JP2578188B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly, to a color silver halide photographic material having high sensitivity, less fogging and excellent storage stability. It relates to a photosensitive material.

[Conventional technology]

The basic performance required of a photographic silver halide emulsion is high sensitivity, low fog, and fine grain.

In order to enhance the sensitivity of the emulsion, (1) increasing the number of photons absorbed by one grain, (2) increasing the efficiency of converting photoelectrons generated by light absorption into silver clusters (latent images), And (3) it is necessary to increase developing activity in order to effectively use the latent image formed. Increasing the size of silver halide grains increases the number of absorbed photons in one grain, but worsens graininess. Increasing the development activity is also an effective means for increasing the sensitivity. However, in the case of parallel type development such as color development, graininess generally deteriorates. In order to increase the sensitivity without deterioration in graininess, it is most preferable to increase the efficiency of converting photoelectrons into a latent image, that is, to increase the quantum sensitivity. In order to increase the quantum sensitivity, it is necessary to remove inefficient processes such as recombination and latent image dispersion as much as possible.

It is known that a reduction sensitization method in which small silver nuclei having no development activity are formed inside or on the surface of silver halide is effective for preventing recombination.

Attempts at reduction sensitization have long been considered. Carroll
(Carroll) reduced tin compounds in US Patent No. 2,487,850, Lowe et al. Reduced polyamine compounds in US Patent No. 2,512,925, and Fallens (Farence) reduced thiourea dioxide compounds in British Patent No. 789,823. It has been disclosed that it is useful as a sensitizer. Further Co
llier is Photographic Science and Engine
ering 23: 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She is dimethylamine borane, stannous chloride, hydrazine, high
A method of pH aging and low pAg aging was adopted. The method of reduction sensitization is further disclosed in U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930,867. Regarding not only the selection of reduction sensitizers, but also the invention of reduction sensitization methods, JP-B-57-33572 and JP-B-58-1410
No. Among these, conventionally known reduction sensitizers are listed, and ascorbic acid is described therein. However, compounds such as thiourea dioxide are considered to be preferred, and thiourea dioxide, silver ripened and hydrazine are shown in the examples. Therefore, favorable properties of the ascorbic acid compound as a reduction sensitizer have not been found in practice. Further, the method of use is disclosed in JP-A-57-179835. A technique for improving the storage stability of the reduction-sensitized emulsion is also disclosed in JP-A-57-8283.
Nos. 1 and 60-178445, however, do not meet the level of sufficient improvement.

Although much research has been conducted in this way, the sensitivity increase width was insufficient compared with the hydrogen sensitization in which the photosensitive material was treated with hydrogen gas under vacuum. This is the Journal of
This is reported by Moisar et al. In Imaging Science Vol. 29, p. 233 (1985).

[Problems to be solved by the invention]

The conventional technology of reduction sensitization is insufficient for recent demands for high-sensitivity, high-quality photographic materials. Further, the emulsion using such a sensitizing technique has a disadvantage that the storage stabilizer is poor.

[Object of the invention]

A first object of the present invention is to provide a silver halide photographic material having high sensitivity, good granularity, low fog, and excellent storage stability. Another object of the present invention is to provide a color light-sensitive material having high sensitivity, low fog and good storage stability.

(Means for Solving the Problems) The object of the present invention has been achieved by the following silver halide photographic materials described in (1) and (2).

(1) at least one of ascorbic acid or a derivative thereof
Contains silver halide grains reduction sensitized by a seed,
And a silver halide photographic light-sensitive material having, on a support, an emulsion layer containing a nitrogen-containing heterocyclic compound having a mercapto group represented by the following general formula [II].

General formula [II] In the formula, R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group substituted with at least one -COOM or -SO ₃ M,
M represents a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium.

(2) The silver halide photographic material as described in (1) above, wherein R ¹ represents a phenyl group substituted with at least one —COOM or —SO ₃ M.

 Hereinafter, the present invention will be described in detail.

The production process of a silver halide emulsion is roughly divided into processes such as grain formation, desalting, chemical sensitization and coating. The formation of silver halide grains is further divided into nucleation, physical ripening, and growth.
These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed.

Reduction sensitization can be performed in principle at any step in the production process of a silver halide emulsion. That is, reduction sensitization is performed at the time of nucleation, which is the initial stage of grain formation, and at the time of physical ripening,
It may be performed at the time of growth, or before, after or simultaneously with sulfur sensitization, selenium sensitization, or gold sensitization.

In the present invention, it is preferred to carry out 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 compound”) include the following.

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) DL-sodium ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-6-di Acetate (A-10) L-ascorbic acid-5,6-O-isopropylidene To add the above ascorbic acid compound in the production process of the silver halide emulsion of the present invention, disperse them directly in the emulsion. Alternatively, it may be dissolved in a single or mixed solvent of water, methanol, ethanol and the like and added during the production process.

It is desirable to use a large amount of the ascorbic acid compound used in the present invention as compared with the amount in which a reduction sensitizer is conventionally preferably used. For example, Japanese Patent Publication No. 57-33572 states that the amount of reducing agent usually does not exceed 0.75 × 10 ^-2 milliequivalents (g × 10 ⁻⁴ mol / Ag × mol) per g of silver ion. Amount (as ascorbic acid, 10 ^-7 to 10
^(-5 mol / Ag x mol) is effective in many cases. (The converted value is based on the inventors). US-2,487,
No. 850 describes "1.times.10.sup.- ^{7 to} 44.times.10.sup.- ⁶ mol as an addition amount in which a tin compound can be used as a reduction sensitizer". JP-A-57-179835 states that it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mole of silver halide, and about 0.01 mg to about 3 mg of stannous chloride. ing. The preferred amount of the ascorbic acid compound to be used in the present invention depends on factors such as the grain size of the emulsion, the halogen composition, the temperature for preparing the emulsion, pH and pAg, but is preferably from 5 × 10 ^-5 mol per mol of silver halide. 1 × 10
It is desirable to select from the range of ^-1 mol. It is more preferable to select from the range of 5 × 10 ^-4 mol to 1 × 10 ^-2 mol. It is particularly preferable to select from the range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol.

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

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted. Stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds as reduction sensitizers,
Borane compounds and the like are known.

In the present invention, the nitrogen-containing heterocyclic compound having a mercapto group may be added at any step of the production process of the silver halide emulsion. For example, it may be at the time of nucleation, which is the initial stage of grain formation, at the time of physical ripening, or at the time of growth, and may be performed prior to chemical sensitization or after chemical sensitization. Further, it may be added immediately before coating. With respect to the addition in the coating step, when the compound represented by the formula (I) or (II) is generally diffusible, it may be added to the same layer as the emulsion of the present invention or may have a water permeable relationship. Any of them can achieve the object of the present invention even when added to a certain other layer to be coated. The addition amount of the nitrogen-containing heterocyclic compound having a mercapto group must be appropriately selected, but is preferably in the range of 10 ^-6 to 10 ^-2 mol per mol of silver halide.

In the present invention, as the nitrogen-containing heterocyclic compound having a mercapto group, a compound represented by the following general formula [II] is particularly preferable, and a compound represented by the general formula [III] is more preferable.

General formula [II] In the general formula [II], R ¹ is at least one —COOM
Or substituted by -SO ₃ M, aliphatic group, an aromatic group or a heterocyclic group, M represents a hydrogen atom, an alkali metal, quaternary ammonium or quaternary phosphonium.

Hereinafter, the nitrogen-containing heterocyclic compound having a mercapto group represented by the general formula [II] used in the present invention will be described in detail.

As the aliphatic group represented by R ¹ in the general formula [II], specifically, a linear or branched alkyl group having 1 to 20 carbon atoms (eg, methyl, propyl, hexyl, dodecyl, isopropyl), Specific examples of the cycloalkyl group having 20 (eg, cyclopropyl, cyclohexyl) and the aromatic group include aryl groups having 6 to 20 carbon atoms (eg, phenyl,
Naphthyl) and a heterocyclic group, specifically, 1
A 5-membered ring containing more than one nitrogen, oxygen or sulfur atom,
6-membered or 7-membered heterocycles (eg, morpholino, piperidino, pyridine), and those which form a condensed ring at an appropriate position (eg, a quinoline ring, a pyrimidine ring, an isoquinoline ring) are also included. .

Further, the above linear or branched alkyl group, cycloalkyl group, aryl group and heterocyclic group are -COOM or-
It may have a substituent in addition to SO ₃ M. As these substituents, specifically, a halogen atom (F, Cl, Br),
Alkyl group (eg, methyl, ethyl), aryl group (eg, phenyl, p-chlorophenyl), alkoxy group (eg, methoxy, methoxyethoxy), aryloxy group (eg, phenoxy), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl) A sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), a sulfamoyl group (eg, diethylsulfamoyl, unsubstituted sulfamoyl), a carbamoyl group (eg, unsubstituted carbamoyl, diethylcarbamoyl), an amide group (eg, acetamido, benzamide), Ureido group (for example, methylureide, phenylureide), alkoxycarbonylamino group (for example, methoxycarbonylamino), aryloxycarbonylamino group (for example, phenoxycal Nylamino), alkoxycarbonyl group (eg, methoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (eg, unsubstituted amino, dimethylamino), alkyl Examples include a sulfinyl group (for example, methoxysulfinyl), an arylsulfinyl group (for example, phenylsulfinyl), an alkylthio group (for example, methylthio), and an arylthio group (for example, phenylthio). Two or more substituents may be substituted, and the substituents may be the same or different.

Among the nitrogen-containing heterocyclic compounds having a mercapto group represented by the general formula [II], particularly preferred are those represented by the general formula [III].

General formula [III] R ^{2 in the} general formula [III] represents a phenyl group substituted with at least one -COOM or -SO ₃ M, and the phenyl group is substituted with another substituent other than -COOM or -SO ₃ M. It may be. Specific examples of the other substituents include the same substituents as those described above for the linear or branched alkyl group, cycloalkyl group, aryl group, and heterocyclic group represented by R ¹ . Where −COOM, −SO ₃ M
When there are two or more, they may be the same or different. M means the same as those represented by the general formula [II].

Preferred specific examples (1) to (N) of the nitrogen-containing heterocyclic compound having a mercapto group used in the present invention are shown in Table A below.
List (22). However, the present invention is not limited to these specific examples. Table A also shows nitrogen-containing heterocyclic compounds (23) to (30) having a mercapto group outside the present invention as reference examples.

The compound can be easily synthesized by using a reaction between isothiocyanate and sodium azide, as is generally well known. Hereinafter, references and patents relating to these synthesis methods are listed for reference.

U.S. Pat.No.3,266,897, JP-B-42-21842, JP-A-56
−111,846, UK Patent 1,275,701, DA Berges (Be
rges) et al., Journal of Heterocyclic Chemistry, No. 1
Volume 5, page 981 (1978), RG Dubenko,
VD Panchenko, “Khimiia
Geterotsiklicheskikh Soedinenii) ”, Part 1, (Azo
le oder Jhaschie Geterotsikly, 1967, 199-201
page).

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

It is already known in the photographic field to use the above-mentioned nitrogen-containing heterocyclic compounds having a mercapto group. For example, Japanese Patent Application Laid-Open No. 62-89952 describes a combination of a nitrogen-containing heterocyclic compound having a mercapto group and a cyanine dye, thereby preventing fog and achieving high sensitivity.
However, it was unexpectedly expected from these techniques that the storage stability of the silver halide photographic light-sensitive material reduced and enhanced with the ascorbic acid compound of the present invention could be improved.

In the reduction ring-extending step of the present invention, it is preferable to add at least one compound selected from the compounds represented by formulas (IV), (V) and (VI) during the production process of the silver halide emulsion. .

[IV] R-SO ₂ S-M [V] R-SO ₂ S-R ¹ [VI] R-SO ₂ S-Lm-SSO ₂ -R ^{2 In the} formula, even if R, R ¹ and R ² are the same, It may be different and 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 the general formulas (IV), (V) and (VI) will be described in more detail. When R, R ¹ and R ² are an aliphatic group, preferably an alkyl group having 1 to 22 carbon atoms, From two
22 alkenyl groups and alkynyl groups, 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 t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic group represented by R, R ¹ and R ² preferably has 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R ¹ and R ² is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium, for example, pyrrolidine, piperidine, pyridine, tetrahydrofuran, Examples thereof include thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidizole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole and thiazazole.

Examples of the substituent for R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyl), an aryl group (eg, phenyl, naphthyl, tolyl), a hydroxy group, Halogen atoms (eg, fluorine, chlorine, bromine, iodine, etc.), aryloxy groups (eg, phenoxy), alkylthio groups (eg, methylthio, butylthio), arylthio groups (eg, phenylthio), acyl groups (eg, acetyl, propionyl, butyryl, valeryl), A sulfonyl group (eg, methylsulfonyl, phenylsulfonyl),
Acylamino group (eg, acetylamino, benzamino), sulfonylamino group (methanesulfonylamino,
Benzsulfonylamino), an acyloxy group (eg, acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group and the like.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group for L include CH _{2
n (n = 1~12), -CH} 2 -CH = CH-CH 2 -, -CH 2 C≡CCH 2 -, A xylylene group, and the like. 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 the metal ion include a lithium ion, a sodium ion, and a potassium ion. As an organic cation, an ammonium ion (for example, ammonium,
Tetramethylammonium, tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), guanidine group and the like.

The compound of the general formula [IV] can be easily synthesized by the methods described in JP-A-54-1019 and British Patent 972,211.

The compound represented by the general formula [IV], [V] or [VI] is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. Further 10 ^-6 to 10 ^-2 , especially 10 ^-5 to 10
An addition amount of ^-3 mol / mol Ag is preferred.

In order to add the compounds represented by the general formulas [I] to [III] during the production process, a method usually used for adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or hardly soluble in water is a suitable organic solvent that is miscible with water, for example, alcohols, glycols, ketones, esters, amides and the like. Among them, it can be dissolved in a solvent that does not adversely affect the photographic properties and added as a solution.

The compound represented by the compound [IV], [V] or [VI] may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization. Preferred is a method in which the compound is added before or during the reduction enrichment.

The silver halide grains used in the present invention may be normal crystals containing no twin planes, for example, as described in P.163, edited by the Photographic Society of Japan, Photograph of Basic Silver Salt Photography of the Photo Industry (Corona), for example, Select from twin twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, non-parallel multiple twins containing two or more non-parallel twin planes according to the purpose. Can be used. In the case of a normal crystal, a cubic body composed of (100) planes, an octahedron composed of (111) planes, and a dodecahedral particle composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 are used. Can be used. Furthermore, Journal of Imagi
(h11) plane particle represented by (211), (hh1) plane particle represented by (331), and (210) plane represented by (ngk30, 247 p. 1986) Plane particles and (hk1) plane particles represented by the (321) plane also need to be devised in the preparation method, but can be selected and used depending on the purpose. For example, tetradecahedral particles in which (100) and (111) planes coexist in one particle, particles in which (100) and (110) planes coexist, or particles in which (111) and (110) planes coexist. Particles in which one surface or many surfaces coexist can be selected and used depending on the purpose.

The grain size of the silver halide may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

Narrow particle size distribution such that 80% or more of all particles fall within ± 30% of average particle size by number or weight of particles.
So-called monodisperse silver halide emulsions can be used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more monodispersed silver halide emulsions having different grain sizes in the emulsion layer having substantially the same color sensitivity are mixed in the same layer or separated. Layers can be overlaid. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), “Digital Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VLZelikmanet a)
l, Making and Coating Photographic Emulsion, Focal P
ress, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-side mixing method, a simultaneous mixing method,
Any of these combinations and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion comprising the regular grains,
It is obtained by controlling pAg and pH during particle formation.
For more information, see, for example, Photographic Science and Eng
ineering, Vol. 6, pp. 159-165 (1962);
Journal of Pho
tographic Science), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Pra
ctice (1930)), p. 131; Gatov p., Photographic Science and Engineering (Gutoff, Pho)
tographic Science and Engineering), Vol. 14, 248-2
57 pages (1970); U.S. Patent Nos. 4,434,226 and 4,414,310
No. 4,433,048, No. 4,439,520 and British Patent No. 2,
It can be easily prepared by the method described in, for example, No. 112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, and are described in detail in U.S. Pat. No. 4,434,226 cited above.

As the emulsion of the present invention, tabular grains are preferred. Particularly, tabular grains in which grains having an aspect ratio of 3 to 8 account for 50% or more of the total projected area are preferred.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. These emulsion grains are described in GB 1,027,146.
And U.S. Pat. Nos. 3,505,068 and 4,444,877 and JP-A-60-143331. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. Typical examples are JP-B-43-13162 and JP-A-61-2.
These are core-shell type or double structure type particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions, as disclosed in JP-A No. 15540, JP-A-60-222845 and JP-A-61-75337. In such particles, the shape of the core portion and the entire shape with the shell may be the same or different. Specifically, the core portion has a cubic shape, and the shape of the shell-containing particles may be cubic or octahedral. Conversely, the core may be octahedral, and the particles with shells may have a cubic or octahedral shape. In addition, although the core portion is a clear regular particle, the shape of the particle with a shell may be slightly distorted or irregular. Further, instead of a mere double structure, a triple structure as disclosed in JP-A-60-222844 or a multilayer structure more than that, or a different composition on the surface of a core-shell double structure particle may be used. Silver halide.

In order to give a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. Examples thereof are disclosed in JP-A-59-133540, JP-A-58-108526, EP199290A2, JP-B-58-24772 and JP-A-59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of a bonding structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure such as silver rhodanate or silver carbonate can be combined with silver halide to form a bonding structure. A non-silver salt compound such as PbO may be used as long as it can form a junction structure.

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, on the other hand, May have a low silver iodide content and a high shell portion. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa.

In addition, the boundary portion having a different halogen composition of the grains having these structures may be a clear boundary, or may be an unclear boundary formed by a mixed crystal due to a composition difference. It may have a structural change.

The silver halide emulsion used in the present invention is EP-0096727B1, E
P-0064412B1 and other treatments for imparting roundness to particles, or DE-2306447C2, JP-A-60-221
Modification of the surface as disclosed in 320 may be performed.

The silver halide emulsion used in the present invention is preferably a surface latent image type, but an internal latent image type emulsion may be used by selecting a developing solution or development conditions as disclosed in JP-A-59-133542. it can. Also, a shallow internal latent image type emulsion covered with a thin shell can be used according to the purpose.

Silver halide solvents are useful to promote ripening.
For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, these ripening agents can be incorporated in their entirety in a dispersion medium in a reactor before adding silver and silver halide salts, or 1 or 2 The above halide salts, silver salts or peptizers can be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As the ripening agent other than the halogen ion, ammonia or an amine compound, a thiocyanate salt, for example, an alkali metal thiocyanate salt, particularly a sodium and potassium thiocyanate salt, and an ammonium thiocyanate salt can be used.

In the present invention, it is extremely important to perform chemical sensitization typified by sulfur sensitization and gold sensitization, and a remarkable effect is obtained when chemical sensitization is performed. The location of chemical sensitization depends on the composition, structure, and shape of the emulsion grains, and on the intended use in which the emulsion is used. There is a case where a chemical sensitizing nucleus is embedded in the inside of a grain, a case where the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, or a case where a chemical sensitizing nucleus is formed on the surface. Although effective in the case of the effects of the present invention, etc., it is particularly preferable to form a chemical sensitizing nucleus near the surface.
That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization is described in THJames, The Photographic Process, Fourth Edition, Macmillan, 1977, (THJames, The Theory of the Photogra
phic Process, 4th ed, Macmillan, 1977), using active gelatin as described on pages 67-76, or as described in Research Disclosure, Volume 120, April 1974, 12008; Research Disclosure, Volume 34, 19
June 1975, 13452, U.S. Patent Nos. 2,642,361, 3,297,44
No. 6, No. 3,772,031, No. 3,857,711, No. 3,901,714,
Nos. 4,266,081 and 3,904,415, and British Patent 1,315,755, at pAg 5-10, pH 5-8 and temperature 30-80 ° C., sulfur, selenium, tellurium, gold,
It can be carried out using 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. Patent Nos. 3,857,711, 4,266,018 and 4,054.
No. 4,457, a sulfur-containing compound or hypo,
The reaction is performed in the presence of a sulfur-containing compound such as a thiourea-based compound and a rhodanin-based compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. Chemical sensitizing aids used include azaindene, azapyridazine, azapyrimidine,
Compounds known to suppress fog and increase sensitivity during chemical sensitization are used. Examples of chemical sensitization aid modifiers are U.S. Pat.Nos. 2,131,038 and 3,411,914,
No. 3,554,757, JP-A-58-126526 and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines A thioketo compound such as oxadolinthione; azaindenes; for example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes and the like; Many compounds known as antifoggants or stabilizers can be added. For example, U.S. Pat.
Nos. 3,982,947 and JP-B-52-28,660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. The dyes used include:
Cyanine dye, merocyanine dye, complex cyanine dye,
Complex merocyanine dyes, holopolar cyanine dyes, hexyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are cyanine dyes,
It is a dye belonging to merocyanine dyes and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; Nucleus fused with an aromatic hydrocarbon ring, that is, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In a merocyanine dye or a complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These ring sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat.Nos. 2,688,545, 2,977,229, 3,397,060 and 3,5
22,052, 3,527,641, 3,617,293, 3,628,96
No. 4, No. 3,666,480, No. 3,672,898, No. 3,679,428
Nos. 3,703,377, 3,769,301, 3,814,609,
3,837,862, 4,026,707, UK Patent 1,344,281
No. 1,507,803, JP-B 43-4936, 53-12,375
And JP-A-52-110,618 and JP-A-52-109,925.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but as described in U.S. Pat.Nos. 3,628,969 and 4,225,666, it is added at the same time as a chemical sensitizer and spectrally sensitized. Sensitization can be carried out simultaneously with chemical sensitization or prior to chemical sensitization as described in JP-A-58-113,928. Sensitization can also be started. Furthermore, separately adding these compounds as taught in U.S. Pat.No.4,225,666,
That is, it is also possible to add a part of these compounds prior to chemical sensitization and add the remainder after chemical sensitization,
At any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756.

The addition amount is 4 × 10 ^-6 to 8 × per mol of silver halide.
Although it can be used in an amount of 10 ^-3 mol, a silver halide grain size of about 5 × 10 ^-5 to 2
× 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the photosensitive material according to the present technology, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18716.
(1979, November), and the relevant locations are summarized in the table below.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020
And Nos. 1,476,760 and the like.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable.
4,310,619, 4,351,897, EP 73,636,
U.S. Patent Nos. 3,061,432 and 3,725,067, Research
Disclosure No. 24220 (June 1984)
-33552, Research Disclosure No.24230 (1
Jun. 984), JP-A-60-43659, U.S. Pat.
Nos. 0 and 4,540,654 are particularly preferable.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,022, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Preferred are those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767 and EP 161,626A.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in, for example, Research Disclosure No. 17643.
VII-G, U.S. Pat.No. 4,163,670, JP-B-57-3941
3, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
For example, U.S. Patent No. 4,366,237, UK Patent No. 2,125,570
No., European Patent No. 96,570, West German Patent (Published) No. 3,234,53
Those described in No. 3 are preferred.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
Nos. 34, 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, UK Patent No. 2,097,140,
JP-A-2,131,188, JP-A-59-157638, JP-A-59-170840
Those described in the above item are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include, for example, competing couplers described in U.S. Patent No. 4,130,427 and the like, U.S. Patent Nos. 4,283,472 and 4,338,3
No. 93, No. 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compounds or DIR coupler releasing couplers described in JP-A-62-24252, etc. or DIR coupler releasing couplers or redox, European Patent 17th
No. 3,302A, couplers releasing dyes that recolor after release, for example, RD Nos. 11449 and 24241, JP-A-61-201247
Bleaching accelerator releasing couplers described in, for example, U.S. Pat.
4,553,477.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

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

Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalates (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate), phosphorus Acid or phosphonic acid esters (e.g., trifel phosphate, 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 (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenol (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, tris Octyl citrate), aniline derivatives (eg, N, N
-Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like.
Further, as an auxiliary solvent, the boiling point is about 30 ℃ or more, preferably
An organic solvent having a temperature of 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, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

When the present invention is used for a color photographing material, the present invention can be applied to photosensitive materials having various structures and photosensitive materials in which a layer structure and a special color material are combined.

A representative example will be described. JP-B-47-49031, JP-B-4
No. 9-3843, JP-B-50-21248, JP-A-59-38147,
JP-A-59-60437, JP-A-60-227256, JP-A-61-4
No. 043, JP-A-61-43743, JP-A-61-42657, etc., in which the coupling speed and diffusion of a color coupler are combined with the layer constitution. JP-B-49-15495, U.S. Pat.No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, JP-B-53-37017, JP-B-53-37018,
JP-A-51-49027, JP-A-52-143016, JP-A-53-9
No. 7424, JP-A-53-97831, JP-A-62-200350, JP-A-59-177551, the arrangement of the high-sensitivity layer and the low-sensitivity layer and the arrangement of layers having different color sensitivity were defined. And the like.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

The color photographic light-sensitive material according to the present invention is described in RD.
Developing can be carried out by the usual methods described in 17643, pp. 28-29, and No. 18716, 651, left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 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 sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, 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, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amounts of these developers are
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (II), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc .; persulfate; bromate; permanganate; nitrobenzenes, etc. Can be. Among these, iron aminopolycarboxylates (II) such as ethylenediaminetetraacetic acid (III) complex salt
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Acid salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the 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 the like. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ion described in JP-A-61-131632,
The method of reducing magnesium ions can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

In the processing of the photosensitive material of the present invention, the pH of the washing water is 4-
9, preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally, the temperature is 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8,543, JP-A-58-14,834, and JP-A-60-220,345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

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 the processing.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-144,547.
No. 115,438 and the like.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-6
It is also applicable to the photothermographic materials described in 1-238056, European Patent 210,660A2, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Double twinned silver iodobromide grains having an average iodine content of 20 mol% and an average equivalent sphere diameter of 0.8 μm were used as seed crystals, and the core-shell ratio was controlled by a control double jet method in an aqueous gelatin solution.
An emulsion comprising twinned silver iodobromide grains having an average sphere equivalent diameter of 1.2 μm was formed so that the iodine content of the shell was 1: 2 and the iodine content of the shell was 4 mol%.

After grain formation, the emulsion is subjected to a normal desalinated water washing step at 40 ° C.
It was redispersed under the conditions of pAg8.9 and pH6.1. The emulsion thus obtained was named Em-A.

Em-A at 60 ° C using sodium thiosulfate and chloroauric acid
The emulsion optimally sensitized to gold and sulfur at this temperature was designated as Em1.

Next, gold-sulfur sensitization was carried out in the same manner as in Em1, and after completion of the gold-sulfur sensitization, the nitrogen-containing heterocyclic compound (1) containing a mercapto group was added at 1 × 10 ^-6 mol, 1 × 10 ^-5 mol per mol of silver. Emulsions were prepared in various amounts, and the resulting emulsions were named Em2 and Em3.

Further, sodium thiosulfate, chloroauric acid, and ascorbic acid compound A-1 were added to Em-A to prepare gold-sulfur sensitized and reduction sensitized emulsions, which were named Em4 to Em6.

Gold-sulfur sensitization and reduction sensitization were performed in the same manner as in Em4-6, and at the end of reduction sensitization, the nitrogen-containing heterocyclic compound (1) containing a mercapto group was added in an amount of 1 × 10 ^-6 mol, 1 mol / mol silver. ×
Em- ⁵ was prepared by adding ^10-5 mol.

Em13 to 36 shown in Table 1-1 and Table 1-2 were prepared in the same manner as in Em4 to 12, except that the types of the ascorbic acid compound and the nitrogen-containing heterocyclic compound having a mercapto group were changed. However, for Em31 to Em36, the nitrogen-containing heterocyclic compound having a mercapto group was added prior to the start of chemical sensitization.

The emulsion and the protective layer were coated on the triacetyl cellulose film support provided with the undercoat layer in the coating amounts shown in Table 1-3.

Table 1-3 (1) Emulsion layer Emulsion: Emulsions Em1 to Em36 (silver 1.7 × 10
^-2 mol / m ² ) ・ Coupler (1.5 × 10 ^-3 mol / m ² ) ・ Tricresyl phosphate (1.10 g / m ² ) ・ gelatin (2.30 g / m ² ) (2) protective layer ・ 2,4-dichlorotriazine-6-hydroxy-s-triazine sodium salt (0.08 g / m ²⁾ Gelatin (1.80 g / m ² ) These samples were exposed to sensitometry and subjected to the following color development processing.

The density of the treated sample was measured with a green filter. The obtained photographic performance results are shown in Tables 1-1 and 1-2.

The results were based on the fog value and sensitivity value of the fresh performance (immediately after sample preparation) of Em1. Repeat the same sample for 60
C., 30% RH for 3 days, and exposed and developed in the same manner to determine fog and sensitivity. The results are shown in Tables 1-1 and 1-2.

 The development treatment used here was performed at 38 ° C. under the following conditions.

1. Color development ... 2 minutes 45 seconds 2. Bleaching ... 6 minutes 30 seconds 3. Rinse ... 3 minutes 15 seconds 4. Settle down ... 6 minutes 30 seconds 5. Rinse ... 3 minutes 15 seconds 6. Stable: 3 minutes 15 seconds The composition of the processing solution used in each process is as follows.

Color developer Sodium nitrilotriacetate 1.4 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino)-
2-Methyl-aniline sulfate 4.5 g Add water 1 Bleaching solution Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Add water 1 Fixing solution Tetrapolyline Sodium citrate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (700 g /) 175.0 ml Sodium bisulfite 4.6 g Water was added 1 Stabilizer Formalin 8.0 mL Water was added 1 Exposure was performed in 1/100 sec. .

The light source was adjusted to a color temperature of 4800K using a filter, and blue light was extracted using a blue filter (BPN42, manufactured by Fuji Photo Film Co., Ltd.). The sensitivity was compared at +0.2 optical density from fog.

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

Example 2 The following dyes were added to the chemically sensitized 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 a sensitometric experiment was performed.

Dye Group 1 (Red Dye) Dye group 2 (green dye) Dye Group 3 (Blue Dye) Sensitizing Dye VIII 2.2 × 10 ^-4 mol / mol Ag Sensitometry experiments showed that instead of the blue filter of Example 1 Exposure was performed using a yellow filter (SC-52, manufactured by Fuji Photo Film Co., Ltd.), and the emulsion containing the blue-sensitive dye was exposed without using the above filter. Other conditions are the same as in the first embodiment.
Table 2-1 shows 1/100 of each of sample Nos. -201, -202 and -203.
Sample No. 204 to 206, 207 to 209, 210 to 212, 213 to 21
5, and shows a sensitivity of 216 to 218.

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

As is clear from Table 2-1, the emulsion of the present invention has reduced fog, high sensitivity, and excellent storage stability.

Example 3 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multilayer manner to prepare a sample 301 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there are multiple utilities, only one of them is listed as a representative.

U: UV absorber, HBS: High boiling point organic solvent, EX: Coupler, S: Additive (Sample 301) First layer: Antihalation layer Black colloidal silver: Silver 0.18 Gelatin: 0.40 Second layer: Intermediate layer 2,5 -Di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin: 1.04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size: 0.1%)
6 μ, coefficient of variation with respect to particle size 0.15) ... silver 0.55 sensitizing dye I ... 6.9 x 10 ^-5 sensitizing dye II ... 1.8 x 10 ^-5 sensitizing dye III ... 3.1 x 10 ^-4 sensitizing dye IV ... 4.0 x 10 ^-5 EX-2 ... 0.350 HBS-1 ... 0.005 EX-10 ... 0.020 Gelatin ... 1.20 Fourth 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 ... 5.1 x ^10-5 sensitizing dye II ... 1.4 x ^10-5 sensitizing dye III ... 2.3 x ^10-4 sensitizing dye IV ... 3.0 × 10 ^-5 EX-2 ... 0.400 EX-3 ... 0.050 EX-10 ... 0.015 Gelatin ... 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion I ... Silver 1.60 EX-3 ... 0.240 EX- 4 ... 0.120 HBS-1 ... 0.22 HBS-2 ... 0.10 Gelatin ... 1.63 6th layer (intermediate layer) EX-5 ... 0.040 HBS-1 ... 0.020 Gelatin ... 0.80 7th layer (first green-sensitive emulsion layer) Silver bromide emulsion (silver iodide 6 mol%, average grain size of 0.
6μ, average aspect ratio 6.0, average thickness 0.15μ)… Silver 0.40
Sensitizing dye V: 3.0 × 10 ^-5 Sensitizing dye VI: 1.0 × 10 ^-4 Sensitizing dye VII: 3.8 × 10 ^-4 EX-6: 0.260 EX-1: 0.021 EX-7: 0.030 EX-8: 0.025 HBS-1 ... 0.100 HBS-4 ... 0.010 Gelatin ... 0.75 Eighth layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0.1%)
7 μ, coefficient of variation relating to particle size 0.18) Silver 0.80 sensitizing dye V 2.1 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.180 EX-8 ... 0.010 EX-1 ... 0.008 EX-7 ... 0.012 HBS-1 ... 0.160 HBS-4 ... 0.008 Gelatin ... 1.10 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion II ... silver 1.2 EX-6 ... 0.065 EX-11 ... 0.030 EX-1 ... 0.025 HBS-1 ... 0.25 HBS-2 ... 0.10 Gelatin ... 1.74 Layer 10 (yellow filter layer) Yellow colloidal silver ... silver 0.05 EX-5 ... 0.08 HBS-3 ... 0.03 Gelatin ... 0.95 Eleventh layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size: 0,1)
6μ, average aspect ratio 5.7, average thickness 0.15μ) ... Silver 0.24 Sensitizing dye VII ... 3.5 × ^10-4 EX-9 ... 0.85 EX-8 ... 0.12 HBS-1 ... 0.28 Gelatin ... 1.28 12th layer (2nd blue) Sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.1
8μ, coefficient of variation relating to particle size 0.16)… Silver 0.45 Sensitizing dye VIII… 2.1 × 10 ^-4 EX-9… 0.20 EX-10… 0.015 HBS-1… 0.03 Gelatin… 0.46 13th layer (3rd blue-sensitive emulsion layer) Silver iodobromide emulsion III ... silver 0.77 EX-9 ... 0.20 HBS-1 ... 0.07 gelatin ... 0.69 14th layer (first protective layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0.07 µm) )
... Silver 0.5 U-4 ... 0.11 U-5 ... 0.17 HBS-1 ... 0.90 Gelatin ... 1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (1.5 m in diameter) ... 0.54 S-1 ... 0.15 S-2 ... 0.05 gelatin... 0.72 In addition to the above components, gelatin hardener H-1 and a surfactant were added to each layer. The structural formula of the compound used is represented by
It is shown in the table.

Silver iodobromide emulsion I of the fifth layer, silver iodobromide emulsion of the ninth layer
Samples 302 to 306 were prepared in the same manner as in Sample 301, except that the silver iodobromide emulsion III of the 13th layer was changed as shown in Table 3-1 (A).
Was prepared.

These samples were subjected to sensitometric exposure and subjected to the following color development processing.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 3-1 shows the obtained results.
It is shown in (B).

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

Regarding the results of the photographic performance, the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each expressed as a relative sensitivity when the fresh sensitivity of Sample 301 was set to 100.

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

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fixed 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stable 1 minute 05 seconds The processing liquid composition used in each process is as follows. Was.

Color developing solution Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5 g Add water 1.0 pH 10.0 Bleach solution Ferric ammonium ammonium diaminetetraacetate 100.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water 1.0 pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0 pH 6.6 Stabilizer Formalin (40%) 2.0ml Polyoxyethylene-p -Monononyl phenyl ether (average degree of polymerization 10) 0.3 g As is clear from Tables 3-1 (A) and (B), the emulsions of the present invention have reduced fog, high sensitivity, and excellent storage stability.

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

Processing method Process Time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° Bleaching and fixing 3 minutes 15 seconds 38 ° C Rinse with water (1) 40 seconds 35 ° C Rinse with water (2) 1 minute 00 seconds 35 ° C Stability 40 seconds 38 ° C Drying 1 minute 15 seconds 55 ° C Next, the composition of the processing solution is described.

(Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water 1.0 pH 10.05 (Bleaching solution) (g) Ferric ammonium ethylenediaminetetraacetate dihydrate 120.
0 Disodium ethylenediaminetetraacetate 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0ml Add water 1.0 pH 6.3 (Bleaching fixer) (g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.
0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Add water 1.0 pH 7.2 (Washing solution) Tap water is replaced with H-type strongly acidic cation exchange resin ( Water is passed through a mixed-bed column filled with Rohm and Haas Amberlite IR-120B) and an OH-type anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3 mg / L or less. Subsequently, 20 mg / L of sodium diisocyanurate and 1.5 g / L of sodium sulfate were added. The pH of this solution is in the range 6.5-7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Water is added to 1.0 pH 5.0-8.0 The present invention The samples 304 and 306 of Example 3 were also produced by this treatment.
The results were as good as.

Example 5 Samples 301 to 306 of Example 5 were exposed in the same manner as in Example 3, and then processed by the following method using an automatic developing machine.

Processing method Process Time Processing temperature Color development 2 minutes 30 seconds 40 ° C Bleaching and fixing 3 minutes 00 seconds 40 ° C Washing (1) 20 seconds 35 ° C Washing (2) 20 seconds 35 ° C Stable 20 seconds 35 ° C Drying 50 seconds 65 ° C. Next, the composition of the processing solution will be described.

(Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water 1.0 pH 10.05 (Bleach-fix solution) (g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.
0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleaching accelerator 0.01 mol 1.0 pH 6.0 by adding water (washing solution) Fill tap water with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) Water was passed through the mixed bed column to treat the calcium and magnesium ion concentrations to 3 mg / L or less, and then 20 mg / L of sodium diisocyanurate and 1.5 g / L of sodium sulfate were added.

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

(Stabilizing solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Water is added to 1.0 pH 5.0-8.0 The present invention The samples 304 and 306 of Example 3 were also produced by this treatment.
The results were as good as.

Example 6 A sample 401, which is a multilayer color photographic material comprising the following layers, was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The coating amount was expressed in units of g / m ² . However, for silver halide and colloidal silver, the amount expressed in g / m ^{2 of} silver is
The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there are multiple utilities, only one of them is listed as a representative.

UV: UV absorber, Solv: high boiling organic solvent, W: coating aid,
H: Hardener, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additives First layer: Antihalation layer Black colloidal silver Silver coating amount 0.2 Gelatin 2.2 UV-1 0.1 UV-2 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 Second layer: Intermediate layer Fine particle silver bromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.15 Gelatin 1.0 Cpd-2 0.2 Third Layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter 0.7 μ, variation coefficient of equivalent spherical diameter 14%, tetrahedral grains) Silver coating amount 0.26 iodobromide Silver emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter)
0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetrahedral particles) Silver coating amount 0.2 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExS -4 0.4 × 10 ^-4 mol ExS-1 0.33 ExS-2 0.009 ExS-3 0.0023 ExS-4 0.14 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, Ball equivalent diameter
1.0μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio 4.0) Silver coating amount 0.55 gelatin 0.7 ExS-1 3 × 10 ^-4 ExS-2 1 × 10 ^-4 ExS-3 0.3 × 10 ^-4 ExS-4 0.3 × 10 ^-4 ExC-3 0.05 ExC-4 0.10 ExC-6 0.08 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion I (high internal AgI type, equivalent sphere diameter 1.2 μm, Coefficient of variation of sphere equivalent diameter 28%) Silver coating amount 0.9 Gelatin 0.6 ExS-1 2 × 10 ^-4 ExS-2 0.6 × 10 ^-4 ExS-3 0.2 × 10 ^-4 ExC-4 0.07 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 6th layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter 0.7 μm, spherical) Coefficient of variation of equivalent diameter 14%, tetrahedral grain) Silver coating amount 0.2 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetrahedral particles) Silver coating amount 0.1 Gelatin 1.2 ExS-5 5 × 10 ^-4 ExS-6 2 × 10 ^-4 ExS-7 1 × 10 ^-4 ExM-1 0.41 ExM-2 0.10 ExM-5 0.03 Solv-1 0.2 Solv-5 0.03 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent sphere diameter 1.0 μm, equivalent sphere) Coefficient of variation of diameter 25%, plate-like particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 ExS-6 1.4 × 10 ^-4 ExS-7 0.7 × 10 ^-4 ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 Solv-5 0.03 Ninth layer: Intermediate layer Gelatin 0.5 Tenth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion II (internal high AgI type, equivalent spherical diameter 1.2 μ, equivalent coefficient of equivalent spherical diameter 28%) Silver coating amount 1.0 gelatin 0.8 ExS-5 2 × 10 ^-4 ExS-6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ^-4 ExM-3 0.01 ExM-4 0.04 ExC-4 0.005 Solv-1 0.2 Layer 11: Yellow filter layer Cpd- 3 0.05 Gelatin 0.5 Solv-1 0.1 12th layer: Intermediate layer Gelatin 0.5 Cpd-2 0.1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 0.7) μ, Coefficient of variation of sphere equivalent diameter 14%, tetrahedral particle) Silver coating amount 0.1 Silver iodobromide emulsion (AgI 4.0 mol%, internal high iodine type, equivalent diameter of sphere 0.4μ, variation coefficient of equivalent sphere diameter 22%, 14-sided particles) Silver coating amount 0.05 Gelatin 1. 0 ExS-8 3 × 10 ^-4 ExY-1 0.53 ExY-2 0.02 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent sphere diameter) 1.0μ, coefficient of variation of sphere equivalent diameter 16%, tetrahedral particles) Silver coating amount 0.19 Gelatin 0.3 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer Fine particle silver iodobromide ( AgI 2 mol%, uniform type, sphere equivalent diameter 0.13
μ) Silver coating amount 0.2 gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide agent III (Internal high AgI type, equivalent spherical diameter 1.2μ, coefficient of variation of equivalent spherical diameter 28%) Silver coating amount 1.0 gelatin 0.5 ExS-8 1.5 × 10 ^-4 ExY-1 0.2 Solv-4 0.07 17th layer: 1st protective layer Gelatin 1.8 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 18th layer: 2nd protective Layer Fine particle silver bromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.18 Gelatin 0.7 Polymethyl methacrylate particles (diameter 1.5μ) 0.2 W-1 0.02 H-1 0.4 Cpd-5 1.0 Table C shows the structural formula of the compound used. Shown in

5th layer silver iodobromide emulsion I, 10th layer silver iodobromide emulsion
Samples 402 to 406 were prepared in the same manner as in Sample 401 except that the silver iodobromide emulsion III of the 16th layer was changed as shown in Table 4-1 (A).
Was prepared.

These samples were subjected to sensitometric exposure and subjected to the same color development processing as in Example 3.

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

The same sample was stored at 60 ° C. and 30% RH for 3 days, and exposed and developed in the same manner to determine fog and sensitivity. Table 4-1 (B)
At 60 ° C., 30% RH for 3 days.

Regarding the results of the photographic performance, the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each expressed as a relative sensitivity when the fresh sensitivity of Sample 401 was set to 100.

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

Example 7 A sample 501, which is a multilayer color light-sensitive material having the following composition, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there are multiple utilities, only one of them is listed as a representative.

UV; UV absorber, Solv; High boiling organic solvent, ExF; Dye, Ex
S; Sensitizing dye, ExC; Cyan coupler, ExM; Magenta coupler, ExY; Yellow coupler, Cpd; Additive 1st layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.9 UV-1 0.03 UV-2 0.06 UV-3 ... 0.07 Solv-2 ... 0.08 ExF-1 ... 0.01 ExF-2 ... 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol% uniform sphere equivalent diameter 0.4μ, sphere) Coefficient of variation of equivalent diameter 37%, plate-like particle diameter / thickness ratio 3.0) Silver coating amount… 0.4 Gelatin… 0.8 ExS-1… 2.3 × 10 ^-4 ExS-2… 1.4 × 10 ^-4 ExS-5… 2.3 × 10 ^-4 ExS-7 ... 8.0 × 10 ^-6 ExC-1 ... 0.17 ExC-2 ... 0.03 ExC-3 ... 0.13 Third layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio) 2: 1 internal height
AgI sphere equivalent diameter 0.65μ, coefficient of variation of sphere equivalent diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount… 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, sphere equivalent diameter 0.4)
μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter / thickness ratio
3.0) Silver coating amount ... 0.1 Gelatin ... 1.0 ExS-1 ... 2 x 10 ^-4 ExS-2 ... 1.2 x 10 ^-4 ExS-5 ... 2 x 10 ^-4 ExS-7 ... 7 x 10 ^-6 ExC-1 ... 0.31 ExC-2 ... 0.01 ExC-3 ... 0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion I (internal high AgI type with a core-shell ratio of 1: 2, sphere equivalent diameter 0.75μ, sphere equivalent diameter (Coefficient of variation: 25%) Silver coating amount: 0.9 Gelatin ... 0.8 ExS-1 ... 1.6 x ^10-4 ExS-2 ... 1.6 x ^10-4 ExS-5 ... 1.6 x ^10-4 ExS-7 ... 6 x ^10-4 ExC -1 ... 0.07 ExC-4 ... 0.05 Solv-1 ... 0.07 Solv-2 ... 0.20 Cpd-7 ... 4.6 x 10 ^-4 Fifth layer (intermediate layer) Gelatin ... 0.6 UV-4 ... 0.03 UV-5 ... 0.04 Cpd- 1 ... 0.1 polyethyl acrylate latex ... 0.08 Solv-1 ... 0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol% uniform type. Equivalent sphere diameter 0.7μ, Coefficient of variation of sphere equivalent diameter 37%, plate-like particles, diameter / thickness ratio 2.0) Silver coating amount: 0.18 Gelatin: 0.4 ExS− ^{... 2 × 10 -4 ExS-4} ... 7 × 10 -4 ExS-5 ... 1 × 10 -4 ExM-5 ... 0.11 ExM-7 ... 0.03 ExY-8 ... 0.01 Solv-1 ... 0.09 Solv-4 ... 0.01 second 7 layers (medium-speed green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface height of core-shell ratio 1: 1)
AgI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particle, diameter / thickness ratio 4.0) Silver coating amount 0.27 Gelatin 0.6 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5… 1 × 10 ^-4 ExM-5… 0.17 ExM-7… 0.04 ExY-8… 0.02 Solv-1… 0.14 Solv-4… 0.02 8th layer (high-sensitivity green-sensitive emulsion layer) Silver bromide emulsion II (core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.75μ, coefficient of variation of sphere equivalent diameter 25%) Silver coating amount… 0.7 Gelatin… 0.8 ExS-4… 5.2 × 10 ^-4 ExS -5 ... 1 x 10 ^-4 ExS-8 ... 0.3 x 10 ^-4 ExM-5 ... 0.1 ExM-6 ... 0.03 ExY-8 ... 0.02 ExC-1 ... 0.02 ExC-4 ... 0.01 Solv-1 ... 0.25 Solv-2 ... 0.06 Solv-4 ... 0.01 Cpd-7 ... 1 × 10 ^-4 9th layer (intermediate layer) Gelatin ... 0.6 Cpd-1 ... 0.04 Polyethyl acrylate latex ... 0.12 Solv-1 ... 0.02 10th layer (for red sensitive layer) Donor layer of multilayer effect) Silver iodobromide emulsion (AgI 6 mol%, core Shell height 2: 1 internal height
AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount: 0.68 Silver iodobromide emulsion (AgI 4 mol% uniform type, equivalent sphere equivalent diameter) Coefficient of variation: 37%, plate-like particles, diameter / thickness ratio: 3.0) Silver coating: 0.19 Gelatin: 1.0 ExS-3: 6 × 10 ^-4 ExM-10: 0.19 Solv-1: 0.20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0.8 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.07 Cpd-6 0.002 H-1 0.13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion ( AgI 4.5 mol%, uniform AgI type, equivalent sphere diameter 0.
7μ, coefficient of variation of sphere equivalent diameter 15%, plate-like grains, diameter / thickness ratio 7.0) coated silver amount… 0.3 silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 0.3)
μ, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter / thickness ratio
7.0) Silver coating… 0.15 Gelatin… 1.8 ExS-6… 9 × 10 ^-4 ExC-1… 0.06 ExC-4… 0.03 ExY-9… 0.14 ExY-11… 0.89 Solv-1… 0.42 Layer 13 (intermediate layer) Gelatin: 0.7 ExY-12: 0.20 Solv-1: 0.34 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion III (internal high AgI type with a core-shell ratio of 1: 2, sphere equivalent diameter 0.75μ, sphere) (Coefficient of variation of equivalent diameter: 25%) Silver coating amount: 0.5 Gelatin: 0.5 ExS-6: 1 × 10 ^-4 ExY-9: 0.01 ExY-11: 0.20 ExC-1: 0.02 Solv-1: 0.10 15th layer (No. 1 protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter)
0.07μ) Silver coating amount 0.12 Gelatin 0.9 UV-4 0.11 UV-5 0.16 Solv-5 0.02 H-1 0.13 Cpd-5 0.10 Polyethyl acrylate latex 0.09 16th layer (second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter)
0.07μ) Silver coating amount 0.36 Gelatin 0.55 Polymethyl methacrylate particles (1.5μ in diameter) 0.2 H-1 0.17 In addition to the above components, an emulsion stabilizer Cpd-3
(0.07 g / m ² ) Surfactant Cpd-4 (0.03 g / m ² ) was added as a coating aid.

 Table D shows the structural formulas of the compounds used.

In Em-1 of Example 1, the average equivalent sphere diameter of the seed crystal was set to 0.
The emulsion prepared in the same manner as in Em-1 of Example 1 except that the emulsion had a diameter of 5 μm and thus had an average equivalent spherical diameter of the final grains of 0.75 μm was designated as Em-201.

Em-201 was reduced and sensitized by using gold / sulfur sensitized comparative emulsion Em-202 and gold / sulfur sensitized plus ascorbic acid compound A-1 in the same manner as in Example 1. After completion, the emulsion Em-203 of the present invention was prepared by adding 1.times.10.sup.- ⁵ mol of the heterocyclic compound (1) containing a mercapto group per mol of silver.

Next, emulsions obtained by sensitizing these emulsions Em-202 and Em-203 in the same manner as in Example 2 were prepared, and a silver iodobromide emulsion of the fourth layer, a silver iodobromide emulsion of the eighth layer, A comparison was made in the same manner as in Examples 3 and 6 using 14 layers of silver iodobromide emulsion, and the same effect of the present invention was confirmed.

Claims (2)

(57) [Claims] 1. A nitrogen-containing heterocyclic compound having a mercapto group represented by the following general formula [II] containing silver halide grains reduced and sensitized by at least one of ascorbic acid or a derivative thereof. A silver halide photographic light-sensitive material comprising an emulsion layer on a support. General formula [II] In the formula, R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group substituted with at least one —COOM or —SO ₃ M;
Represents a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium. 2. The silver halide photographic material according to claim 1, wherein R ¹ represents a phenyl group substituted with at least one —COOM or —SO ₃ M.