urethane compounds described in No. 135.628.

The silver halide color light-sensitive material of the present invention may contain various types of niphenyl-3, if necessary, for the purpose of promoting color development.
~Pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A No. 56-64, No. 339, No. 57144.547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at temperatures of 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or conversely, lower temperatures can be used to improve image quality and stability of processing solutions. can be achieved. 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. 3,674,499 may be carried out.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is of course not limited to these Examples.

(Example 1) Average iodine content is 20 mol%, average equivalent sphere diameter is 0.7 μm
An aqueous silver nitrate solution and an aqueous solution of a mixture of potassium bromide and potassium iodide were added at a predetermined temperature for 40 minutes by a controlled double jet method in an aqueous gelatin solution using double twinned silver iodobromide particles as seed crystals, An emulsion was formed consisting of twinned grains having an average equivalent sphere diameter of 1.0 .mu.m and having a core-shell ratio of 1:2 and a shell iodine content of 2 mol %.

After grain formation, the emulsion is subjected to a normal desalting water washing process and then washed for 40'
14g was redispersed with C under the conditions of 8.9 and pH 6.0.

In this way, emulsion Em-1 was prepared. In contrast,
Emulsion Em-2 was prepared in exactly the same manner as emulsion Em1, except that 3.7 x 10 -5 mol of the compound 1-10 per mol of silver was added to the reaction pot 2 minutes before the start of shell formation to form grains. did.

Also, except for changing compound 1-10 to 1-2, emulsion Em
Emulsion Em-3 was prepared in exactly the same manner as Em-2.

When forming grains in the same manner as in emulsion Em-1, 1 minute after the start of shell formation, thiourea dioxide was added at 1.2×1 per mole of silver.
Emulsion Em-4 was prepared in exactly the same manner as emulsion Em-1 except that 0-'mol was added.

Silver 1 dimethylamine borane instead of thiourea dioxide
Emulsion Em except that 1.2X10-' was added per mole
Emulsion Em-5 was prepared in exactly the same manner as Em-4. Also,
Emulsion Em except that 2.5XIO-'' mole of L-ascorbic acid was added per mole of silver instead of thiourea dioxide.
Emulsion Em-6 was prepared in exactly the same manner as in Example-4.

Furthermore, when performing grain formation similar to emulsion Em-1, the thiosulfonic acid compound listed in Table 1 was added in the amount listed in Table 1 1 minute before the start of shell formation.
Emulsions Em-7 to Em-12 shown in Table 1 were prepared in exactly the same manner as Emulsion Em-1, except that the reduction sensitizer shown in Table 1 was added in the amount shown in Table 1 after 10 minutes.

After adding sensitizing dye 1 in an amount of 4.6 x 10-' mol per mol of silver to the emulsions Em, -1 to 12 thus prepared, optimal gold-sulfur sensitization was carried out using sodium thiosulfate and chloroauric acid. Emulsions 101 to 112 were prepared.

In addition, 4 sensitizing dyes 2 were added to emulsions Em-1 to Em-12 per mole of silver.
．． Optimal gold-sulfur sensitization using sodium thiosulfate and chloroauric acid after addition of 6 x 10-' moles resulted in emulsions 113-1.
24 was produced.

Sensitizing dyestuff C2, H5 (CH2) 3SO3K (C)12)! S
(Also, after adding 4.6 x 10-' moles of sensitizing dye A-11 listed in Table 8 to emulsion Em-1-12 per mole of silver, the total sulfur was increased optimally using sodium thiosulfate and chloroauric acid. Emulsions 125 to 136 were prepared.

In addition, for milk iFJEm-1 to 12, sensitizing dye B listed in Table 8
Emulsions 137 to 148 were prepared by adding 4.6XIO-' mol of -11 per mol of silver and optimally total sulfur sensitization using sodium thiosulfate and chloroauric acid.

An emulsion layer and a protective layer were coated on a triacetylcellulose support provided with an undercoat layer in the coating amounts shown below, and samples 1001 to 104 were prepared using emulsions 101 to 148.
8 was produced.

(1) Emulsion layer/emulsion... Emulsions 101 to 148 shown in Table 1-4 (silver 1
．． 7X10-"mol/mal ・Coupler (1,5X10-mol/I") C,H5 ・Tricresyl phosphate (1,I Og/1) ・Gelatin (2,30g/g+") (2) Protective layer - 2,4-dichlorotriazine-6-hydroxy s-triazine sodium salt (0.08 g/mz) - Gelatin (1,80 g/+w'') Evaluation of pressure characteristics was performed as follows. Under controlled humidity conditions of 40% relative humidity, the coated sample was fixed at one end with the emulsion side facing inside, and folded while rotating 180 degrees at a bending speed of 360 degrees/second along a stainless steel vibrator having a diameter of 10 am. These folds were made 10 seconds before exposure.

These samples were given a 1/100 second sensitometric exposure through a continuous wedge at a color temperature of 4800'';
The following color development process was performed.

The development process used here was carried out at 38°C under the following conditions.

1. Color development ------1 ------2 minutes 45 seconds Soil Bleaching ------- 6 minutes 30 seconds 3, Washing ---m ------3 Minute 15 seconds 4, Fixing ----～------- 6 minutes 30 seconds 5, Washing -
-1----・--3 minutes 15 seconds 6, stable ・--m
--3 minutes and 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.4g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4 g hydroxylamine sulfate 2.4 g 4-(N-ethyl-N-βhydroxyethylamino)-2 Add methyl-aniline sulfate solution to bleach solution Ammonium Bromide Aqueous ammonia (27%) Ethylenediamine-4 Ferric acetate sodium salt Ethylenediamine-Tetraacetic acid disodium salt Add ammonium nitrate water to fix fixing solution Sodium tetrapolyphosphate Sodium sulfite Ammonium thiosulfate (70%) Add sodium bisulfite water to stabilize solution 4.5 g 1 160.0 g 4 .0ta1 20 1 5 f 2, Og 4.0g 175, b 1 4.6g 1 Formalin 8.0a+f Add water II! The concentration of the treated sample was measured using a green filter.

The resulting sensitivity and fog were evaluated for the portions with and without bending.

The sensitivity was expressed as the relative value of the reciprocal of the exposure amount required for the optical density to become higher than the fog by 0.2.

The results thus obtained are shown in Table 2.

As is clear from Table 2, samples 1031 to 103 of the present invention
6 and samples 1043 to 1048 are for comparison samples,
Comparative sample 1004 with high sensitivity and reduction sensitization
For Samples 1012 and 1016 to 1024, the change in sensitivity to pressure was small, and the effects of the present invention are remarkable.

In addition, samples 1035.1036.1047 were subjected to reduction sensitization using L-ascorbic acid during the growth of silver halide grains.
The effect is particularly remarkable at 1048°.

Example 2 In the emulsion Em-1 described in Example 1, sensitizing dye V was added at 3.5 x 10-S mol per mol of silver, sensitizing dye ■ was added at 3.0 x 10-' mol per mol of silver, and sensitizing dye 1 was added. 8.0% per mole of silver.
After adding 0.times.10@-5 mol, total sulfur sensitization was carried out optimally using sodium thiosulfate and chloroauric acid to prepare emulsion 201.

In addition, in the emulsion Em-12 described in Example 1, sensitizing dye V was added at 3.5X10-' mol per mol of silver, sensitizing dye ■ was added at 3.0XIO-' mol per mol of silver, and sensitizing dye I was added at 3.0XIO-' mol per mol of silver. After adding 8.0 x 10-' moles per mole, optimal total sulfur sensitization was carried out using sodium thiosulfate and chloroauric acid, resulting in emulsion 202.
was created.

Emulsion 203 was also prepared in exactly the same manner as emulsion 202 except that sensitizing dye 1 was replaced with the same amount of sensitizing dye 2.

Further, emulsion 204 was prepared in exactly the same manner as emulsion 202 except that sensitizing dye i was replaced with the same amount of sensitizing dye A-11.

Emulsion 205 was also prepared in exactly the same manner as emulsion 202 except that sensitizing dye 1 was replaced with the same amount of sensitizing dye B-11.

on a subbed cellulose triacetate film support.
Samples 2001 to 2005, which are multilayer color light-sensitive materials, were prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/- units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount is expressed in moles.

(Sample 101) 1st layer (antihalation layer) black colloidal silver gelatin 2nd layer (middle layer) 25-G-L-pentadecyl hydroquinone X-1 X-3 X-12 -1 -2 -3 B5-1 B5-2 gelatin Third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Silver 0.18 1.40 0.18 0.07 0.02 0.002 0.06 0.08 0.10 0.10 0.02 1.04 0.25 0.25 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-2 X-10 -1 -2 -3 B5-1 gelatin 4th layer (second red-sensitive emulsion layer) Emulsion F Sensitizing dye I Sensitizing dye■ Sensitizing dye■ X-2 X-3 X-10 -1 -2 6,9X 10-' 1.8 x 10-' 3, lX10-' 0.335 0.20 0.07 0.05 0.07 0.060 0.87 Silver 1.0 5, lX1O-5 1,4X 10-' 2.3XIO”’ 0.400 0.050 0.015 0.07 0.05 -3 gelatin 5th layer (3rd red-sensitive emulsion layer) emulsion Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-3 X-4 X-2 B5-1 B5-2 gelatin 6th layer (middle layer) X-5 B5-1 gelatin 7th layer (first green emulsion layer) Emulsion A Emulsion B Silver 0.07 1.30 1.60 5.4X10-5 1.4X10-5 2.4X10-' 0.010 0.080 0.097 0.22 0.10 1.63 0.040 0.020 0.80 Silver Silver 0.15 0.15 Sensitizing dye V Sensitizing dye■ Sensitizing dye■ X-6 X-1 X-7 X-8 B5-1 B5-3 gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye■ Sensitizing dye■ X-6 X-8 X-7 B5-1 B5-3 3.0X10-5 1.0X10-' 3.8X10-' 0.260 0.021 0.030 0.025 o,io.

O,010 0,63 Silver 0.45 2, I Emulsion layer) Emulsion X-13 listed in Table 3 X-11 X-1 B5-1 B5-2 Gelatin 1st O layer (yellow filter layer) Yellow colloidal silver Blue sensitive emulsion layer) Emulsion A Emulsion B Emulsion E Sensitizing dye ■ X-9 0.50 Silver 1.2 0.015 0.100 0.025 0.25 0.10 1.54 Silver 0.05 0.08 0.03 0.95 Silver 0.08 Silver 0.07 Silver 0.07 3.5X10 0.721 X-8 B5-1 Gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion F Sensitizing dye■ Eχ- 9 X-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ X-9 B5-1 Gelatin 14th layer (first protective layer) Emulsion H -4 -5 0,042 0,28 1,10 Silver 0.45 2, lX10-' 0.154 0.00? 0.05 0.78 Silver 0.77 2.2X10-' 0.20 0.07 0.69 Silver 0.20 0.11 0.17 HB S-10,05 Gelatin 1.00 15th layer Protection N) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.543-
1 0.20 gelatin
1.20 In addition to the above ingredients, a gelatin hardening agent H1 and a surfactant were added to each layer.

The contents of emulsions A to H used are shown below. Table C also shows the names or structural formulas of the compounds used.

These samples were subjected to the same treatment as in Example 1 for evaluation of pressure characteristics, and were exposed to light in the same manner as in Example 1.

Further, color development was carried out in the same manner as in Example 1 except that the color development time was changed to 3 minutes and 15 seconds, and the density was measured using a green filter.

The resulting sensitivity and fog were evaluated for the portions with and without bending.

The sensitivity was expressed as the relative value of the reciprocal of the exposure amount required for the optical density to become higher than the fog by 0.15.

The results thus obtained are shown in Table 3.

As is clear from Table 3, the sample of the present invention 2004°200
No. 5 is higher than the comparative sample, and the fog and sensitivity change with respect to pressure are small, and the effect of the present invention is remarkable.

Example 3 Average iodine content is 20 mol%, average equivalent sphere diameter is 0.7 μm
Using octahedral silver iodobromide grains as seed crystals, silver nitrate aqueous solution and potassium bromide aqueous solution were added at a predetermined temperature for 20 minutes in a gelatin aqueous solution using a controlled double jet method to obtain a core-shell ratio of 1:2 on average. Equivalent ball diameter 1.0
An emulsion consisting of monodisperse octahedral grains of μm was formed.

After grain formation, the emulsion is subjected to a normal desalting water washing process and then washed for 40'
It was redispersed in C under the conditions of pAg 9.0 and pH 6.5.

In this way, emulsion Em-13 was prepared.

In contrast, 1 minute before the start of shell formation, the compound 1-2
was added in an amount of 5XIO-' mole per mole of silver, and 1.0X10-' of L-ascorbic acid was added 2 minutes after the start of shell form a.
Emulsion Em-14 was prepared in exactly the same manner as Em-13 except that only 1 molar amount was added.

Emulsions Em-13 and Em-14 thus prepared were optimally sensitized to total sulfur using sodium thiosulfate and chloroauric acid to prepare emulsions 301 and 302.

Multilayer color light-sensitive materials 3001 to 3005 were prepared by coating each layer of &11 as shown below on an undercoated cellulose triacetate film support.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/m'' units, and for silver halide, the coating amount is expressed in terms of silver.However, for sensitizing dyes, the same layer The coating amount per mole of silver halide is shown in mole units.

1st layer (antihalation layer) Black colloidal silver 0.13 gelatin 1. OU -60,05 U-20,I U-70,1 HB S -20,02 Second layer (intermediate layer) Gelatin 1.0 Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (Silver iodide 7 mol%, average grain size 0.7 μ, coefficient of variation 13%) 1.72 Gelatin 0.9 Sensitizing dye IX
2.0X10-' Sensitizing Dye I
II 1. QXlo-'sensitizing dye U O,3X10-'E
X-180,40 EX-190,047 EX-300,05 HBS-10,10 HBS-50,10 4th layer (middle N) Gelatin 0.4EX-21
0,10 8B S -50,05 5th layer (second red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 5 mol%, average grain size 1.3 μm, coefficient of variation 16%) 2.30 Gelatin 1.0 sensitizing dye IX
1.5X10-' Sensitizing Dye III 2. OX 10-'
Sensitizing dye II O,5X 1
0-'EX-200,150 EX-I8 0.027HB
S -50,050 HBS-20,060 6i (intermediate layer) Gelatin 1.0EX-26
0.05 CPd~2 0.058 B
S-20,05 7th layer (first green-sensitive layer) Monodispersed silver iodobromide emulsion (iodide w & 7 mol% average grain size 0.4
μ stiffness, coefficient of variation 19%) 0.64 Monodisperse silver iodobromide emulsion (m6 mol% iodide, average grain size 0.7μ, coefficient of variation 18%) 0.40 Gelatin sensitizing dye■ Sensitizing dye■ Table Sensitizing dye X-23 X-22 X-24 B5-5 B5-2 8th layer (intermediate layer) Gelatin X-22 B5-5 9th layer (second green-sensitive emulsion layer) Emulsion gelatin sensitizing dye described ■ Sensitizing dye ■ Sensitizing dye described in Table 4 Eχ-22 1,0 IXIO-'4X10-'lXl0-' 0.20 0.6I O,084 0,25 0,45 0,4 0,10 0,05 2,23 1,5 1,5X10-'2.3X10-'1.5X10-' 0.020 X-25 B5-2 10th layer (middle layer) Yellow colloidal silver gelatin X-25 Silver bromide emulsion (silver iodide 5 mol%, average grain size 0.9μ-1 coefficient of variation 17%) Gelatin sensitizing dye XV Sensitizing dye XVI X-27 X-28 X-30 B5-5 0.009 0. 088 0.12 1.2 0.006 0.3 0.3 0.20 0.20 2.0 IXIO-'IX10-' 0.63 0.57 0.035 0.05 12th layer ( 2 blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (8 mol% silver iodide, average grain size 1.3 μm, coefficient of variation 18%) Gelatin sensitizing dye XV Sensitizing dye XVI X-27 X-28 X-31 B5-2 13th layer (intermediate layer) Gelatin X-29 -6- -7 BS-2 14th layer (protective layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol% 1, 11 O.5 5XlO -'
2 Gelatin E.5 Polymethyl methacrylate particles (average 1.5μ) 0. I S3 0.23 4
-1 and gelatin hardening agent H-3 were added to the other surfactants. The names or structural formulas of the compounds used are shown in Table C and Table I below.

These samples were subjected to the same treatment as in Example 1 for evaluation of pressure characteristics, and were exposed to light in the same manner as in Example 1.

Furthermore, the following color development treatment was performed.

*Replenishment amount; 35+am per 1m length of photosensitive material.

A processing solution having the following composition was also prepared.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriamine pentabutyl acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-Ethyl-N β-hydroxyethylamino)-2 Methylaniline Add sulfate water and H (bleaching solution) L3-diaminopropane tetranodic acid iron (I [[) ammonium 5, 0 4, 0 30, 0 1, 3 1, 2a+g 2, 0 3, 6 4, 7 6. 2 1, Offfi 1. H 10,00 10.15 Mother liquor (g) Replenisher (g) 0.25 mol 0.30 mol 1.3-cyanobrobantetraacetic acid Ammonium bromide Acetate Ammonium nitrate Add water and adjust pH with acetic acid and ammonia (fixing) Liquid) Ethylenediamine tetranodic acid Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution H (700g/R) Rhodanammoniumthiourea 3.6-cythia 18~ Octanediol 3.0 5 0 0 1.0f pH 4,3 Mother liquor (g) 1 .5 IO30 8,0 4,0 20 0 0 ■, 0e pH3,5 Replenisher (g) 1.8 12.0 10.0 170, Omf 200. Omj! ioo, o 150.0 3.0 5.0 3.0 5.0 Add water 1. Of 1. Of ammonia acetate p)! 6.5 6.7
(Stable solution) Common formalin for mother solution and replenisher solution (37%) L2a+15-
Chloro-2-methyl-4-isothiazolin-3-one
6. On+g2-Methyl-4-isothiazolin 3-one 3.0mg Surfactant 0.4 (C1oHz, O
+CH2CH2O+-r-0H: 1 ethylene glycol 1.0 Add water
1.01 pH 5.0-7.0 The concentration of the treated sample was measured using a green filter.

The resulting sensitivity and fog were evaluated for the portions with and without bending.

The sensitivity is expressed as the relative value of the reciprocal of the exposure amount required for the optical density to become 0.15 higher than the fog.

The results thus obtained are shown in Table 4.

As is clear from Table 4, sample 3004.300 of the present invention
Sample No. 5 is inferior to the comparative sample, and the fog and sensitivity change against pressure are small, and the effect of the present invention is remarkable.

Table A CH, SO, 5Na C, H2OO, S Na CjH, S O, S K C4H, SO, S L 1 ChHIffS OzS Na Ce HI 7 S Oz S N a Engineering) 2) -3) = 4) 5) 6) -7) CH, (CH,), CHCH, SO, S -NH4Cz
H5 (1-8) C+oHt+5OtSNa(19)
C+zHzsS O! S N a (110) C
+hHzsS OzS Na(1-12)t-C,H
9SO2SNa(1-13)CH,○CH,CH,S
O, S -Na (1 15) CHz-CHCHzS○2SNa (I-23
) (■ 24) (I-25) (I-26) (1-27) (I 33) →CHCHth2" CHCHth-1 (■ 28) (n-1) C, H2S O2S -CH3 (I-29 ) (It-2) 5H 7SO□S CH, CH.

K S S 0z (CHz) = S ()zs K (■ 3) (1-30) N a S S S 0x (CHz), S OzS N a
(1-31) (II-4) N a S SO, (CH,), S (CH,)4S
○, 5NaN-32) (11-5) CzHsS ChS CHzCHzCN)suz:)IN
a (II-12) (If-I3) (II-11) (I[-16) (■ 17) (■ 23) (II-18) CzHsSOzSCHzCHtCHzCHzOH (II
-24) (II-19) CH.

(■ 22) CH, S　S　oz(c　H2), SO,S　CH.

(III-2) CtHsSOzSCIItCHzSOtCHxCHzS
SOzCzHs (III-4) CHICH! 0H (III-7) Cz Hs S OZ S S S Oz Cz Hs
(III-8) (n) C3H7SOzSSSOzC8Ht(n) Table C CIl X IJ X-3 H X X EX-7 U-1 -2 -3 EX-10 H CHl tHs Js C! )ISO503G Sensitizing dye XI Sensitizing dye X■ Sensitizing dye■ (Ni1jz)3sυ! Na Sensitizing dye ■ Sensitizing dye ■ (CHz) aso, G (cHz), SO, H-N (C, FIS)! -1 -1 CHg=CHSO2CHt-CONHCHt [CHz =CHSOx CHz C0NHCHz Sensitizing dye XV Sensitizing dye XVt -6 -7 Compound CPd2 0H H -3 CL=CH502 CHz=CHSOx H2 C1l.

EX-18 EX-21 EX-22 EX-23 l EX-19 EX-20 EX-24 EX-25 EX 26 nμ EX-27 EX 0 H3 EX-31 H EX-28 X-28CJ EX-29 B5-5 tHs -1 -3 -4

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer is formed by the following general formula [
I], [II] or [III] containing a silver halide emulsion reduction-sensitized in the presence of at least one compound selected from compounds represented by formulas [A], [III];
A silver halide photographic material containing at least one sensitizing dye represented by [B] or [C]. [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. [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [C] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^3 and R^4 are Represents an alkyl group. R^5 represents a hydrogen atom, an alkyl group or an aryl group. X^■ represents an anion, and n represents a numerical value for adjusting the charge of the entire molecule, and when an inner salt is formed, n=0. (2) The silver halide photographic material according to claim (1), which contains a silver halide emulsion reduction-sensitized with ascorbic acid or an ascorbic acid derivative.