JPH02222939A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material which has a high sensitivity, less fogging and particularly the high sensitivity of a dye sensitization area by providing silver halide emulsion layers contg. silver halide particles which contain a specific ratio of silver iodide in the particle surface subjected to specific sensitization on a base. CONSTITUTION:The silver halide emulsion layers contg. the silver halide particles which are subjected to reduction sensitization during particle growth, are subjected to at least one of gold sensitization, sulfur sensitization or noble metal sensitization and contain >=5mol% silver iodide in the particle surface are provided on the base. The silver halide particles are subjected to the reduction sensitization during the growth of the silver halide particles in the formation of the above-mentioned particles. A stannous salt, hydrazine deriv., foramidine sulfinic acid, silane compd., borane compd., etc., are usable as the reduction sensitizing agent. The photosensitive material which has the high sensitivity, the less fogging and particularly the high sensitivity in the color sensitization area is obtd. in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and more particularly, it is reduced sensitized during grain formation and has a specific amount of silver iodide on its surface. The present invention relates to a silver halide photographic light-sensitive material which contains photosensitive silver halide grains and has high sensitivity and little fog, particularly high sensitivity in the color sensitized region.

(Prior Art) The basic properties required of a silver halide emulsion for shadowing are high sensitivity, low fog, and fine grain.

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

Increasing the size increases the number of photons absorbed by one particle, but
Decrease image quality. Increasing development activity is also an effective means for increasing sensitivity, but in the case of parallel type 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.

In addition, JaIIIes et al. have shown that when a type of reduction sensitization is performed in which a coated film of a gold-sulfur sensitized emulsion is vacuum degassed and then heat treated in a hydrogen gas atmosphere, it is possible to achieve normal reduction sensitization. We found that the sensitivity can be increased at a lower fog level compared to the conventional method. This sensitization method is well known as hydrogen sensitization, and is effective as a means of increasing sensitivity on a laboratory scale. Furthermore, hydrogen sensitization is actually used in the field of astrophotography.

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

Carrot I U.S. Patent No. 2.48
No. 7,850 discloses tin compounds, Lowe et al. No. 2,512.925 discloses polyamine compounds, Fallens et al. British Patent No. 789.823 discloses thiourea dioxide-based compounds. was disclosed to be useful as a reduction sensitizer. Furthermore, Co11ier (Korea) is a Photographer.
c 5ctenca and Engineering
Vol. 23, p. 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She is dimethylamine poran, stannous chloride, hydrazine,
A method of high pH ripening and low pAgP formation was adopted. The method of reduction sensitization is further described in U.S. Pat. No. 2.518.698, U.S. Pat. ．． No. 917, No. 3.779,777, No. 3.930,867
It is also disclosed in the issue. Not only the selection of reduction aggravating agents but also the method of using reducing agents are disclosed in Japanese Patent Publications No. 57-33572, No. 58-141 (1), and Japanese Patent Application Laid-open No. 179835-1983. Techniques for improving storage stability are also disclosed in JP-A No. 57-82831 and JP-A No. 60-178445. Despite these many studies, photosensitive materials have not been treated with hydrogen gas under vacuum. Compared to hydrogen sensitization, the increase in sensitivity was insufficient.
It is reported by Mofsar et al. in vol. 29, p. 233 (1985).

In addition, the above-mentioned literature lists conventionally known reduction sensitizers, 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 ripening, and hydrazine. Therefore, favorable properties of ascorbic acid compounds as reduction sensitizers have not been found. Regarding further innovations, JP-A-57-179
No. 835.

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 reached a sufficient level of improvement. At the same time, improvements in the storage stability of photographic materials containing reduction-sensitized emulsions have been awaited.

(Problems to be Solved by the Invention) The conventional technology of reduction sensitization has not been sufficient to meet the recent demands for photographic materials with high sensitivity and high image quality. Hydrogen sensitization also has the disadvantage that if the photosensitive material is left in the air after hydrogen sensitization, the sensitizing effect is lost. Therefore, it is difficult to utilize this sensitization method in the case of photographic materials for which special equipment cannot be used.

Further, when color sensitization is performed, there is a problem that the increase in sensitivity due to reduction sensitization is reduced.

(Objective of the Invention) The object of the present invention is to provide a silver halide photographic material with high sensitivity and low fog (especially high sensitivity in the color sensitization region). To provide a color photographic material with high sensitivity and little fog, which is less susceptible to deterioration.

[Means to solve the problem]

The objects of the present invention have been achieved by silver halide photographic materials described in (1) to (6) below.

(1) Silver iodide with a grain surface of 5 mol% or more that has been reduction sensitized during grain growth and has been subjected to at least one of gold sensitization, sulfur sensitization, or noble metal sensitization in an arbitrary step. 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains on a support.

(2) The silver halide photographic material described in (1) above, which is reduction sensitized in the presence of at least one compound represented by formula [I], [II], or (III).

(T) R-3O, S-M (It) R-3O, S-R' (II[] R30-3Lm 5SOz R
``In the formula, RSR' and R2 may be the same or different,
represents 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
It is.

The compound of general formula (H or [) is (1) or I
It may also be a polymer containing a divalent group derived from the structure shown in II) as a repeating unit. Also, when possible, R, R'11. R''L may be bonded to each other to form a ring.

(3) The silver halide photographic material described in (1) above, which contains silver halide grains that have been reduction sensitized and then gold/sulfur sensitized.

(4) The silver halide photographic material described in (1) above, which is reduction sensitized with at least one ascorbic acid or its derivative.

(5) Silver halide grains are 5X per mole of halogen northern limit
The silver halide photographic material according to (4), which has been subjected to reduction sensitization with 10"' mol -5 mol to 1 x 10 -' acid or a derivative thereof.

(6) The silver halide photographic material described in (4) above, which is subjected to reduction sensitization in the presence of at least one compound represented by formula (1), [11) or (III).

The present invention will be explained in detail below.

In the production of silver halide grains, which is a feature of the present invention, reduction sensitization is performed during growth of the silver halide grains. Growing means that silver halide grains are undergoing physical ripening, addition of a water-soluble root salt and a water-soluble alkali halide (precipitation, Pr
"ecipitation" also means that it is included during the further precipitation step after reduction sensitization with the addition of these substances temporarily stopped.

The reduction sensitization of the present invention refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of adding a reduction sensitizer to a silver halide emulsion, and a pA. g1-7 low 1
) A method of growing or aging in an Ag atmosphere,
It is possible to choose either a method of growing or aging in a high pH atmosphere of pH 8 to 11, which is called high pH ripening. 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, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, etc. are known. For the reduction enhancement 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 are stannous chloride, thiourea dioxide, and dimethylamine borane. The amount of these reduction sensitizers to be added depends on the emulsion manufacturing conditions, so it is necessary to select the amount to be added.
A suitable range is from ' to 104 moles.

These reduction sensitizers are dissolved in water or a solvent such as alcohols, glycols, ketones, esters, amides, etc., 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. In addition, a reduction sensitizer is added in advance to an aqueous solution of water-soluble root salt or water-soluble alkali halide. : Silver halide grains may be precipitated using these aqueous solutions. 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.

It is particularly preferred that the reduction sensitization of the present invention is carried out using ascorbic acid or one of its derivatives.

Specific examples of ascorbic acid and its derivatives (hereinafter referred to as "ascorbic acid compound j") include the following.

(^-1) (^-2) (A-3) (A-4) (A-5) (^-6) (A-7) (A-8) (A-9) (A-10) L-ascorbic acid L-sodium ascorbate L-potassium ascorbate DL-ascorbic acid D-sodium ascorbate L-ascorbic acid-6-acetate-ascorbic acid-6-palmitate monoascorbic acid-6-benzoate L- Ascorbic acid-6-diacetate L-Ascorbic acid-5,6-0-isopropylidene In order to add the above-mentioned ascorbic acid compounds in the manufacturing process of the silver halide emulsion of the present invention, they are directly dispersed in the emulsion. Alternatively, it may be added during the production process by being dissolved in a solvent such as water, methanol, ethanol, etc. alone or in a mixed solvent.

It is desirable to use the ascorbic acid compound used in the present invention in a larger amount than the amount in which conventional reduction sensitizers are preferably used. For example, Japanese Patent Publication No. 57-33572 states that ``The amount of reducing agent is usually 0.75x1 per gram of silver ion.''
not exceeding 0" milliequivalents (8 x 10" moles/A, g
Ascorbic acid and shite, 10-7 to 10-5 mol/A
g X mol) is often effective. ” (converted value is by the inventors). US-2,
487,850, ``The amount of tin compound that can be used as a reduction sensitizer is 5 mol to 1 x 10-' to 4 mol.
4 x 10-' moles.

Furthermore, in JP-A No. 57-179835, the amount of thiourea dioxide added is about 0.01 to about 2 per mole of silver halide.
(2) It is stated that it is appropriate to use about 0.01 ■ to about 3 ■ as stannous chloride. The ascorbic acid compound used in the present invention depends on the grain size of the emulsion, the halogen composition,
The preferred amount to be added depends on factors such as the temperature, pH, and pAg of emulsion preparation, but it is 5 per mole of silver halide.
It is desirable to select from the range of X 10-' mol to 1 x 10-1 mol. More preferably 5X10-'mol to 1
It is preferable to select from the range of x IO'''z mol. Particularly preferable is 5 mol to 1 x 10-' mol - 5 mol to 1 x
10-'' moles.

Although the ascorbic acid compound of the present invention may be added at any stage of the emulsion manufacturing process, it is particularly preferred 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 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 the solution of the reduction sensitizer in several portions as the particles are formed and continuously add the solution over a long period of time even in addition L7.

Although the reduction sensitization method using the ascorbic acid compound of the present invention is superior to conventional reduction sensitization methods in terms of sensitivity, fog, and stability over time, other reduction sensitization methods In some cases, it is more preferable to combine with The combination methods include adding a known reducing agent to a silver halide emulsion, growing or ripening in an atmosphere with a low PAg of pAg 1 to 7, which is called silver ripening.
7. Either a method of growing or aging in a high pH atmosphere of pH 8 to 11, which is called high pH aging, can be selected. Among these, the method of adding a reduction sensitizer is preferred since the level of reduction sensitization can be finely adjusted.

Although stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds are known as reduction sensitizers, ascorbic acid compounds are superior to these known reduction sensitizers. gives the result.

In addition to the reduction sensitization of the present invention, chemical sensitizations include sulfur sensitization, gold sensitization, and noble metals of group I of the periodic table (e.g., Pd, Pt
Exacerbations due to 5I d) and combinations of these sensitizations can be employed. Among these, gold sensitization or sulfur sensitization is preferred, and gold plus sulfur sensitization (also referred to as "gold/sulfur sensitization") is particularly preferred, and gold/sulfur sensitization is performed after the reduction sensitization of the present invention. is preferable.

To explain in more detail the compounds of general formulas (1), (If) and CIII), when R, R' and Rz are aliphatic groups, saturated or unsaturated, linear, branched or cyclic, aliphatic carbonized It is a hydrogen group, preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group 2 having 2 to 22 carbon atoms, or an alkynyl group, which 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 furyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R, R1 and R: include monocyclic or condensed ring aromatic groups, preferably those having 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R1 and Rz includes nitrogen, oxygen,
3 to 1 having at least one element selected from sulfur, selenium, and tellurium and having at least one carbon atom
A 5-membered ring, preferably a 3- to 6-membered ring, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole,
Examples include imidazole, benzothiazole, benzoxazole, k-zimidazole, selenazole, benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadeazole ring.

Substituents for R5R1 and Rt include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethoxy, octyl), aryl groups (e.g. phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (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 groups (e.g. methylsulfonyl, phenylsulfonyl) ), acylamino group (e.g. acetylamino, benzoylamino), sulfonylamino group (e.g. methanesulfonylamino, benzenesulfonylamino), acyloxy group (e.g. acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group , -3O2SM
group, -5oxR' group.

The divalent linking group represented by C,N.

An atom or atomic group containing at least one selected from S and 0. Specifically, alkylene group, alkenylene group, alkynylene group, arylene group, -〇-1-3-
-NH--CO--5oz-, etc., alone or in combination.

L is preferably a divalent aliphatic group or a divalent aromatic group. As the divalent aliphatic group of L, for example, ACHz h
(n = 1-12), CHt CH=CH
CHz -CHtCECCH, -tetrabutylammonium, etc.), phosphonium ion (
(tetraphenylphosphonium), guanidyl group, etc.

When general formula (1) to III) is a polymer,
Examples of the repeating unit include the following.

can give. (2) Examples of the divalent aromatic group include a phenylene group and a naphthylene group.

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. Examples of organic cations include ammonium ions (ammonium and tetramethylammonium), and these polymers may be homopolymers or copolymers with other copolymerizable monomers.

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

The compound of general formula (1) is disclosed in JP-A-54-1019; British Patent No. 972+211; Journal of O
rganic Chemistry (Journal of Organic Chemistry) Volume 53, Page 396 (1988
) and Ches+tcal Abstracts, Vol. 59, 9776 e.

The compound represented by the general formula (I), (II) or (I[I) contains 10-' to 10-' per mole of silver halide.
It is preferable to add molar amount. Further 10-' to 1
The amount added is particularly preferably from 10-' to 10-3 mol to 1 mol of Ag.

In order to add the compounds represented by general formulas (I) to (III) during the manufacturing process, methods commonly used for adding additives to photographic emulsions can be applied.

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

The compound represented by compound (1), ([1) or (III) may be present at any stage of reduction sensitization during grain growth. Preferably, the compound is added before or during reduction sensitization. Particularly preferably, it is added so as to coexist with the reduction sensitizer.

The most preferred general formula of the compound for the present invention is a compound represented by general formula (1).

It was completely unexpected that the surface of the silver halide grains of the present invention contained 5 mol % or more of silver iodide, thereby making the above-mentioned reduction sensitization effect more pronounced.

Various conventionally known methods can be employed to control the silver iodide content near the surface of the grains. A method in which an aqueous solution of a water-soluble root salt and an aqueous solution of a halide containing a water-soluble iodide are further added to silver halide grains grown in the presence of a protective colloid; an aqueous solution of a halide containing a water-soluble iodide is added. A method can be selected from among the methods of ripening by adding a hardly soluble iodide such as silver iodide or silver iodobromide. Alternatively, a method may be used in which iodide is distributed near the surface by physically ripening silver halide grains containing iodide.

5 to 30 contained on the surface of the silver halide grains of the present invention.
In the case of cubic or octahedral crystals, the mole % of silver iodide is preferably distributed as uniformly as possible on the surface of the grains, preferably in a layered structure in which the entire surface of the grain is covered with a layer containing silver iodide. However, in grains such as tetradecahedrons in which 111) and (100) planes coexist, or in grains such as tabular grains in which main planes and side surfaces coexist, only specific planes are mainly covered with a layer containing silver iodide. It is also a preferred form of the present invention. In other words, the present invention also includes cases where not all but part of the surface of the grain is covered with a layer containing silver iodide.

When the surface of the present invention forms a layer containing 5 mol% or more of silver iodide, a spectral sensitizing dye such as cyanine or merocyanine, or an antifoggant or stabilizer such as a mercapto compound, an azole compound, or an azaindene compound is present. The preferred method is to do so. Similarly, it may also be preferable to have a silver halide solvent such as thiocyanic acid, thioether, ammonia, etc. present.

The silver iodide content on the surface of the silver halide grains of the present invention can be detected by various surface elemental analysis methods.

It is useful to use methods such as XPS, Auger electron spectroscopy, and TSS. The simplest and most accurate method is XPS (X-ray Photoelect).
ronSpectroscopy), and the surface silver iodide content of the present invention is defined by the value measured by this method.

X P S (X-ray Photoelectr
It is said that the depth that can be analyzed by surface analysis (on 5 pectroscopy) is about 10 people.

Regarding the principle of the XPS method used to analyze the iodine content near the surface of silver halide grains, please refer to "Electron Spectroscopy" by Atsushi Aihara et al. (Imori Library 16, published by Imori Publishing, 1978). can do.

The standard measurement method for XPS is
This is a method of observing the intensity of iodine (1) and silver (Ag) photoelectrons (usually I 3 dsyt, Ag-3d, 7t) emitted from silver halide grains in an appropriate sample format. .

To determine the iodine content, a calibration curve of the photoelectron intensity ratio of iodine (1) and silver (Ag) (intensity (I) 7 intensity (Ag)) is calculated using several types of standard samples with known iodine contents. can be calculated from this calibration curve. In the case of a silver halide emulsion, XPS measurement must be performed after gelatin adsorbed on the surface of silver halide grains is decomposed and removed using a protease or the like.

In the present invention, the silver halide whose grain surface contains 5 mol% or more of silver iodide means that the silver iodide content is 5 mol when the emulsion grains contained in one emulsion are analyzed by surface elemental analysis. % or more.

In this case, if two or more types of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as centrifugation or separation before analyzing the same type of emulsion. More preferably, it refers to an emulsion having a silver iodide content of 5 to 30 mol% when measured by standard XPS.

The effect of the present invention is remarkable when the surface of the grain contains 5 mol% or more of silver iodide;
More preferred are grains whose surfaces contain 10 to 15 mol % of silver iodide.

The surface halogen composition other than silver iodide is preferably silver bromide, but may also contain up to 10 mol % of silver chloride.

The average silver halide composition of the entire grain of the reduction-sensitized silver halide grains of the present invention is silver iodobromide or silver iodochlorobromide containing 1 to 30 mol % of silver iodide. Preferably 7~
It contains 20 mol% of silver iodide and may contain up to 10 mol% of silver chloride.

In the emulsion layer of the photographic light-sensitive material of the present invention, silver iodobromide and silver iodochlorobromide grains which have not been reduction sensitized can be used alone or in combination with the silver halide grains of the present invention. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to 30 mole percent silver iodide.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes;
For example, a single twin with one twin plane, two parallel twin planes
Depending on the purpose, it can be selected from among parallel multiple twins containing two or more nonparallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, and the like.

In the case of a normal crystal, a cube consisting of (100) planes, (11
1) 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. Further J
our own of I++aging 5ctenca
Vol. 30, p. 247 As reported in 1986, (hl) plane particles with (211) as a representative, (331)
) is representative of (hhl) plane particles, (hkO) plane particles are representative of (210) planes, and (hkO) plane particles are representative of (324) planes.
kl) Planar particles also require some ingenuity in the preparation method, but they can be selected and used depending on the purpose. (1,00) plane and (111
) A tetradecahedral particle in which faces coexist in one particle, (100)
Particles in which two planes or a large number of planes coexist, such as particles in which a plane and a (110) plane coexist, or particles in which a (111) 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 or used together with reduction sensitizers may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and have a narrow distribution. The emulsion may be a monodisperse emulsion having a polydispersity or a polydisperse emulsion having 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 used in a layered manner.

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 Phys
ique PhotographiquePaul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry J.

Published by Focal Press (G, F, Duffin, Pho
tographicEn+ulsion Chemises
try (Focal Press+ 1966),
Zelikman et al., “Production and Coating of Photographic Emulsions J,” published by Focal Press (V.L., Zelikman et al.
Making and Coating Photog
rapic Emulsion, Focal Pr
ess.

(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 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 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 PAg and pH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and Engineering) Volume 6, pp. 159-165 (1962); Journal of Photographic Science (Journa
l ofPhotographtc 5ctenc
e) + vol. 12, pp. 242-251 (1964),
U.S. Patent No. 3,655,394 and British Patent No. 1.
No. 413.748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by Cleve Photography.
Theory and Practice (1930
)) + 131 pages; Gutoff, Photographic Science and Engineering (Gutoff, P.
photography5science and en
gineering) + Vol. 14, pp. 248-257 (1970);
, 439,520 and British Patent No. 2.112.15
It can be easily prepared by the method described in No. 7, etc. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the above-cited U.S. Pat. No. 4,434,226. .

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 --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded together by epitaxial bonding, and the silver halide emulsion of the present invention may have a distribution or structure in terms of halogen composition in its grains. It is preferable to have. Typical examples are Japanese Patent Publication No. 43-13162 and Japanese Patent Publication No. 61-21554.
01, JP 60-222845, JP 61-753
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. 37.

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, 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 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 PbO may also be used if a bonded structure is possible.

In the case of grains such as silver iodobromide having these structures, for example, in core-shell type grains, the silver iodide content in the core portion is preferably higher than that in the shell portion. Conversely, the grains may have a low silver iodide content in the core part and a high content in the shell part. 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 EP-009672.
781, EP-0064412B1, etc., or DE
-2306447C2, surface modification as disclosed in JP-A-60-221320 may be performed.

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. Further, a latent image type emulsion covered with a thin shell can also be used depending on the case.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have more than 1J amount of halogen ions present in the reactor to promote ripening. Therefore,
It is 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.

In addition to reduction sensitization, the silver halide grains of the present invention can be sulfur sensitized.
At least one of gold sensitization or noble metal sensitization is performed at any step of the silver halide emulsion manufacturing process, typically during grain formation. These chemical sensitizations vary depending on the composition, structure, and shape of the emulsion grains, and the intended use of the emulsion, but are typically performed at a grain growth stage after the reduction sensitization of the present invention. . There are cases in which chemical sensitizing nuclei are embedded inside the particle, in cases in which they are embedded in a shallow position from the particle surface, and in cases where chemical sensitizing nuclei are created on the surface1.
Although the effect of the present invention is 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.

In addition to reduction sensitization, chemical sensitization that can be preferably carried out 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.
The Photographic Process, 4th edition, published by Macmillan, 1977% t
T.H.James, The Theory o
f thePhotographic Processes
s+4th ed+Macmillan+ 1977)
It can be carried out using activated gelatin as described in Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, Vol. 34, June 1975, 1.
3452, U.S. Patent No. 2,642.361, 3,2
No. 97,446, No. 3,772.031, No. 3,85
No. 7,711, No. 3,901.714, No. 4,266
．． No. 018 and No. 3,904,115, and pA as described in British Patent No. 1,315,755.
sulfur, selenium, chill layer, gold, platinum, palladium, iridium, or a combination of these exacerbants at a pH of 5 to 10, a pH of 5 to 8, and a temperature of 30 to 8 °C. These chemical sensitizations are most preferably carried out in the presence of gold compounds and thiocyanate compounds and as described in U.S. Pat. Sulfur-containing compounds such as hypo, thiourea compounds, rhodanine compounds, etc. are carried out in the presence of a sulfur-containing 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 inhibit fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Patent No. 2,131
．． No. 038, 3.4LL No. 914, 3,554.7
No. 57, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention does not exhibit any drawbacks even when reduction sensitization is combined with other chemical sensitization. In particular, conventionally it has been difficult to use both gold sensitization and reduction sensitization because fog increases, but the emulsion of the present invention shows favorable effects even when gold sensitization is used in combination. The preferred amount of gold sensitizer is 5 mol to 1× per mol of silver halide.
The amount is 10-' to 5 mol to 1 x 10-' mol, more preferably 5 mol to 1 x 10-' to 5 x 10-' mol.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 x 101 to 10 sulfur sensitizer per mole of silver halide.
1 mol, more preferably 1xio-' to 5X
10-' mole.

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

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, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines 1 mercaptotriazines; Poly( For example, U.S. Pat. No. 3,954
, No. 474, No. 3.982,947, Special Publication No. 1972-2
8.660 can be used.

The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. 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 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, pyridine nucleus, oxazoline nucleus, thiozoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei 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, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus,
A benzoxadole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole 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. Pat. Nos. 2,688,545 and 2,9
77.229, 3.397.060, 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-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 sensitizing dye may be added to the emulsion at any stage of emulsion preparation known to be useful. It is most commonly carried out after the completion of chemical sensitization and before application; however, U.S. Pat.
Also, as described in JP-A No. 4.225.666, it is also described in JP-A-58-113,928 that spectral sensitization can be performed at the same time as chemical sensitization by adding it at the same time as a chemical sensitizer. It can be carried out prior to chemical sensitization as described above, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, U.S. Patent No. 4
．． 225,666 by adding these said compounds separately, i.e., some of these compounds are added prior to chemical sensitization and the rest are added after chemical sensitization. is also possible, as described in U.S. Pat. No. 4.183.
No. 756, or at any time during silver halide grain formation.

The amount added is 4X10-h to 8 per mole of silver halide.
Although XlO-' moles can be used, about 5X10-' to 2X10-' moles are more effective for the more preferred silver halide grain size of 0.2 to 1.2 μm.

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 + Item 17643 (December 1978) and Item +++ 18716 (November 1979).
The relevant sections are summarized in the table below.

Additive type 1 Chemical sensitizer 2 Sensitivity enhancer 4 Brightening agent Anti-stain agent Dye image stabilizer Hardener Binder Plasticizer, lubricant RD17643 Page 23 Page 24 Page 25 Page right column 25 Page 26 Page 26 Page 27 RD18716 Page 648 Right column Same as above 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) Sou 17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4,022,620, 4.3
No. 26.024, No. 4.401.752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425,020,
Those described in the same No. L476.760 are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, for example, US Pat.
．． 310,619, 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432
No. 3.725.067, Research Disclosure Nn24220 (June 1984), JP-A-60-33552, Research Disclosure Nα24230 (June 1984), JP-A-60-4
3659, U.S. Pat. No. 4,500,630, U.S. Pat.
．． Particularly preferred are those described in No. 540,654.

Cyan couplers include phenolic and suphthol couplers, such as those described in U.S. Pat. No. 4.052.
No. 212, No. 4.146.396, No. 4.228
．． No. 233, No. 4.296.200, No. 2,36
9.929, 2.801.171, 2.7
No. 72.162, No. 2.895.826, No. 3.
No. 772.002, No. 3.758.308, No. 4
．． No. 334.011, No. 4.327,173, West German Patent Publication No. 3.329.729, European Patent No. 121.
No. 365A, U.S. Patent No. 3,446.622, U.S. Patent No. 4
．． Preferred are those described in European Patent No. 333.999, European Patent No. 4.451.559, European Patent No. 4,427.767, and European Patent No. 161.626A.

Colored couplers for correcting unnecessary absorption of coloring dyes include, for example, Research Disclosure Nα176.
Section 43 ■-G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,
No. 929, No. 4.138.258, British Patent No. 1,
146,368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include, for example, U.S. Pat. No. 4.366.237, British Patent No. 2.
125.570, European Patent No. 96.570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.36'7,282, British Patent Tube 2.10
2.173 etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include, for example, the aforementioned RD176.
Patent described in 43.4-1, JP-A-57-151
No. 944, No. 57-154234, No. 60-1842
No. 48, US Pat. No. 4,248,962 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2, 097.14.
No. 0, No. 2.131, No. 188, JP-A-59-15
Those described in No. 7638 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include, for example, the competitive couplers described in U.S. Pat. No. 4,130,427, and U.S. Pat.
No. 4,338.393, No. 4,310.61
Multi-equivalent coupler described in No. 8 etc., JP-A-60-1859
50, DIR redox compound or DIR coupler releasing coupler or D described in JP-A-62-24252 etc.
IR couplers emitting couplers or redox, couplers which release dyes that fade after separation as described in EP 173.302 A, such as R, D, Nα 11449
, 24241, and the bleach accelerator-releasing couplers described in JP-A-61-201247, e.g., U.S. Pat. No. 4,55
Examples include the ligand-releasing couplers described in No. 3.477.

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.

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., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). ), esters of phosphoric or phosphonic acids (e.g. triphenol phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (e.g. 2-ethylhexyl phosphate), ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone),
Alcohols or phenols M (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 (
For example, N,N-dibutyl-2-butoxy-5-ter
t-octylaniline), hydrocarbons (e.g. paraffin, dodecylbenzene, diisopropylnaphthalene)
Examples include. In addition, as an auxiliary solvent, the boiling point is approximately 3
An organic solvent having a temperature of 0°C or more, preferably 50°C or more and about 160°C or less can be used, and typical examples include ethyl acetate, methyl acetate, ethyl propionate, methyl ethyl ketone cyclohexanone, 2-ethoxyethyl acetate, and dimethyl formamide. It will be done.

Specific examples of the latex dispersion process, effects, and latex for impregnation include U.S. Pat. It is described in.

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

When the present invention is used in color photographic materials, it can be applied to photosensitive materials with various configurations and photosensitive materials in which layer configurations and special color materials are combined.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 50-21248, JP 59-38147, JP 59-60437
No., JP-A-60=227256, JP-A-61-404
No. 3, JP-A-61-43743, JP-A-61-426
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, such as No. 57. Special Public Service 1977-
No. 15495, U.S. Patent No. 3,843,469, etc.
Form in which the color-sensitive layer is divided into two or more layers, Special Publication No. 53-3
7017, JP 53-37018, JP 51-
No. 49027, JP-A-52-143016, JP-A-5
3-97424, JP-A-53-97831, JP-A-62-200350, JP-A-59-1775
Examples include those such as No. 51 which stipulates the arrangement of high-sensitivity layers and low-sensitivity layers 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. Page 28 of Nn17643 and Nα1871
6, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention is based on the above-mentioned R.D.
k17643, pages 28-29, and the same No. 18
Development processing can be carried out by the usual methods described in 651 left column to right column of 716.

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, representative examples of which are 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
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-)luenesulfonates, and the like. 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,
It is common to include development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds. In addition, as necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, and triethylenediamine (1,4-diazabicyclo[22,2]octane) may be added. constant agents, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, 1- An auxiliary developing agent such as phenyl-3-virapritone, a viscosity imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N. N'N'-
Tetramethylenephosphonic acid, ethylene diamine di(0
-Hydroxyphenylacetic acid) and their salts can be cited as representative examples.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-pyrazolidone, or aminophenols such as N-methyl-P-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than f. 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, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (II).
Compounds of polyvalent metals such as I), chromium (■), and copper (I[), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (DI or cobal) (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic 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 (nl) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (■) 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 (I[r) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

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 found in U.S. Pat. No. 3,893.
It is described in the specification in No. 858 and the like. 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 fixing agents include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most commonly used. Can be used widely. 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
our own 5ociety of
Motion Picture andTe1evi
sion Engineers Volume 64, P, 24
8-253 (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 listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial Sterilization, sterilization, and anti-mildew techniques'' and ``Encyclopedia of anti-bacterial and anti-mildew agents'' published by the Japanese Society of Antibacterial and Antifungal Agents can also be used.

The pH 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 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 30 seconds to 5 minutes at 25-40'C. A range 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 Nos. 57-8,543 and 58-14
．． All known methods described in No. 834 and No. 60-220.345 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 chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other 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.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64, No. 339, and JP-A No. 57-144, 54.
No. 7, and No. 58-115.438.

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, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved.

In addition, West German Patent No. 2.226,7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

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 European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, and the like.

Examples will be shown and explained below.

Example 1 Double twinned silver iodobromide grains with an average iodine content of 20 mol%, an average equivalent sphere diameter of 0.8μ, a grain size variation coefficient of 19%, and an average aspect ratio of 5.0 were used as seed crystals. Shelling was carried out for 30 minutes by a controlled double jet method in an aqueous gelatin solution under conditions such that the silver potential was 140 mV. The ratio of the core to the shell should be 2:2 in terms of silver content, and the composition of the halogen solution should be adjusted according to the iodine content of the shell.
The content was controlled to be from mol % to 7.5 mol %. (Prescriptions A to E shown in Table 1) Table 1 During shell formation, reduction sensitization was performed using dimethylamine borane (DMAB) and a thiosulfonic acid compound in amounts and methods shown in Table 2.

Table 2 After grain formation, the emulsion was subjected to a normal desalination washing process and then redispersed at 40° C. under conditions of pH 8.9 and pH 6.3.

Each emulsion then contained 6XIO per 11 moles of halogenide.
-'Mole of sodium thiosulfate and 2×10-'Mole of chloroauric acid were used for optimal chemical sensitization. In addition, prior to chemical sensitization, an emulsion was prepared to which a spectral sensitizing dye having the following structural formula was added.0 dyes A and B were halogenated m in the emulsion, respectively.
2.5X10-' mol, respectively, per 1 mol; 3.
0XlO-' moles were added.

The emulsion and protective layer were coated on a triacetylcellulose film support provided with an undercoat layer in the coating amounts shown in Table 3.

Table 3 (1) Emulsion layer Emulsion... Emulsion shown in Table 4 (silver 1.7 x 10-' mol/rrr) Coupler (1,5 x 10-' mol/layer) Tricresyl phosphate (1,10 g/rrf) Gelatin (2,30g/po) (2) Protective layer 2.4-dichlorotriazine-6-hydroxy-5-)
Lyazine sodium salt (0.08 g/nf) Gelatin (1.80 g/nf) These samples were exposed to light for sensitometry and subjected to the following color development process.

The concentration of the treated sample was measured using a green filter.

The results of the photographic performance obtained are shown in Table 4.

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

1. Color development... 2 minutes 45 seconds 2. Drifting
White... 6 minutes 30 seconds 3, wash with water...
・・・・・・ 3 minutes 15 seconds 4, established ・・・・・・
6 minutes 30 seconds 5, water washing 3 minutes 15 seconds 6, stability 3 minutes 15 seconds The treatment composition used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.4 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide hydroxylamine sulfate 4-(N-ethyl-N-β hydroxyethylamino)-2 Methyl-aniline sulfate water Add bleach solution ammonium bromide aqueous ammonia (28% w/w) ethylenediamine-ferric tetraacetate I.lium trihydrate glacial acetic acid water fixer solution sodium tetrapolyphosphate sodium sulfite ammonium thiosulfate (700 g/i , ) Add sodium bisulfite water to stabilize the solution 1.4g 2.4g 4.5g 160.0g 25.0nf! 30g 4m 1 2.0g 60g 175.0ml.

4.6g 11° formalin 8. (1wf water was added and 11 exposures were carried out using a regular wedge exposure at 1 second and 1/100 second.

The light source used was one whose color temperature was adjusted to 4800'K using a filter, and furthermore, a blue filter (BP N42 manufactured by Fuji Photo Film) or a yellow filter was used. Sensitivity goes from fog to 0 in optical density.
．． Comparison was made on two points. Sensitivity was expressed as relative sensitivity, with the blue sensitivity of the sample using Emulsion 1 being 100 and the negative blue sensitivity of Emulsions 2 and 3 being 100. Table 4 shows exposure time 1.
/100 second samples are shown.

For example, emulsions Nα2 and Nα9 are both emulsions that are not subjected to reduction sensitization and use dye A as the spectral sensitizing dye, so it is possible to see the influence of the surface silver iodide content when reduction sensitization is not performed. When the mol% of surface Ag I was changed from 2.5 to 7.5 mol%, both blue sensitivity and minus blue sensitivity decreased.

However, for example, the relationship between emulsions Nα5 and 12 is that they are reduction sensitized emulsions that use dye A as the spectral sensitizing dye, and when reduction sensitized, the surface Agl mol% 2
．． It is clear that the blue sensitivity corresponding to a change of 5 to 7.5 mol% and the negative blue sensitivity are on the contrary increasing.

Example 2 Chemically sensitized emulsion prepared in Example 1 1. 4. Red-sensitive, green-sensitive and blue-sensitive emulsions were prepared for No. 811 by adding the following dyes to the emulsions.

Dye group 1 (red dye) Dye group 2 (green sensitive dye) Dye group 3 (blue sensitive dye) Sensitizing dye ■ 2.2 x 10-' mol 1 mol Ag Cellulose triacetate primed with these emulsions Sample 201, which is a multilayer color light-sensitive material, was prepared by coating layers having the compositions shown below on a film support.

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

(Sample 201) 1st layer: antihalation layer black colloidal silver ... silver 0.18 gelatin ... 1.40 2nd layer;
Intermediate layer 2.5-G-pentadecylhydroquinone...0.18EX-
1... 0.07 EX-3---0,02 EX-12... 0.002 U-t... 0.06
U-2... 0.08 U-3... 0.10 HBS-1... 0.10 HBS-2... 0.02 Gelatin... 1.04 3rd
Layer (first red-glare emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, coefficient of variation regarding particle size 0.15)
...Silver 0.55 sensitizing dye■
... 6.9X10-' sensitizing dye n
... 1.8X10-' sensitizing dye■
... 3. lX10-'sensitizing dye■
... 4.0X10-'EX-2... 0.
350 HB S-1... 0.005 EX-10... 0.020 Gelatin... 1.20 4th
Layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.7μ, average aspect ratio 5.5, average thickness 0.2μ
) ... Silver 1.0 sensitizing dye I Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-2 X-3 X-10 Gelatin 5th layer (third red-sensitive emulsion layer) Silver iodobromide emulsion ■ X-3 X-4 B5-1 B5-2 Gelatin 6th layer (intermediate layer) X-5 B5-1 Gelatin 7th layer (first green emulsion layer) 5, lX10-'1.4X10-' 2 , 3 X 10- ' 3.0 10 ・ 1.63 ・ ・ ・ 0.040 ・ ・ ・ 0.020 ・ ・ ・ 0.80 Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0
．． 6μ, average aspect ratio 6.0, average thickness 0.15)
...Silver 0.40 sensitizing dye V
... 3.0X10-'sensitizing dye■
... 1.0X10-'sensitizing dye■
... 3.8X10-'EX-6...
0.260 EX-1... 0.021 EX-7... 0.030 EX-8... 0.025 HB S -1... 0.100 HBS-4... o, ot.

Gelatin...0275 No. 8
Layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0)
．． 7μ, coefficient of variation regarding particle size 0.18)
...Silver 0.80 sensitizing dye V
... 2. lX10-'sensitizing dye■
... 7.0X10-'sensitizing dye■
... 2.6X10-'X-6 X-8 -1 B5-1 B5-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver Silver 1.2 ・ 0.065 ・ 0.030 ・ 0.025 ・ 0.25 ・ 0.10 ・ 1.74 ・ Silver 0.05 ・ 0.08 ・ 0.03 ・ 0.95 11th layer (11th layer 1 blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 5.7, average thickness 0.15)
... iIO, 24 sensitizing dye ■
... 3.5X10-'EX-9...
0.85 EX-8... 0.12 HBS-1... 0.28 Gelatin... 1.28 1st
2 layers (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.8 μ, coefficient of variation regarding grain size 0°16)
...Silver 0.45 sensitizing dye■
... 2. I X 10"'EX-9・
... 0.20 EX-10--0,015 HBS-1... 0.03 Gelatin... 0.46 1st
3 layers (third blue-sensitive emulsion layer) Silver iodobromide emulsion■...Silver 0.77EX
-9・ ・ ・ 0.20 HBS-1・ ・ ・ 0.07 Gelatin ... 0.69 1st
4 layers (first protective layer) Silver iodobromide emulsion (iodide!I 1 mol%, average grain size 0.0
7μ) ...Silver 0.5U-4...
0.11 0-5 ... 0.17H
BS-1...0.90 Gelatin...1.00 1st
5 layers (second protective layer) Polymethyl acrylate particles (diameter 1.5 μm) ... 0,54
S-1...0.15 3-2...0.05
Gelatin: 0.72 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer. The structural formulas of the compounds used are shown in Table 8.

Silver iodobromide emulsion I in the fifth layer, silver iodobromide emulsion ■ in the ninth layer
, Sample 2 except that the silver iodobromide emulsion ■ in the 13th layer was changed.
Samples 202 to 204 were prepared in the same manner as 01.

These samples were exposed to light for sensitometry, and then 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. The results obtained are shown in Table 5.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities when the sensitivity of sample 201 was taken as 100.

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

Color development 3 minutes 15 seconds Bleached white 6 minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0 gl-
Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide
1.4g potassium iodide
1.3mg Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5g Add water 1.02p H10.0 Bleach solution Ethylenediaminetetraacetic acid Ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Add aqueous ammonium nitrate and H Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Ammonium thiosulfate aqueous solution (70%) Add sodium bisulfite aqueous solution and H Stable Liquid formalin (40%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add water 10.0 g 150.0 g 1, O, Og 1.02 6.0 1, Og 4.0 g 175, On/! 4.6g 1, Ol 6.6 2, On+j2 0.3g 1.0j2 As is clear from Table 5, the emulsion of the present invention has the effect of increasing sensitivity with almost no increase in fog.

Example 3 Average iodine content is 20 mol%, average equivalent sphere diameter is 0.9 μm
, by the controlled tuple jet method under conditions such that the silver potential was 140 mV in an aqueous gelatin solution using silver iodobromide double twinned grains with a particle size variation coefficient of 19% and an average aspect ratio of 5.0 as seed crystals. The shell was attached for 30 minutes. The ratio of core to shell should be 1:2 in terms of silver content, and the composition of the halogen solution should be set to 0 as the iodine content of the shell.
The content was controlled to be from mol% to 5.0 mol%.

One minute after the start of shell formation, L-ascorbic acid or L-ascorbic acid and thiosulfonic acid compound 1-2 was added. Also added as comparative reducing agents were stannous chloride and thiourea dioxide.

Table 6 summarizes the formulation contents of Emulsions 31 to 40.

The emulsion and protective layer were coated on a triacetylcellulose film support provided with an undercoat layer in the coating amounts shown in Table 7.

Table 7 (1) Emulsion layer Emulsion... Emulsion shown in Tables 8 and 9 (silver 1.7 x 10-' mol/rrf) Coupler (1,5 x 10-' mol/rrf) Tricresyl phosphate (1,10 g /B) Gelatin (2,30g/B) Protective layer 2. After formation of 4-dichlorotriazine-6-hydro particles,
The emulsion was subjected to a normal desalting water washing process and then p A g at 40"C.
8.9, pH 6.3. Each emulsion was then optimally chemically sensitized using 6 x 10'' moles of sodium thiosulfate and 2 x 10'' moles of chloroauric acid per mole of silver halide. Each of the spectral sensitizing dyes of the formula is halogenated IJ!
2.5XIO-' and 3.0X10-' per mole
An emulsion containing molar addition was prepared.

Dye A Dye B Xy-5-)Ryazine sodium salt (0.08 g/Po) Gelatin (1.80 g/Po) These samples were exposed to light for sensitometry as described below, and then subjected to the following color development process. went.

The concentration of the treated sample was measured using a green filter.

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

1. Color development... 2 minutes 45 seconds 2. Drifting
White... 6 minutes 30 seconds 3, wash with water...
・・・ 3 minutes 15 seconds 4, established ・・・ 6 minutes 3
0 seconds 5, wash with water 3 minutes 15 seconds 6, low
3 minutes and 15 seconds The processing composition used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.4g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate 2゜4g 4-(N-ethyl-N-βhydroxyethylamino)-2 Add methyl-aniline sulfate solution to bleach solution Ammonium Bromide Aqueous ammonia (28% w/w) Ethylenediamine-4 Sodium ferric acetate trihydrate Add glacial acetic acid water and fix solution Sodium tetrapolyphosphate Sodium sulfite Ammonium periosulfate (700 g/l) Add sodium bisulfite water Stabilizer Add formalin water 4.5 g 160,0 g 25.0 mj2 Table 8 shows the photographic properties of the samples which were chemically sensitized by adding spectral sensitizing dye A to emulsions 31 to 40. Exposure was performed at 1/100 second through a yellow filter. Sensitivity is fog+
Evaluation was made at a concentration of 0.2. Table 8 shows the photographic properties immediately after coating as well as the photographic properties after the sample was left in an atmosphere of 23° C. and 55% relative humidity for two months.

30g 4mf 2.0g 4.0g 1.75.0mff1 4.6g j2 8,0 m! ! 1! Table 9 shows the photographic properties of samples chemically sensitized using emulsions 31, 32, 35 and 40 in Table 6 without using any spectral sensitizing dye and with the addition of spectral sensitizing dye B. . Samples without spectral sensitizing dye were exposed through a blue filter, while samples with dye B added were exposed through a yellow filter at 1/100 seconds. Sensitivity is fog +0.2
It was evaluated at the concentration of

From Table 8, it can be seen that the emulsion reduction-sensitized using L-ascorbic acid had a surface iodine content of 2.5 mol% (
It can be seen that higher sensitivity can be achieved when the concentration is 5.7 mol% (emulsion-34) and 7.5 mol% (emulsion-40) compared to emulsion-32).

Similarly, Table 9 shows that the combination of surface iodine content and reduction sensitization using L-ascorbic acid gives favorable results. Further, from a comparison of Emulsions 39 and 40, it can be seen that a combination of L-ascorbic acid and thiosulfonic acid gives more favorable results. Emulsions 37, 38 and 4
0, reduction sensitization using L-ascorbic acid not only gives better results than those using other reducing agents, but also reduces the increase in fog and decrease in sensitivity that occur when the coated sample is aged. It can be seen that it has the favorable property of being significantly less.

Example 4 Chemically sensitized emulsion 32,35°38.4 prepared in Example 3
Red-sensitive, green-sensitive and blue-sensitive emulsions were prepared by adding a dye to 0.

Samples 301 to 30, which are multilayer color light-sensitive materials, were prepared by coating each layer with the composition shown below on a triacetate cellulose film support that was undercoated with these emulsions.
4 was produced.

(Composition of photosensitive layer) The coating amount is a number in units of g/rtf. However, for silver halide and colloidal silver, the amounts are expressed in g/g of silver, and for sensitizing dyes, the number of moles is expressed per mole of silver halide in the same layer.

1st layer: Haleyshiron prevention layer Black colloidal silver vA coating amount 0.2 Gelatin 2.2 UV-10.I UV -20.2 Cp d -10.05 Solv-10.01 So.1 v -20.01 Solv-30,08 2nd layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin xC-4 pd-2 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide Emulsion (Ag 18.5 mol%, internal high AgI type, equivalent sphere diameter 0.1 μ, coefficient of variation of equivalent sphere diameter 25%, diameter/thickness ratio 3.0) Silver coating amount Silver iodobromide emulsion (AgI 4.0 mol %, internal high Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particle) 1.0 0.03 0, 2 0.42 Gelatin xS-I xS-2 xS-3 xC -I xC-2 Silver coating amount 0.33 1,0 4.5X10-'mol 1.5X10-'mol 0.4X10-'mol 0.40 0.11 ExC-3 ExC-4 olv-1 4th layer : Second red-sensitive emulsion layer Silver iodobromide emulsion (Ag 18.5 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3. 0) Silver coating amount 0.55 0.7 3X10-' 5 mol~1x10-'0.3X10-' 0.10 0.55 0.025 0.20 0.009 0.023 0.24 Gelatin xS -1 xS-2 xS-3 ExC-L ExC-2 ExC-4 olv-1 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion 1 (Ag r 11.3 mol%, internal high Agl type, Equivalent sphere diameter 1.4μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter/thickness ratio 6.0) Silver coating amount 1.29 0,6 2X10-'0.6X10-'0.2X10-' 0.08 0.01 0.06 0.12 0.12 Gelatin xS-1 xS-2 xS-3 ExC-2 ExC-4 ExC-5 olv-1 olv-2 6th layer: Intermediate layer gelatin PD-4 olv-1 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (A, gI 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate shape 1.0 0.1 0.1 Grain, diameter/thickness ratio 3.0) Silver coating amount 0.28 Silver iodobromide emulsion (Ag 114.0 mol%, internal high AgJ type, equivalent sphere diameter 0.7μ, Coefficient of variation of equivalent sphere diameter 38%, plate-like particles, diameter/thickness ratio 2.0) Silver coating amount 0.1 Gelatin 1.2ExS-
55X10-'ExS-62X10-'ExS-71'X10"' ExM-10,50 ExM-20,10 ExM-50,03 Solv-10,2 Solv-40,03 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high iodine type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating amount 0 .47 0.35 3.5X10-'1.4X10-'0.7X10-' 0.12 0.01 0.01 0.15 0.03 Gelatin xS-5 Ex S--5 xS-7 xM- 1 xM-2 xM-3 otv-1 olv-4 9th layer: Intermediate layer gelatin 0.5 No. 101
i: Third green emulsion layer silver iodobromide emulsion ■ (Ag111.3 mol%, internal high Agl
Mold, equivalent sphere diameter 1.4 μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter/thickness ratio 6.0) Silver coating amount 1.3 Gelatin 0, 8 ExS-5 ExS-6 ExS-7 xM-3 xM-4 ExC=4 pd-5 Solv-1 11th layer: Yellow filter layer pd-3 Gelatin Solv-1 12th layer: Intermediate layer gelatin pd-2 13th layer: 1st blue emulsion layer Silver bromide emulsion (Ag 110 mol%, internal high iodine type, equivalent sphere diameter 0.7, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) μ, 2X10-'0.8X10"'0.8X10-' 0. 01 0.04 0.005 0.01 0, 2 0.05 0.5 0, 1 0.5 0, 1 Silver coating amount Silver iodobromide emulsion (Ag 14.0 mol%, internal high cord type, sphere equivalent) Diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.1 0.05 ], 0 3X10-' 0.60 0.02 0.15 Gelatin ExS-8 xY-1 xY -2 Solv-1 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Ag 119.0 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 16%, tetradecahedron Particles) Silver coating amount 0.19 0.3 2×10 0.22 Gelatin ExS-8 xY-1 Solv-1 15th layer: Intermediate layer fine grain silver iodobromide (Ag 12 mol%, uniform type 1 sphere equivalent diameter 0 .13μ) Silver coating amount Gelatin 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion m (Ag 111.3 mol%, internal height A
gI type, equivalent sphere diameter 1.4. μ8, coefficient of variation of equivalent sphere diameter 2
8%, plate-like particles, diameter/thickness ratio 6.0) Silver coating amount 1.35 0,5 1.5XIO-' 0.2 0.07 Gelatin ExS-9 xY-1 Solv-1 17th layer: 1 protective layer gelatin V-1 V-2 0,07 0,2 0°36 1.8 0,1 0°2 Solv-10,01 Solv-20,01 18th layer: 2nd protective layer fine grain silver chloride ( Equivalent sphere diameter 0.07 μ) Silver coating amount 0.36 Gelatin 0.70 Polymethyl methacrylate particles (diameter 1.5 μ) 0.2 W-10,02 H-10,4 Cpd-61,0 Sample 301 The chemical structural formulas of the compounds used in the preparation of -304 are shown in Table 0 below.

These samples were exposed to light for sensitometry, and then subjected to the following color development process.

The concentration of the treatment agent sample was measured using a red filter, a green filter, and a blue filter. The results obtained are shown in Table 10.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities, with the sensitivity of Sample 302 being 100.

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

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 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 diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-11-diphosphone 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0 g potassium bromide
1.4g potassium iodide
1.3■ Hydroxylamine sulfate 4-(N-ethyl-N-β hydroxyethylamino)-2-methylaniline sulfate Add H Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium salt odor Add ammonium chloride ammonium nitrate water and fix H Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 2.4 g 4.5 g 1.01 10.0 00, Og 10, 0 g 150, 0 g 10, 0 g 1, OR 6, 0 1,0g 4.0 Ammonium 1,000 sulfate aqueous solution (70%) Add sodium bisulfite water and add H Stabilizing liquid formalin (40%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add water In addition, 175.0 m 1 4.6 g 1.02 6.6 2, 0 m 1 0.3 g 1.02 As is clear from Table 10, the emulsion of the present invention has a high sensitivity with almost no increase in fog. It turns out that it is effective.

Samples 303 and 304 were left in an atmosphere of 23° C. and 55% relative humidity for two months, and then subjected to sensitometric exposure and color development. 303 showed a decrease in sensitivity due to increased fog in all of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer, but
304 had no change.

(Effects) Conventionally, it has been difficult to increase sensitivity by reduction sensitization with color-sensitized emulsions. The present inventor has determined that the silver iodide content on the surface is 5 to 5.
It has been found that reduction sensitization of silver halide grains with a concentration of 30 mol % can specifically increase the sensitivity in the color sensitization region. For example, if double-structured silver halide grains are not reduction sensitized during grain growth, an increase in the silver iodide content in the shell portion will instead result in a decrease in sensitivity in the color sensitized region.

Another unexpected effect is that the photographic material of the present invention is less susceptible to deterioration due to natural radiation.

Table A CHsSOzSNa CtH,So,5Na C3H,SO□5K CJ*50g5Li- CmH1ssOtsNa CmH1?5O1sNa CHs(CHt)sCHCF! zSOzS-NH4C!
H.

CtoHt+5O1SNa C+JzsSOtSNa C+6Hs:+5OxSNat C4Fl*5O2SNa C1130CHtCHzSO,S -NaCHt =
CHCHtso zsNaKSSO! (CH2) z
sOzsKNaSSOz (CHz) 4sOzsNa
NaSSO2 (CHz) 4S (C)Iz) 4sO
zsNaSO2SNa:5Ug5Na CJsSOzS CL C81 (17SO□5CIhCIk CZH5SO□5CHzCHzCN CZ) I, SO2SC1, CHICl, CH20HCJ
sSOtSSSOzCJs (n)C+HwSOzSSSOzC3Ht(n)X: y=2/H molar ratio) CJsSOtSCHzCHzSOzC)lzc)lzs
sO□CJs Table U-, 1 H X-4 X-5 H x : y=7 : (Weight ratio) X-1 X-2 (i) CJqOCONH .

EX-11 EX-12 HBS-1 Tricresyl phosphate Table B5-2 Dibutyl phthalate UV -] B5-3 Bis(2-ethylhexyl) phthalate B5-4 CHz=C[-5Oz CHzCONHCutUV~
2 CH,=CB-3O□-CH2=CONH=CH2 Sensitizing dye ■ C1) CaHqOCOCNH (i) C,H,0COCNH OCHz CHz S CHCOOH (n) CIz H1s OCH,CH,5CHCOOH C1! H25 CH2 ■ xC-4 Shit ExM-4 ExS-2 ExS-3 ExS-5 Shi! ExS-1 ExS-6 ExS-7 ExS-8 ExS-9 Solv-1 Solv-2 Solv-3 COOC+zHzs pd-4 H+1(n) p d-5 pd-6 Solv-4 pd-2 pd-3 Old

Claims (6)

[Claims] (1) Silver iodide with a grain surface of 5 mol% or more that has been reduction sensitized during grain growth and has been subjected to at least one of gold sensitization, sulfur sensitization, or noble metal sensitization in an arbitrary step. 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains on a support. (2) The claim (
1) The silver halide photographic material described above. [I] R-SO_2S-M [II] R-SO_2S-R^1 [III] RSO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different, It 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. Further, when possible, R, R^1, R^2, and L may be bonded to each other to form a ring. (3) The silver halide photographic material according to claim (1), which contains silver halide grains which have been reduction sensitized and then gold/sulfur sensitized. (4) The silver halide photographic material according to claim (1), which is reduction sensitized with at least one of ascorbic acid or its derivatives. (5) Silver halide grains are 5x per mole of silver halide
4. The silver halide photographic material according to claim 4, wherein the silver halide photographic material is subjected to reduction sensitization with 10^-^5 mol to 1 x 10^-^1 mol of ascorbic acid or a derivative thereof. (6) The silver halide photographic material according to claim (4), which has been subjected to reduction sensitization in the presence of at least one compound represented by the general formula [I], [II] 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.