JPH02168247A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve preservation stability of a silver halide photographic sensitive material by forming on a base body an emulsion layer contg. silver halide particles which have been reduction-sensitized with ascorbic acid or a deriv. thereof, and contg. also an N-contg. heterocyclic compd. having a specified mercapto group in the emulsion layer. CONSTITUTION:The silver halide photographic sensitive material has on a base body an emulsion layer contg. silver halide particles which have been reduction-sensitized with ascorbic acid or a deriv. thereof, and contg. also an N-contg. compd. having a mercapto group, expressed by, for example, the formula I, wherein Z is a group of nonmetal atoms necessary for forming an N-contg. heterocyclic ring; M is an H atom, alkali metal atom, quaternary ammonium group, or quaternary phosphonium group. Preferred amt. of the N-contg. heterocyclic compd. having the mercato group, to be added is 10<-6>-10<-2> mole per 1 mole silver halide. Thus, the preservation stability of the silver halide photographic sensitive material is improved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a color silver halide photograph with high sensitivity, little fogging, and excellent storage stability. Regarding photosensitive materials.

[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, (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 of silver halide grains increases the number of photons absorbed by one grain, but deteriorates the grain shape. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel type development such as color development, graininess immediately deteriorates.

In order to increase sensitivity without deteriorating graininess, it is most preferable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity.To increase quantum sensitivity, recombination, latent image dispersion, etc. It is necessary to eliminate as many inefficient processes 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. 2.48
7.1150, a polyamine compound in Lowe et al. No. 2.512.925, and a thiourea dioxide-based compound in British Patent No. 789.823 by Fallens et al. It was disclosed that it is useful as a reducing aggravating agent. In addition, Co11ier (Korea) uses Photograp
hic 5science and engineering
g, Vol. 23, p. 113 (1979), compares the properties of silver nuclei produced by various reduction sensitization methods. She used dimethylamine borane, stannous chloride, hydrazine, high pH aging, and low IJAg aging. The method of reduction sensitization is further described in U.S. Patent No. 2,518.69.
No. 8, No. 3,201,254, No. 3.411,9
No. 17, No. 3.779.777, No. 3.930.
It is also disclosed in No. 867. Special Publication No. 57-3357 regarding not only the selection of reduction exacerbators but also the improvement of reduction sensitization methods.
No. 2, No. 584410.

Among them, conventionally known reduction aggravating agents are listed, and ascorbic acid is mentioned among them. However, compounds such as thiourea dioxide are preferred, and the one shown in the examples is thiourea dioxide, 11? Sei,
It is hydrazine. Therefore, favorable properties of ascorbic acid compounds as reduction sensitizers have not actually been discovered.

Furthermore, the method of use is disclosed in JP-A-57-179835. Furthermore, regarding techniques for improving the storage stability of reduction-sensitized emulsions, JP-A-57-82831 and JP-A-601
Although it is disclosed in No. 78445, it has not reached a sufficient level of improvement.

Despite many studies as described above, the increase in sensitivity has not been sufficient compared to hydrogen sensitization in which photosensitive materials are treated with hydrogen gas under vacuum. This is Journa
It is reported by Molsar et al. in Imaging 5science, Vol. 29, p. 233 (1985).

[Problem that the invention seeks to solve]

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. Furthermore, emulsions produced using such sensitization techniques had the disadvantage of poor storage stability.

[Purpose of the invention]

The first object of the present invention is to provide a silver halide photographic material that has high sensitivity, good graininess, little fog, and good storage stability. A second object is to provide a color photosensitive material with high sensitivity, little fogging, and good storage stability.

(Means for Solving the Problems) The objects of the present invention have been achieved by the silver halide photographic materials described in (1) to 4) below.

(1) At least one ascorbic acid or its derivative
Contains silver halide grains reduction sensitized by seeds,
A silver halide photographic light-sensitive material, further comprising an emulsion layer containing a nitrogen-containing heterocyclic compound having a mercapto group on a support.

(2) The silver halide photographic material described in (1) above, wherein the nitrogen-containing heterocyclic compound having a mercapto group is represented by the following formula (1).

In the formula, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and M represents a hydrogen atom, an alkali metal, quaternary ammonium, or quaternary phosphonium.

(3) Formula (1) is expressed by the following formula (U) above (2
) silver halide photographic materials.

where R1 is at least one -COOM or -3O,
It represents an aliphatic group, aromatic group or heterocyclic group substituted with M, and M has the same meaning as in 2(1).

(4) R' is at least one -COOM or -3Oj
The silver halide photographic material according to (3) above, in which M has a 1110 phenyl group.

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, desalination chemical sensitization, and coating. Formation of silver halide grains is further divided into nucleation, physical ripening, growth, etc. These steps are not performed uniformly; the order of the steps may be reversed, or the steps may be repeated.

In principle, reduction sensitization can be carried out at any step in the production process of silver halide emulsions. That is, 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 before, after, or simultaneously with sulfur sensitization, selenium sensitization, or gold sensitization. Good too.

In the present invention, it is preferable to carry out the sensitization before or simultaneously with sulfur sensitization, selenium sensitization, or gold sensitization.

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

(^-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-
3) Potassium L-ascorbate (A-4)
D L-Ascorbic acid (A-5) Sodium D-Ascorbate (^-6) L-Ascorbic acid-6-acetate (8-7) L-Ascorbic acid-6-palmitate (A-8) L-Ascorbic acid -6-benzoate (A-9) L-ascorbic acid-6-diacetate (A-10) L-ascorbic acid-5,6-0-isopropylidene The above ascorbic acid compound is added to the silver halide emulsion of the present invention. In order to add them during the manufacturing process, they may be directly dispersed in the emulsion, or they may be dissolved in a single or mixed solvent of water, methanol, ethanol, etc. and added during the manufacturing process.

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 ions.''
Not to exceed 0-"ff1 per milliliter (8xto" moles/A g X moles). Amount of 0.1 to 10 μ per kg of silver nitrate (to-' to 10-S mol/kg as ascorbic acid)
A g X moles) are 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 1X10-'~44X1
0-'mol'.

Furthermore, in JP-A-57-179835, it is appropriate to use about 0.01 mg to about 2 cm of thiourea dioxide and about 0.01 mg to about 3 cm of stannous chloride per mole of silver halide. It is stated that there is. The ascorbic acid compound used in the present invention depends on the emulsion grain size, halogen composition, emulsion preparation temperature, and pH.

The preferred amount to be added depends on factors such as PAg, but it is 5 x 10-' mol to I
It is desirable to select from the range of 1 O-' moles.

More preferably, it is selected from the range of 5X10-'mol-1xto-''mol, particularly preferably lX
It is selected from the range of 10-' mol to 1 x 10-'' mol.

In some cases, it is more preferable to combine the reduction sensitization method using the ascorbic acid compound of the present invention with other reduction sensitization methods.&11 A method for combining is adding a known reducing agent to the silver halide emulsion. The method, called silver ripening, is grown in a low PAg atmosphere with a pAg of 1 to 7.
Alternatively, there is a method of aging, called high pH aging.
Either a method of growing in an atmosphere with a high pH of 8 to 11 or a method of aging can be selected.

The method of adding a reduction enhancer is a preferred method in that the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, 1m salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, etc. are known.

In the present invention, the nitrogen-containing heterocyclic compound having a mercapto group may be added at any step of the silver halide emulsion production process, for example, during nucleation at the initial stage of grain formation, during physical ripening, or during growth. It may be added before or after chemical sensitization, and it may be added immediately before coating. Additions in the coating process are generally expressed by formula (I) or formula ( When the compound represented by n) is diffusive, it can be added to the same layer as the emulsion of the present invention, or added to another layer that is coated in multiple layers that has water permeability. However, the object of the present invention can be achieved.

The amount of the nitrogen-containing heterocyclic compound having a mercapto group to be added must be appropriately selected, but is preferably in the range of 10-'' to 10-'' mol per mol of silver halide.

Further, in the present invention, as the nitrogen-containing heterocyclic compound, a compound represented by the general formula (1) described below is preferable, a compound represented by the general formula (II) is particularly preferable, and a compound represented by the general formula (III) is more preferable. More preferred are the compounds shown.

In the general formula (1), Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and M represents a hydrogen atom, an alkali metal, quaternary ammonium, or quaternary phosphonium.

In the general formula, R1 is at least one -COO
It represents an aliphatic group, aromatic group or heterocyclic group substituted with M or -30,M, and M has the same meaning as in formula (!).

Hereinafter, the nitrogen-containing heterocyclic compounds represented by the general formulas (1) and (II) used in the present invention will be explained in detail.

Specifically, the aliphatic group represented by R1 in the general formula (n) is a linear or branched alkyl group having 1 to 20 carbon atoms (
Examples of aromatic groups include methyl, propyl, hexyl, dodecyl, isopropyl), cycloalkyl groups having 1 to 20 carbon atoms (e.g. cyclopropyl, cyclohexyl), and aromatic groups such as aryl groups having 6 to 20 carbon atoms (e.g. phenyl). , naphthyl), and the heterocyclic group specifically includes 5 containing one or more nitrogen, oxygen or sulfur atoms, etc.
A membered ring, a 6-membered ring, or a 7-membered heterocycle (e.g., morpholino, piperidino, pyridine), which further forms a fused ring at an appropriate position (e.g., a quinoline ring, a pyrimidine ring, an isoquinolinyl, ring).

In addition, the above-mentioned linear or branched alkyl group, cycloalkyl group, aryl group, and hetero Ig may have a substituent in addition to -COOM, -3o, and M. Specifically, these substituents include is a halogen atom (F, C
1,Br), alkyl groups (e.g. methyl, ethyl), aryl groups (e.g. tI, -!phenyl, P-chlorophenyl), alkoxy groups (e.g. methoxy, methoxyethoxy), aryloxy groups (e.g. phenoxy), sulfonyl & (e.g., methanesulfonyl, p-toluenesulfonyl), sulfonamide group (e.g., methanesulfonamide, benzenesulfonamide), sulfamoyl group (e.g., diethylsulfamoyl, unsubstituted sulfamoyl), carbamoyl group (e.g., fig<' fl iQ
carbamoyl, diethylcarbamoyl), amide groups (e.g. acetamide, benzamide), ureido groups (e.g. methylureido, phenylureido), alkoxycarbonylamino groups (e.g. methoxycarbonylamino)
, aryloxycarbonylamino group (e.g. phenoxycarbonylamino), alkoxycarbonyl group (e.g. methoxycarbonyl), aryloxycarbonyl group (e.g. phenoxycarbonyl), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (
Examples include unsubstituted amino, dimethylamino), alkylsulfinyl groups (e.g. methoxysulfinyl), arylsulfinyl groups (e.g. phenylsulfinyl), alkylthio groups (e.g. methylthio), and arylthio groups (e.g. phenylthio), and their substitution Two or more groups may be substituted, and the substituents may be the same or different.

-II Among the nitrogen-containing heterocyclic compounds represented by the formulas (1) and (If), particularly preferred are the nitrogen-containing heterocyclic compounds represented by the general formula (III).
) can be mentioned.

z R1 in the general formula (III) represents a phenyl group substituted with at least one C00M or -3O,M, and this phenyl group is further substituted with another substituent other than -COOM or -3O,M. Specific examples of other substituents that may be used include the same substituents as the linear or branched alkyl group, cycloalkyl group, aryl group, and heterocyclic group represented by R1.

Here, when there are two or more -COOM and -303M, they may be the same or different. M means the same thing as represented by the general formula (II).

Preferred specific examples of the nitrogen-containing heterocyclic compound having a mercapto group used in the present invention are listed in Table A below.

However, the present invention is not limited to these specific examples.

As is generally well known, the above compound can be easily synthesized by using a reaction between isothiocyanate and sodium azide. below,
For reference, literature and patents related to these synthesis methods are listed.

U.S. Patent No. 3,266.897, Japanese Patent Publication No. 42-2184
No. 2, JP 56-111, 11146, British Patent No. 1,275,701, D, A.

Berges et al., Journal of
Heterocyclink Chemise I. Lee (Journal
oflleterocyclic e! +emist
ry) Volume 15, Page 981 (197B'), I
l, G, Dubenko, V, D.

Panchenko (author)
Khimiia Geterotsiklichesk
ikh 5 oedinenii) ``First river, (eight zo
ne oder Jhaschie GateroLs
ikly.

(1967, pp. 199-201).

This compound may be added to the emulsion in accordance with the usual method for adding photographic emulsion additives. For example, methyl alcohol,
It can be dissolved in ethyl alcohol, methyl cellosolve, acetone, water, or a mixed solvent thereof and added as a solution.

The use of the above compounds 2N) in the photographic field is already known. For example, JP-A No. 62-89952 discloses a combination of a nitrogen-containing heteroartic ring compound having a mercapto group and cyanine coloration, thereby achieving prevention of fog and high sensitivity. However, it was completely unexpected that these techniques could improve the storage stability of silver halide photographic materials reduction-sensitized by the ascorbic acid compound of the present invention.

In the reduction sensitization of the present invention, at least one compound selected from compounds represented by general formulas (IV), (V), and (Vl) may be added during the manufacturing process of the silver halide emulsion. preferable.

(IV) R5ChS M (V) R-3O,SR' (Vl) RSo! S LITI 5SOz
In the formula R'', R, R', and R'' may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, m is 0 or l
It is.

To explain the compounds of general formulas (IV), (V) and (Vl) in more detail, when R, R' and R2 are aliphatic groups, preferably an alkyl group having 1 to 22 carbon atoms, and 2 carbon atoms. These are 22 alkenyl groups and alkynyl groups, which may have a substituent. Examples of the alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, Examples include 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. These may be substituted.

The heterocyclic group of R, R1 and R1 includes nitrogen, oxygen,
A 3- to 15-membered ring containing at least one element selected from sulfur, selenium, and tellurium, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, and selenazole. , benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole,
Examples include oxadiazole and thiadeazole.

Examples of substituents for R, R' and R1 include alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (
For example, methoxy, ethoxy, octyl), aryl groups (
(e.g. phenyl, naphthyl, 1-lyl), hydroxyl group, halogen atom (e.g. fluorine, chlorine, bromine, iodine, etc.)
, aryloxy groups (e.g. pheno; tosi), alkylthio groups (e.g. methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl, valeryl), sulfonyl groups (e.g. methylsulfonyl, phenyl). sulfonyl),
Examples include acylamino groups (eg, acetylamino, benzamino), sulfonylamino groups (methanesulfonylamino, benzsulfonylamino), acyloxy groups (eg, acetoxy, benzoxy), carbo;tosyl groups, cyano groups, sulfo groups, amino groups, and the like.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of divalent aliphatic groups for L include +CHZ
+T (n = 1-12), -CI, -CH=
CH-CH.

-CIIC 30 〇 H□ Can be given. Examples of the divalent aromatic group for L 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.

The compound of general formula (IV) can be easily synthesized by the method described in JP-A-54-1019 and British Patent No. 972.211.

The compound represented by formula (IV), (V) or (Vl) is preferably added in an amount of lo-7 to 10-1 mol per mol of silver halide. Furthermore, lO-! from 10-b!
In particular, the amount added is preferably 10-S to 10-' mol/1 mol Ag.

In order to add the compounds represented by formulas (1) to (I[I) 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 (rV), (V) or (Vl) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization, preferably during reduction. In this method, a compound is added before or during sensitization.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes, such as those described in the Photographic Society of Japan, Basic Silver Salt Photography of the Photographic Industry (Corona Publishing), r', 163, For example, choose from 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. depending on your purpose. It can be used in

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. Furthermore, Jo
Urnal of ImagingScience30
Volume 247 Page 1 As reported in 1986 (2
(11) is a representative (bit) plane particle, (331) is a representative (hhl) plane particle, (210) is a representative particle (
hkO) plane particles and (321) planes are representative (hkl)
Planar particles also require some ingenuity in their preparation, but they can be selected and used depending on the purpose. A tetradecahedral particle in which (100) plane and (l l l) plane coexist in one particle, (100) plane and (
Particles with coexisting (110) planes or (111) planes and (1
10) Particles with coexisting surfaces, etc. Particles with two or many surfaces coexisting can also be selected and used depending on the purpose.

The grain size of 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, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

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 the photosensitive material tMi1, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer in the emulsion layer having substantially the same color sensitivity. Alternatively, it 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 Phys
ique PhotographiquePaul M
1967), 'Photographic Emulsion Chemistry' by Duffin, published by Focal Press (G, F, Duffi)
n.

Photographic [! mulsioh Ch
eraistry (Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (ν, L, Zelikma
neL al, Making and Coatin
g Pl+otograpl+ic['mulsion
, Focal Prass, 1964). In other words, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method for reacting the soluble root salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used.

It is also possible to use a method in which particles are formed under an excess of negative ions (so-called back-mixing method). As one form of the simultaneous 'tlA method, a method of keeping the PAg in the liquid phase in which silver halide is converted, ie, 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, please see Photographic Sciences
and Engineering (PhoLograpXc
5science and Engineering B)
Volume 6, pages 159-165 (19G2); Journal
Off Photographic Science (Journal
of Photographic 5science)
, 12 volumes.

pp. 242-251 (1964), U.S. Patent No. 3.655
, 394 and British Patent No. 1.413.7411.

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 Cripe, Phot.

graphy theory and practice
e (1930)).

t3t1. Gatoff, Photographic Science
and Engineering Link (Gutoff.

PhoLographic 5science and
[! ngineering), Volume 14, 248-25
7 pages (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048,
No. 4,439.520 and British Patent Section 2.112.
It can be easily prepared by the method described in No. 157 and the like. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, 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 Section 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 are JP-B No. 4313162 and JP-A No. 6
1-215540. These particles are of a core-shell type or two-ffi structure type in which the inside and surface layers of the particles have different halogen compositions, as disclosed in JP-A-60-222845 and JP-A-61-75337.

In such particles, the shape of the core portion and the overall shape including the shell may be the same or different.

Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. Further, although the core portion is a clearly regular particle, the shape of the shelled particle may be slightly distorted or irregular.

Moreover, it is not just a double structure, but also
It is possible to form a triple structure as disclosed in No. 4 or a multilayer structure of more than that, 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. 58-10852 (i, EP 19929
0A2, JP 58-24772, JP 59-16
254, etc. 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, a non-silver salt compound 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. Grains with a low silver iodide content and a high shell part may be used. Similarly, grains with a bonded structure may have a high silver iodide content in the host crystal and a relatively high silver iodide content in the bonded crystal. It may be a low particle or vice versa.

In addition, the boundaries between particles having 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 unclear boundaries. It may also be one with extremely continuous structural changes.

The silver halide emulsion used in the present invention is Er'-00967
27Bl, I! P-0064412 old etc., or D[
! -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. A shallow internal latent image type emulsion covered with a thin shell can also be used depending on the purpose.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ψ1 formation can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents can also be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor prior to addition of the daughter and halide salt; 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 the present invention, it is extremely important to perform chemical sensitization such as sulfur sensitization and gold sensitization, and significant effects have been obtained when chemical sensitization is performed. 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 for which the emulsion will be used.When chemical sensitization is embedded inside grains, it is embedded at a shallow position from the grain surface. In some cases, chemical sensitization may occur on the surface.

Although the effects of the present invention are also effective, particularly preferred is the case where chemical sensitization is created near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Chemical sensitization was performed by James (T, Il, Jau+e
The Photographic Process, 4th edition, published by Macmillan, 1977, (T, HoJame
s, The Theory of the Photo
graphic Process, 4th e
d.

Maem fan, 1977), pages 67-76, and can also be carried out using activated gelatin, as described in Research Disclosure, vol. 120, 19.
April 1974, 1200B, Research Disclosure, Volume 34, June 1975, 13452, U.S. Patent No. 2,642,361, No. 3, 297, 446, No. 3,772,031, No. 3, No. 857.711,
No. 3,901,714, No. 4,266.018, and No. 3,904.415, and British Patent Nos. 1 and 3.
PAg5-10. as described in No. 15,755. p
) 15-8 and a temperature of 30-80°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 a gold compound and a thiocyanate compound, and in U.S. Pat.
It is carried out in the presence of a sulfur-containing compound such as a sulfur-containing compound or a hypo-, thiourea-based compound, or rhodanine-based compound.

Chemical sensitization can also be carried out in the presence of chemical sensitization aids. Chemical sensitization aids used include compounds known to suppress capri and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Patent No. 2,131.038, U.S. Pat. Chemistry”, pages 138-143.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, prucaptothiadiazoles , aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes ; Known as anti-capri agents or stabilizers such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted tA(1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.; Additionally, many compounds can be added. For example, U.S. Patent 3,95
No. 4.414, No. 3.982.947, Special Publication No. 1972-
28,660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with medium dyes and others. Dyes used include cyanine dyes, merocyanine dyes, ? U cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxaprine nucleus, thiozoline nucleus, virol 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, i.e., an indolenine nucleus, a benzindolenine nucleus,
indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, nara-1-thiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include pyrazolin-5-one, thiohydantoin, and 2-thioxapridine-2 as nuclei having a ketomethylene structure.
, 4-dione 11, thiasolysine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid (5-6
The shellfish's heterosegmental ring nucleus can be passed through.

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. No. 2,688.545 and U.S. Pat.
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. 3,066.
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. 3,837,8 (i.
No. 2, No. 4.02 (i, No. 707, British Patent No. 1,344)
, No. 281, No. 1.507,803, Special Publication No. 43-4
No. 936, No. 53-12.375, JP-A No. 52-11
No. 0.618 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 that has been known to be useful.
This is most commonly done after the chemical exacerbation is complete and before application, but it is possible to use chemical sensitizers as described in U.S. Pat. Spectral sensitization can be carried out simultaneously with chemical sensitization by adding at the same time, or it can be carried out prior to chemical sensitization as described in JP-A-58113.928. It is also possible to start the spectral sensitization by adding it before the completion of the formation. Furthermore, U.S. Patent No. 4.22
Adding these said compounds separately as taught in No. 5,666, i.e., some of these compounds are added prior to chemical sensitization and the remainder is added after chemical sensitization. is also possible, as described in U.S. Pat. No. 4,183,756.
at any time during the formation of silver halide grains including the method taught in No.

The amount added is 4 x 10-" to 8 per mole of silver halide.
X10-' moles can be used, but for a more preferred silver halide grain size of 0.2 to 1.2 .mu.m, about 5XIO-' to 2X10-" moles are more effective.

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

These additives are described in more detail in Research Disclosure 1 tem 17643 (December 1978) and I Lem 18716 (November 1979), and the relevant sections are summarized in the table below.

Additive type 1 Chemical sensitizer 2 Sensitivity enhancer 4 Brightener Anti-stain agent Dye image stabilizer Hardener binder Plasticizer, lubricant RD1?643 Page 23 Page 24 Page 25 Page right column 25 Page 26 Page 26 Page 27 Page RD1B716 Page 648 Right column Same as above Page 650 Between left and right 1 Page 651 Left column Same as above Page 650 Right column Various color couplers can be used in the present invention.
-(RD) Nal 7643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26.024, No. 4. Preferred are those described in Japanese Patent Publication No. 101,752, Japanese Patent Publication No. 5B-10739, British Patent No. 1,425,020, British Patent No. 1,476.760, and the like.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, such as U.S. Pat.
．． 310.619, 4,351.1397, European Patent No. 73,636, U.S. Patent No. 3,061,43
No. 2, No. 3,725,067, Research Disclosure Nα24220 (June 1984), JP-A-6033552, Research Disclosure N
o.

24230 (June 1984), JP-A-60-436
59, U.S. Patent No. 4,500.630, U.S. Patent No. 4.5
Particularly preferred are those described in No. 40,654.

As cyan couplers, phenolic and NAF!・−
U.S. Patent No. 4.052, 21
No. 2, LL No. 46.396, No. 4,228, 2
No. 33, No. 4,296,200, No. 2,369°929, No. 2.801,171, No. 2,772
．． No. 162, No. 2,895.826, No. 3,77
2.002, 3.758,308, 4.3
No. 34.011, No. 4,327.173, West German Patent Publication No. 3,329,729, European Patent No. 121,36
5A, U.S. Patent No. 3.446.62'2, U.S. Patent No. 4.
No. 333,999, No. 4.451.559, No. 4
, 427,767 and European Patent No. 161.626A are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes include, for example, Research Disclosure Na176.
Section 43 ■-G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,92
No. 9, No. 4.138.258, British Patent No. 1.14
6,368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include, for example, U.S. Patent No. 4,366.237 and British Patent No. 2.
125.570, European Patent No. 96,570, and West German Patent Publication No. 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. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2.097,14.
No. 0, No. 2.131.188, JP-A-59-157
Those described in No. 63111 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, etc., and U.S. Pat.
No. 4, 33fl, 393, No. 4.31
Multi-equivalent couplers described in No. 0,618 etc., JP-A-60-
185950, D described in JP-A No. 62-24252, etc.
IR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redoxes, couplers which release dyes that recolor after separation as described in EP 173,302A, such as R, D, No.
11449, 24241, JP-A-61-2012
For example, the bleach accelerator releasing couplers described in US Pat. No. 4,553,477 and the like are mentioned.

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'
Specific examples of high boiling point solvents of C or higher include phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate-1
), esters of phosphoric or phosphonic acids (e.g.
Trifel phosphate-1~, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (e.g. 2-ethylhexyl benzoate, dodecyl benzoate) ,2
-ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecanamide,
N,N-diethyl laurylamide, N-tetradecylpyrrolidone), alcohols or phenols (e.g. instearyl alcohol, 2,4-di-tert-
amylphenol), aliphatic carboxylic acid esters (e.g., bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate), aniline derivatives (e.g., N,N-dibutyl -2-butoxy-5-tert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or more, preferably 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 process and effects of latex dispersion and specific examples of latex for impregnation are described in US Pat. No. 4.1!39,363 and West German Patent No. 1! It is described in IJI (OLS) No. 2,541,274 and IJI (OLS) No. 2.541.230.

The present invention can be applied to various color photosensitive materials. -Most used or 1! ! Color negative film for IT pictures, color reversal film for slides or television,
Typical examples include 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 59-38147, JP 59-60437,
JP-A-60-227256, JP-A-61-4043, JP-A-61-43743, JP-A-61-42 (i5
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, such as No. 7. Special Public Service 1977-1
No. 5495, U.S. Pat. No. 3,843,469, in which the color-sensitive layer is divided into 2N or more layers, Japanese Patent Publication No. 1983-37
No. 017, Japanese Patent Publication No. 53-37018, Japanese Patent Publication No. 5149
No. 027, JP-A-52-143016, JP-A-53-
No. 97424, JP-A-53-97831, JP-A-62
Examples include those in which the arrangement of high-sensitivity layers and low-sensitivity layers and the arrangement of layers with different color sensitivities are stipulated, such as No. 200350 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 Na17643, and the same N (L1871
6, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD, N
α17643, pages 28-29, and Nα1B716
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
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pHL additives such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercap 1-compounds. It also generally contains an antifoggant or the like. Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sulfur M [hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]
various preservatives such as octane), ethylene glycol,
Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers such as sodium boron hydride, race agents, 1-phenyl-3- Auxiliary developing agents such as birapritone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,l-diphosphonic acid, nitrilo-N,N,N-1 rimethylenephosphonic acid, ethylenediamine-N,N,N''
Representative examples include N'-tetramethylenephosphonic acid, ethylene glycol (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-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 being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
mj! You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

After color 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, or in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. 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
II), compounds of polyvalent metals such as chromium (V+) and ili (■), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(n[) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. Complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (I[l) complex salts is usually 5.5 to B, but in order to speed up the processing, it is possible to use an even lower p I-1. It can also be processed with

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858 and elsewhere. Additionally, U.S. Pat. No. 4,552.
Compounds described in No. 834 are also preferred. 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 Te1evi-s
ion [! ngineers Volume 64, P, 24
It can be determined by the method described in B-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. 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 JP-A No. 61131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium incyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Sterilization of microorganisms" edited by Sanitation Technology Association , "Bactericidal and Antifungal Techniques" and "Encyclopedia of Antibacterial and Antifungal 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 be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but in general, it is 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds to 5 minutes at 25-40°C. 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 5B-1
All known methods described in No. 4,834 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. .

It is also possible to add various botanical agents and antifungal agents 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
- Pyrazolidone material may be incorporated. Typical compounds are disclosed in JP-A No. 5 (I-64, No. 339, No. 57-144, 54).
No. 7, and No. 5B-115,438.

Various processing liquids in the present invention are used at temperatures ranging from to'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. 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 US Patent No. 4.
The present invention can also be applied to heat-developable photosensitive materials such as those described in JP-A No. 500,626, JP-A No. 1-133449, JP-A No. 59218443, JP-A No. 61-238056, and European Patent No. 210.660A2.

Examples will be described in detail below, but the present invention is not limited thereto.

Example 1 Average iodine content is 20 mol%, average equivalent sphere diameter is 0.8 μm
Using double twinned silver iodobromide grains as seed crystals in a gelatin aqueous solution using a controlled double jet method, the average equivalent sphere diameter is 1 such that the core-shell ratio is 1 = 2 and the iodine content of the shell is 4 mol%. An emulsion consisting of twinned silver iodobromide grains of .2 μm was formed.

After grain formation, the emulsion is subjected to a normal desalting water washing process and then heated to 40°C.
T: Redispersed under the conditions of pA g 8.9 and pH 6.1. The emulsion thus produced was named Em-A.

60 using Em-A with sodium thiosulfate and chloroauric acid.
The emulsion optimally sensitized with gold and sulfur at a temperature of ゛C was designated as Eml.

Next, gold/sulfur sensitization was carried out in the same manner as Ern1, and after completion of the gold/sulfur sensitization, a nitrogen-containing heterocyclic compound containing a mercapto group (
An emulsion was prepared in which 1X10-' mol and 1×1 O-S mol of 1) were added per mol of silver, and 2 m2. Em3
And so.

Further, sodium thiosulfate, chloroauric acid, and ascorbic acid compound A-1 were added to Em-A to prepare emulsions that were subjected to gold/sulfur sensitization and reduction sensitization, and these were designated as Em4-6.

In addition, gold/sulfur sensitization and reduction sensitization were performed in the same manner as Em4 to Em 6, and at the end of reduction sensitization, mercapto group-containing nitrogen-containing heterocyclic compound (1) was added at 1xto' mol per mol of silver.
Em7-12 was prepared by adding 1X10-S mol.

Em13 to 36 shown in Table 1-11 and Table 1-2 were prepared in the same manner as Em 4 to 12 by changing the types of the ascorbic acid compound and the nitrogen-containing heterocyclic compound having a mercapto group. However, for Em31 to Em36, the nitrogen-containing heterocyclic compound having mercap 115 was added prior to the start of chemical sensitization.

The emulsion and the preservative piJ layer were coated on a triacetylcellulose film support provided with an undercoat layer in the coating amounts shown in Table 1-3.

Table 1-3 (1) Emulsion layer/emulsion: Emulsions Eml to Em36 shown in Tables ti to 2
(Silver 1.7 x 10-' mol/e) coupler
(1,5Xl0-”mol/bo)tricresyl phosphate (1,1Og/nf) Gelatin (2,30g/nf) Protective layer 2.4-dichlorotriazine-6-hydroxy-5-triazine sodium salt (0 , 08g/a) Gelatin (1.80g/po) 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 Tables 1-1 and 1-2.

The results were based on the fog value and sensitivity value of Eml's fresh performance (immediately after sample preparation). The same sample was also
It was stored at 0'C and 30% RH for 3 days, exposed and developed in the same manner, and the fog and sensitivity were determined and are shown in Tables 1-1 and 1-2.

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 composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate Sodium sulfite Sodium carbonate Potassium bromide Hydroxylamine sulfate 4-(N-ethyl-N-βhydroxyethylamino)-2 Add methyl-aniline sulfate water and turn it white (! [Ammonium bromide aqueous ammonia (28%) Ethylenediamine-sodium tetraacetate Add glacial acetic acid water to fix fixing solution Sodium tetrapolyphosphate Sodium sulfite 1.4 g 4.0 g 30.0 g 1.4 g 2.4 g 4.5 g 160.0g 25.0 m 1! mI! 2.0 g 4.0 g Ammonium thiosulfate (70%) 175.0 mjl!
Add 4.6 g of sodium bisulfite water 12 Add 8.0 ml of stabilized formalin water 142 Exposure is 1/1
A normal wedge exposure was performed at 00 seconds.

A light source whose color temperature was adjusted to 4800° using a filter was used, and a blue filter (BPN42 manufactured by Fuji Photo Film) was used to extract blue light. Sensitivity was compared based on fog and optical density, which was +0.2.

As is clear from Tables 1-1 and 1-2, the emulsions of the present invention have suppressed fog, high sensitivity, and excellent storage stability.

Example 2 The following dyes were added to the chemically enhanced emulsion prepared in Example 1 as shown in Table 2-1 to prepare a spectrally sensitized emulsion.

The emulsion thus prepared was coated in the same manner as in Example 1, and sensitometry experiments were conducted.

■ ■ Ct II s Word C! II 5 Dye group 1 (red-sensing dye) Dye group 2 (green-sensing dye) Dye group 3 (blue-sensing dye) Sensitizing dye The emulsion with the addition of a blue-sensitive dye was exposed using a yellow filter (5C-52 manufactured by Fuji Photo Film ■) instead of the blue filter of Example 1, and the emulsion with the addition of a blue-sensitive dye was exposed without using the above filter. did. Other conditions are the same as in Example 1. Table 2-1
1 of each of sample No. -201, -202, -203.
/100 second exposure sensitivity as 100, relative sensitivity at tε, sample Nα204 to 206.207 to 20
9.210-212.213-215, and 21
It exhibits a sensitivity of 6 to 218.

The same sample was stored at 60 DEG C. and 30% RH for 3 days, exposed and developed in the same manner, and the fog and sensitivity were determined and are shown in Table 2-1.

As is clear from Table 2-1, the emulsions of the present invention have suppressed fog, high sensitivity, and excellent storage stability.

Example 3 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color photosensitive material, was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/rrf units, and for silver halide, it indicates the coating amount in terms of silver.However, for sensitizing dyes, the halogen in the same layer The coating amount per mole of silveride is shown in moles. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

U: Ultraviolet absorber, HBS i high boiling point organic solvent, EX:
Coupler, S: Additive (Sample 301) 1st layer; antihalation layer black colloidal silver gelatin 2nd layer; intermediate layer 2.5-di-L-pentadecylhydroquinone EX, -1 EX-3 EX-12 J- 1 HB S -1 B5-2 Gelatin 3rd W1 (first red-sensitive emulsion layer) Monodisperse 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 l...6.9X10-' Sensitizing dye ■...Archie, 8XIO-'0.1
8 0.07 0.02 0, OO2 0,06 0,08 0,10 0,10 0,02 1, O4 ... Silver 0.18 ... 0.40 Sensitizing dye ■ Sensitizing dye ■ EX -2 HB S -1 EX-10 Gelatin 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 0.2
u) ・-2FA 1.0 Sensitizing dye 1
...5. lX1O-'sensitizing dye■
...1.4X10-'sensitizing dye■
...2.3X10-' sensitizing dye IV
・3. OX 10-'EX-2・0
．． 400 EX-3... 0.050 EX-10/ 0.015 Gelatin River 1.30 5th layer (
Third red-sensitive emulsion layer) Silver iodobromide emulsion I...3. lX10-' ... 4.0X1 (1' ... 0.350 ... 0.005 ... 0.020 ... 1.20 ... Primate 1.60 EX-3 EX-4 HB S -1 B5-2 Gelatin 6th layer (middle layer) EX-5-0,040 HB S -1-0,020 Gelatin ... O, aO 7th layer
Layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 6. O1 average thickness 0.15
μ) ... Silver 0.40 sensitizing dye V
...3.0X10-S sensitizing dye Vl
-1,0XIO-'sensitizing dye■
...3.8X10-'EX-6-0,260 EX-1・0.021 EX-7・0.030 EX-8 River 0.025 8BS-1 River 0.100 0,240 0, l 20 0.22 0, 1 0 1.63 HBS-4 8th layer of gelatin (2nd green emulsion 1 layer... 0.010... 0.75 Monodisperse silver iodobromide emulsion (119 mol iodide) %, average particle size 0.7μ, coefficient of variation regarding particle size 0.18) Sensitizing dye V Sensitizing dye■ Sensitizing dye■ X-6 X-8 X-1 X-7 B5-1 HB S-4 Gelatin 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion ■ X-6 X-11 X-1 ...1 0.80 ・2. I '...2.6X10-' ... 0.1 80 ... 0.010 ... 0.008 ... 0.012 ... 0.1 60 ... 0.008 ... 1.1 0...tml, 2...0.065...0.030...0.025 HBS-1...0.25 HBS-2...0.10 Gelatin... 1.74 1st
0M (yellow filter layer) Yellow colloidal silver X-5 B5-3 Gelatin No. 117! (First blue emulsion J!l) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0
．． 6μ, average aspect ratio 5.7, average thickness 0.15μ
) ・・・Silver 0.24 concentrating dye■
...3.5XIO-'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... primate 0.05... 0.08 ... 0.03 ... 0.95 0, 1 6)
...S 0.45 sensitizing dye■
...2. lX10-'EX-9...
0.20 EX-10... 0.015 11 B3 S-1... 0.03 Gelatin
... 0.46 13th layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion ■ X-9 II B S -1 Gelatin 14th layer (first protective layer) Silver iodobromide emulsion (silver iodide 1 mol%, average particle size 0.07
μ )
... ill O,5U-4... 0.11 0-5 ... 0.17H
B S -1... 0.90 Gelatin... 1.00 1st
5 layers (2nd layer! i layer) Polymethyl acrylate particles... silver 0.77... 0.20... 0.07... 0.69 (diameter 1.5 tt m) = 0.
543-1 ・
...0.15S-2...0.05 Gelatin...0.72 In addition to the above-mentioned 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.

Fifth layer silver iodobromide emulsion! , 9th layer silver iodobromide emulsion ■
, Sample 302 was prepared in the same manner as Sample 301 except that the silver iodobromide emulsion (■) in the 13th layer was changed as shown in Table 3-1 (A).
~306 were produced.

These samples were exposed to sensitometric light 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. Table 3-1 shows the results obtained.
Shown in (B).

The same sample was stored at 60°C and 30% RH for 3 days, exposed and developed in the same manner, and the fog and sensitivity were determined and shown in Table 3-1.
Shown in (B).

Regarding the results of photographic performance, the sensitivity of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer was determined respectively, and the fresh sensitivity of sample 301 was set to 10.
It is expressed as a relative sensitivity when it is set to 0.

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 washing 3 minutes 15 seconds 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-1,1-diphosphonic acid 2.0g sodium sulfite 4.0g potassium carbonate
30.0 g potassium bromide
Add 1.4 g of potassium iodide hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate H Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid di Sodium salt Ammonium bromide Ammonium nitrate Add water and H Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 1,3 mg g 2.4 g 4.5 g 1.0ffi 10,0 100,0 g 10,0 g 150,0 g 10, 0 g +, OI! 6,0 1.0g 4.0g Ammonium thiosulfate 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 Of 75, 0 m 1 4.6 g 1, Of 6.6 2, 0 m 1 0.3 g 1.02 As is clear from Tables 3-1 (A) and (B), the emulsion of the present invention has a capri It can be seen that the sensitivity is suppressed, the sensitivity is high, and the storage stability is also excellent.

Example 4 Samples 301 to 306 of Example 3 were exposed in the same manner as in Example 3, and then processed by the method described below using an automatic processor.

Processing method Step Processing time Processing temperature Color development
3 minutes 15 seconds 38°C bleaching 1 minute 00 seconds 38°C bleach fixing 3 minutes 15 seconds 38°
C water washing (1) 40 seconds 35°C water washing (2
) 1 minute OO seconds 35°C Stable 40 seconds 38°C Dry 1 minute 15 seconds 55°C Next, the composition of the treatment solution is described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.01-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-Ethyl-N-(β -Hydroxyethyl]amino] -2-Methylaniline sulfate is added to H (Bleach solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Bleach accelerator 3.0 4.0 Add water (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium thiosulfate ammonium sulfite aqueous solution (70%) Aqueous ammonia (27%) Add water to pH (Washing solution) Tap water H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co., Ltd.) and OH type anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co., Ltd.), 0 m I! 6.3 (unit g) 5.0 12.0 50. 0 240, 0 m j2 6, 0 m I! 1.0! 7.2 Water was passed through a mixed bed column packed with Light I R-400) to reduce the concentration of calcium and magnesium ions to 3 m
g/L followed by 20 mg/L of sodium isocyanurate dichloride and 1.5 g of sodium sulfate.
/L was added. The pH of this solution is in the range of 6.5-7.5.

(Stabilizing liquid) (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0ffip H5,0
-8,0 Samples 304 and 306 of the present invention had good results as in Example 3 even after this treatment.

Example 5 Samples 301 to 306 of Example 5 were exposed in the same manner as in Example 3, and then processed using an automatic processor in the manner described below.

Processing method Process Processing time Color development 2 minutes 30 seconds Bleach fixing 3 minutes 00 seconds Washing with water (1) 20 seconds Washing with water (2) 20 seconds Stability 20 seconds Dry 50 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-Ethyl-N-(β- Processing temperature 40″C 40°C 35°C 35°C 35°C 65°C (Unit: g) 2,0 3.0 4.0 30.0 1,4 1,5 mg g 2.4 Hydroxyethyl)amino]-2-methyl Add aniline sulfate solution to pH (bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium thiosulfate ammonium sulfite aqueous solution (70%) Acetic acid (98%) Bleach accelerator Add water to pH [1 4,5 1,07! 10,05 (Unit: g) 50.0 5,0 12.0 260, 0 m 1 5, 0 m 1 0, Oft Le 1.02 6.0 (Washing liquid) Water supply Water is passed through a mixed-bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400) to remove calcium and Treat the magnesium ion concentration to below 3 mg/L, followed by 20 mg of sodium isocyanurate dichloride.
/L and 1.5 g/L of sodium sulfate were added.

The pH of this solution is in the range of 6.5-7.5.

(Stabilizing solution) (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-P-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0! pH5,0-[
1,0 Samples 304 and 306 of the present invention obtained good results as in Example 3 even after this treatment.

Example 6 On a subbed cellulose triacetate film support,
Sample 401, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(One composition of photosensitive layer) The coating amount was expressed in units of g/nf. However, for silver halide and colloidal silver, the amounts are expressed in g/rd small units of silver, and for sensitizing dyes, the number of moles is expressed per 1 mole of halide in the same layer.

Note that the symbols indicating additives have the meanings shown below.

However, if a substance has multiple effects, one of them is listed as a representative.

U■: Ultraviolet absorber, 5olv: High boiling point organic solvent, W:
Coating aid, H: hardening agent, Ext: sensitizing dye, ExC nitrogen coupler, ExM: Mazenk coupler, ExY
: Yellow coupler, Cpd: Additive 1st layer: Antihalation layer Black colloidal silver Silver coating amount 0.2 Gelatin
2.2U V -10, I U V -20,2 Cp d -10,05 Solv-10,01 So! v-20,01 Solv-30,08 2nd N: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1. OCp d
-20,2 3rd rri: 1st red-sensitive emulsion layer silver iodobromide emulsion (Ag 1 10.0 mol%, internal streaks Ag
L type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%,
(Tedecahedral grains) Silver coating amount 0.26 Silver iodobromide emulsion (Ag! 4.0 mol%, internal high Ag
T type, equivalent ball diameter 0.4 μ, coefficient of variation of equivalent ball diameter 22%,
Tedecahedral particles) Silver coating amount 0.2 Gelatin l・0ExS-1
4,5XIO-'mol ExS-21,5X10-'mol ExS-30,4X10-'mol ExS-40,3X10-'mol ExC-10,33 ExC-20,009 ExC-30,023 ExC-6° 0 .14 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag 116 mol%, internal streaks Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/If ratio 4.0) Silver coating amount 0.55 0.7 3XlO-'lXl0-'0.3X10-' 0, 3 X 10 Gelatin Ext-I Ext-2 Ext-3 Ext-4 Ext-4 Ex C-30, 05 ExC-40, 10 ExC-60, 08 No. 57I: Third red-sensitive emulsion layer Silver iodobromide emulsion I (inner tube Agl type, equivalent sphere diameter 1.2μ
, variation coefficient of equivalent ball diameter #31.28%) Silver coating amount 0
．． 9 Gelatin 0.6ExS-1
2X10 ExS-20,6X10-' ExS-3o, 2xto-' ExC-40,07 Ex C-50,06 Solv-10,12 Solv-20,12 6th layer: Intermediate layer gelatin l・OCp d
-40・1 Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (Ag 1 10.0 mol%, internal cylinder Ag
L type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%,
Tedecahedral grains) i-coated ffi 0.2 iodobromide emulsion (
Ag14.0 mol%, inner cylinder AgI type, equivalent sphere diameter 0.4
μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.1 Gelatin 1.2ExS-5
5X10-'ExS-62X10-'ExS-71XIO-' ExM-10,41 ExM-20,10 ExM-50,03 Solv-10,2 Solv-50,03 8th layer: 2nd green-sensitive emulsion layer Odor Silveride emulsion (Ag 110 mol%, internally high iodine type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/1 yen ratio 3.0), coated with gelatin 0.4 0.35ExS-
53,5xto-'ExS-61,4X10-'ExS-70,7X10-' ExM-10,09 ExM-30,01 S o I v -10,15 Solv-50,03 9th layer: Intermediate layer gelatin 0 .5 10th layer: 3rd green-sensitive emulsion layer silver iodobromide emulsion ■ (internal cylinder Agl type, equivalent sphere diameter 1.2μ,
Coefficient of variation of ball equivalent diameter 28%) i Amount of coating
1.0 Gelatin 0.8ExS-52
X10-' ExS-60,8X10 ExS-70,8xlO ExM-30,01 Ex M-40,04 ExC-40,005 Solv-10,2 11th layer: Yellow filter layer CPd-30,05 Gelatin 0.5Solv -1
0,1 12th layer: Intermediate layer gelatin 0.5Cp d −
20,1 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (Ag 110 mol%, internal high iodine type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver coating Amount Ool Silver iodobromide emulsion (AEI 4.0 mol%, internal high iodine type,
Equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particle) mx cloth l O,05 Gelatin 1.0ExS-83
X10 ExY-10,53 ExY-20,02 Solv-10,15 14th layer 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Ag 1 19.0 mol%, internal high Ag
L type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 16%,
Tedecahedral particles) Coating amount 0.19 Gelatin 0.3ExS-82
X10 ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain silver bromide 11 (Ag 12 mol%, uniform type, equivalent sphere diameter 0.13μ) Silver coating amount 0.2 Gelatin 0.36 16th rr
1: Third blue-sensitive emulsion layer silver iodobromide emulsion ■ (internal high Agl type, equivalent sphere diameter 1, 2μ,
Coefficient of variation of equivalent sphere diameter 28%) Silver coating amount 1.0 Gelatin x S-8 ExY-1 olv-4 17th layer: 1st protective layer Gelatin 1.8 U V -1
0,l UV-20・2 Solv-10,01 Solv-20,01 18th layer: 2nd protective layer Fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.18 Gelatin 0.7 Polymethyl Methacrylate particles (diameter 1.5μ) 0.2 W-10,02 8-10,4 Cp d -51,0 Table 0 shows the structural formulas of the compounds used.

0.5 1.5X10-4 0.2 0.07 5th rr! Table 41 (A
) Samples 402 to 406 were prepared in the same manner as sample 401 except for the following changes.

These samples were exposed to light for sensitometry and subjected to the same color development process as in Example 3.

The treated sample was measured four times using a red filter, a green filter, and a blue filter. The obtained results are shown in Table 4-1 (
It is shown in the fresh column of B).

The same sample was stored at 60°C and 30% RH for 3 days, exposed and developed in the same manner, and the fog and sensitivity were determined and shown in Table 4-1 (
It is shown in the column after storage at 60° C. 130% R for 113 days in B).

Regarding the results of photographic performance, red sensitivity layer, green sensitivity 1r! J
, the sensitivity of the blue-sensitive layer is expressed as a relative sensitivity when the fresh sensitivity of sample 401 is set to 100.

As is clear from Tables 4-1 (A) and (B), the emulsions of the present invention have low fog, high sensitivity, and excellent storage stability.

Example 7 On a subbed cellulose triacetate film support,
Sample 501, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in units of g/rrt of silver for silver halide and colloidal silver, and the amount expressed in g/rd small units for coupler additives and gelatin.
Regarding the sensitizing dye, the number of moles is expressed per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

UV, ultraviolet absorber, 5olv; high boiling point organic solvent, EX
F: Dye, EXSj multiplied dye, ExC: Cyan coupler, ExM; Magenta coupler ExY: Yellow coupler, Cpd, additive first layer (antihalation layer) Black colloidal silver...0.15 Gelatin...2. 9UV-1
...0.03 uv-2...0.06 UV-3...0.07 S o 1 v-2-0,08 ExF-1...0.01 ExF-2-0,01 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, uniform, equivalent sphere diameter 0.4
μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particle diameter/thickness ratio 3.0) Coated silver amount...0.4...0.8...2.3X10-'...1. 4X10-'...2.3X10-'...8.0X10-" ...0.17 ...0.03 ...0.13 Gelatin xS-1 xS-2 xS-5 xS-7 ExC-1 ExC-2 ExC-3 3rd layer (mid-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (A, 16 mol%, core-shell ratio 2:1
Internal height Agl: equivalent sphere diameter 0.65μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount...0.65 Silver iodobromide emulsion (Ag 14 mol%) , uniform AgI type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/J¥ ratio 3.0) Coated silver amount...0.1 Gelatin 0. Bow, 0ExS-
1-2X10 ExS-2・ 1.2X10 ExS-5-2Xl0-'ExS-7"・7Xl0-" ExC-1・0.31 ExC-2...0.01 Ex C-3-0, 06 No. 41 (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion! (Internal height Agf with core-shell ratio l:2
Type, sphere equivalent diameter 0.75μ, coefficient of variation of sphere 111 equivalent diameter 25
%) Coated primate ffi Gelatin xS-1 xS-2 xS-5 xS-7 ExC-1 ExC-4 Solv-1 Solv-2 pd-7 5th layer (middle layer) Gelatin V-4 V-5 pd-1 Polyethyl acrylic Solv-1 6th layer (low sensitivity green emulsion layer) ...0.6 ...0.03 ...0.04 ...0. Lu latex...0.08...0.05...0.9...0.8...1.6X10-'...Bow, 6X1(I'...Bow, 6X10-'' ...6 Xl0-' ...0.07 ...0.05 ...0.07 ...0.20 ...4.6 Type: ■, y equivalent diameter 0
．． 7 μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particle, diameter/
Thickness ratio 2.0) Coated silver amount...O,t.

Gelatin...0.4E x
S -3-2X 10 ExS-4...7X10-'ExS-5-IXIO-' Snake x M5...0.11E
x M -7-0,03 ExY-8-0,01 Solv-1-0,09 Solv-4...O,Ol 7th Ji (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion CAg1 4 mol%, core shell ratio 1:l
surface height AgI type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particle, diameter/1 yen ratio 4. O) Gelatin xS-3 xS-4 xS-5 xM-5 Coating i Nagaya...0.27...0
．． 6...2XIO-'...7 X 10-'...I Solv-1・=0.14 S o I v-4・=0.02 8th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion ■ (internal high Agl type with core-shell ratio l:2, equivalent to sphere) Diameter 0.75μ, coefficient of variation of equivalent sphere diameter 25%) Piratin xS-4 xS-5 xS-8 xM-5 ExM-6 xY-O ExC-I ExC-4 Solv l 5olv-'I Solv-4 pd- 7 9th layer (middle layer) Gelatin coating iml...0.7...0
．． 8...5.2xlO-'...I Xl0-'...0.3X10-'...0.1...0.03...0.02...0.02...・0601 ...0.25 ...0.06 ...0.01 ...I XIO ...0.6 Cpd-1 ...0.04 Polyethyl acrylate latex ...O, l 2S
olv-1・=0.02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag 16 mol%, core shell 1t, 21 internal high Agl type, equivalent sphere diameter 0.7μ, sphere Equivalent diameter coefficient of variation 2
5%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount...0.68 Silver iodobromide emulsion (Ag + 4 mol% uniform type, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter /Thickness ratio 3.0) Coating i Nagaya...0.19 Gelatin...1. OE x S −
3-6
2...0.13 Solv-1=0.13 Cpd-1...-0,07 Cp d'-6...0.002 H-1...0.13 12th layer (low sensitivity Blue-sensitive emulsion N) Silver iodobromide emulsion (Ag 14.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount...0.3 Silver iodobromide emulsion (Ag 13 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 30%, plate-like grains, diameter/thickness ratio 7. 0) Coating S Nagaya...
0.15 Gelatin...1.
8ExS-6-9XIO-' Ex C-1-0,06 Ex C-4-0,03 ExY-9...0.14 ExY-11...0.89 So I v-1-0 ,42 13th layer (middle layer) Gelatin...0.7E x
Y -12.=0.20 Solv-1=0.34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion tU <Internal high Ag with core-shell ratio of 1:2
L type, equivalent sphere diameter 0.75μ, coefficient of variation of equivalent sphere diameter 25%
) Coating 1 ffi...0.5 gelatin...0.5E x S
-6-= I Emulsion (Ag1 2 mol%, uniform-Agl type,
Equivalent sphere diameter 0.07μ) Coated silver amount...0.12 Gelatin...0.9UV-
4...0.11 UV-5...0.16 Solv-5-0,02 11-1...0.13 Cpd-5...0. IO Polyethyl acrylate latex...0.09 1st
6 layers (second protective layer) Fine grain silver bromide emulsion (Ag 12 mol%, uniform-Agl type, equivalent sphere diameter 0.07μ) Coating iab±...0.36 gelatin...0.55 polymethyl methacrylate One particle (diameter 1.5μ) ...0.2H-
1... 0.1 7 In addition to the above components, each layer contains an emulsion stabilizer Cpd3 (
0,07g/n () surfactant Cpd-4 (0,03g
/rrr) was added as a coating aid.

The structural formulas of the compounds used are shown in Table 1.

In Ern-1 of Example 1, the average equivalent sphere diameter of the seed crystal was set to 0.5 μm, and therefore the average equivalent sphere diameter of the final particles was 0.7 μm.
9 in the same manner as Em-1 of Example 1 except that the thickness was 5 μm.
The M emulsion is designated as Em-201.

Ern-201 was reduced sensitized in the same manner as in Example 1 using gold/sulfur enhanced comparative emulsion Em-202 and gold/sulfur sensitization plus ascorbic acid compound A-1, and further reduction sensitization was completed. Emulsion Em-203 of the present invention was prepared by adding 1XIO-S mol/mol of mercapto group-containing heterocyclic compound (1).

Then these emulsions Em-202 and Ern-20
Color-sensitized emulsions were prepared in the same manner as in Example 2, and the silver iodobromide emulsion for the fourth layer, the silver iodobromide emulsion for the eighth layer, and the silver iodobromide emulsion for the first four layers. When compared in the same way as Examples 3 and 6, similar effects of the present invention were confirmed.

(13 (11) No. table UOII No. table EX-1 EX-3 EX-4 EX-5 +J-CJ EX-11 EX-12 EX-10 CII.

B5-1 Tricresyl phosphate B5-2 Dibutyl phthalate BS Bis(2-ethylhexyl) Phthalate B5-4 Cll 2= CII SO□-CII□C0NII
-CI+□C11! ””C1l SO2CIl□-
CON+! -C1l□sensitizing dye! ■ ■ (C11ri xsOsNa C! II S C!115 Table U■ IV-2 ExC-2 ExC-3 ExC-6 ExC-4 [ExC CIZII2S ExMl ExY-1 sit xM-4 xM-5 xS-1 xS-2 E -x S -3 (C11z)2SO311N(511sJ+ExS-4 Ct II S ExS-5 ExS olv olv-5 pd-1 ExS-8 ExS olv-1 olv-2 pd-2 pd pd Table ■ CsF+vSO□N II CII□CIl□Cl1Z
OCII□CII□N (Clh)i(L)C411
゜(t)C411q C112=CIISOICIIZCONII Cl1
zolv-4 AN V-5 olv-5 Trihexyl phosphate xF-1 ol ■ Tonocresyl phosphate ExF-2 ExS-1 ExS-4 ExS-5 ■ C1l! C11□ O3K ExS-2 ExS-3 ExS ExS-7 ExS-8 ExC-1 Nll-co-o-c4119- iS.

ExC-3 ExC-4 iso-11,c4-0-CO-Ni10-C11□ C11□-5-C11! -COOII xC-2 xM-5 Shi! CI+3 ExM-6 CxY CxY-9 ExM-7 ExM-10 CxY-11 CxY-12 C! pd pd pd-2 11 Patent attorney Takehiko Suzue 1, patent attorney Takehiko Suzue 1, Indication of patent application No. 63-324598 2, Title of invention Silver halide photographic light-sensitive material 3, Person making amendment case and Relationship Patent applicant (520) Fuji Photo Film Co., Ltd. 4, agent 3-7-2-7 Kasumikaseki, Chiyoda-ku, Tokyo, has submitted the statement in the "Detailed Description of the Invention" section of the statement of contents of the amendment. Correct as shown below.

■) Check the rcT that says “(70%)” on the second line of page 62.
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On page 153 ExC-2 There is a certain thing, On page 156 ExM-0 There is a certain thing, ExM-6 I am corrected.

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SO,K ” Below Up

Claims (4)

[Claims] (1) Having on a support an emulsion layer containing silver halide grains reduction-sensitized with at least one kind of ascorbic acid or its derivatives and containing a nitrogen-containing heterocyclic compound having a mercapto group. A silver halide photographic material characterized by: (2) The silver halide photographic material according to claim (1), wherein the nitrogen-containing heterocyclic compound having a mercapto group is represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the formula, Z is a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and M is a hydrogen atom, an alkali metal, quaternary ammonium, or quaternary phosphonium. show. (3) Claim (2) in which formula (I) is represented by the following formula (II):
) silver halide photographic materials. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the formula, R^1 is at least one -COOM or -SO
_3 Represents an aliphatic group, aromatic group or heterocyclic group substituted with M, where M has the same meaning as in formula (I). (4) R^1 is at least one -COOM or -SO
The silver halide photographic material according to claim 3, which exhibits a 3M-substituted phenyl group.