JP2594357B2 - Silver halide emulsion and silver halide color photographic material using this emulsion - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide emulsion having high sensitivity and low graininess and good graininess. The present invention also relates to high sensitivity and excellent graininess and sharpness. The present invention relates to a silver halide color photographic light-sensitive material having low pressure and improved pressure characteristics.

[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 the developing activity in order to effectively use the latent image formed. Increasing the size increases the number of absorbed photons per particle, but reduces the image quality. 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 causing 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.

Also, James et al. Performed a kind of reduction sensitization in which a coating film of an emulsion sensitized with gold and sulfur was subjected to vacuum degassing, and then heat-treated in an atmosphere of hydrogen gas. It has been found that the sensitivity can be increased at a lower fog level as compared with the feeling. This sensitization method is well known as hydrogen sensitization and is effective as a sensitization means on a laboratory scale. Furthermore, hydrogen sensitization is actually used in the field of astrophotography.

Attempts at reduction sensitization have long been considered. Carroll
(Carroll) in U.S. Pat. No. 2,487,850 for tin compounds, Lowe et al. For polyamine compounds in U.S. Pat. No. 2,512,925, and Fallens (Farence) for U.S. Pat. No. 789,823 for thiourea dioxide compounds. It is disclosed that it is useful as a reduction 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 adopted the dimethylamine borane, stannous chloride, hydrazine, high pH aging, low pAg aging methods. The method of reduction sensitization is further U.S. Pat.Nos. 2,518,698 and 3,201,254,
Nos. 3,411,914, 3,779,777 and 3,930,867. Regarding the method of using the reducing agent as well as the selection of the reduction sensitizer, JP-B-57-33572 and JP-B-58-1410
And JP-A-57-179835. Further, techniques for improving the preservability of the emulsion sensitized by reduction are disclosed in JP-A-57-82831 and JP-A-60-178445.
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 I
maging Science 29: 233 (1985), reported by Moisar et al.

The prior art of reduction sensitization is insufficient for recent demands for high-sensitivity and high-quality photographic materials. The means of hydrogen sensitization also has a disadvantage that the sensitizing effect is lost if the photosensitive material is left in the air after the hydrogen sensitization. Therefore, it is difficult to use this sensitization method in the case of a photographic material in which a special device cannot be used.

[Problems to be solved by the invention]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide emulsion having high sensitivity and less graininess and good graininess. Also. A second object is to provide a photographic material having high sensitivity and good granularity and a photographic material having high sensitivity and less fogging. A third object is to provide a color photosensitive material having high sensitivity and good granularity and a color photosensitive material having high sensitivity and little fog.

A fourth object of the present invention is to provide a silver halide color photographic material having high sensitivity, excellent graininess and sharpness, and improved pressure characteristics.

[Means for solving the problem]

The object of the present invention has been attained by a silver halide emulsion described in the following (1) to (7) and a silver halide color photographic material using the emulsion.

(1) In the production process of a silver halide emulsion, during the growth of silver halide grains, the compound represented by the general formula [I], [II] or [II]
Silver halide prepared by reduction sensitizing at least one compound selected from the compounds represented by formula (I) in the presence of 10 ^-6 to 10 ^-2 mol per mol of silver halide. emulsion.

[I] in _{R-SO 2 S-M [} II] R-SO 2 S-R 1 [III] R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is 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 [I] to [III] may be polymers containing as a repeating unit a divalent group derived from the structure represented by any one of [I] to [III]. When possible, R, R ¹ , R ² , and L may combine with each other to form a ring.

(2) The above-mentioned production is carried out according to the above general formula [I], [II] or [II]
At least one compound selected from the compounds represented by the formula (I) is present in the presence of 10 ^-6 to 10 ^-2 mol per mol of silver halide, reduction sensitization, washing with water and chemical sensitization. The silver halide emulsion according to the above (1).

(3) When the above-mentioned production is carried out by the above-mentioned general formula [I], [II] or [II]
A method in which at least one compound selected from the compounds represented by the formula [I] is present in an amount of 10 ^-6 to 10 ^-2 mol per mol of silver halide, reduction sensitized, washed with water, and then chemically sensitized and spectrally sensitized. The silver halide emulsion according to the above (1), wherein

(4) The silver halide emulsion according to (1), wherein the tabular grains having an aspect ratio of 3 to 8 account for 50% or more of the total projected area of all silver halide grains.

(5) In the step of producing a silver halide emulsion, during the growth of silver halide grains, the compound represented by the general formula [I], [II] or [II]
I] containing a silver halide emulsion produced by a method of reducing and sensitizing at least one compound selected from the compounds represented by formula (I) in the presence of 10 ^-6 to 10 ^-2 mol per mol of silver halide. At least 50% of the total projected area of all silver halide grains in one emulsion layer is occupied by tabular silver halide grains, and the tabular silver halide grains occupying 50% have an average aspect ratio of 3.0 or more; A silver halide color photographic material comprising at least one silver halide emulsion layer on a support.

[I] in _{R-SO 2 S-M [} II] R-SO 2 S-R 1 [III] R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is 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 [I] to [III] may be polymers containing as a repeating unit a divalent group derived from the structure represented by any one of [I] to [III]. When possible, R, R ¹ , R ² , and L may combine with each other to form a ring.

(6) The silver halide color photographic material as described in (5) above, wherein the average aspect ratio of the tabular silver halide grains is 3 to 20.

(7) Tabular silver halide grains having an average aspect ratio of 3 to 20 account for 50% of the total projected area of all silver halide grains.
(5) The silver halide color photographic light-sensitive material as described in (5) above.

 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. Particle formation is divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. Performing the reduction sensitization during the production process of the silver halide emulsion basically means that the reduction sensitization may be performed in any process. Reduction sensitization may be performed at the initial stage of grain formation, such as nucleation, physical ripening, or growth, and may be performed prior to chemical sensitization such as gold sensitization and / or sulfur sensitization or selenium sensitization. It may be performed after chemical sensitization. When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains.
Here, growing is also referred to as a method of performing reduction sensitization in a state where silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. The method also includes a method of further growing after subjecting to reduction sensitization in a heated state.

The reduction sensitization of the present invention refers to a method in which a known reducing agent is added to a silver halide emulsion, and a low pAg of pAg1 to 7, which is called silver ripening.
Ripening or ripening in an atmosphere of high pH, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening. Also, two or more methods can be used in combination.

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

Stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid as reduction sensitizers,
Silane compounds, borane compounds and the like are known. The present invention can be used by selecting from these known compounds,
Two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, and dimethylamine borane are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. It may be added at any stage of the emulsion production process,
Particularly preferred is a method of adding during the grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

The thiosulfonic acid-based compounds of the general formulas (I), (II) and (III) will be described in more detail. When R, R ¹ and R ² are an aliphatic group, they are saturated or unsaturated, linear or branched. Or a cyclic, aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, even if these have a substituent. Good. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl,
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 includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group represented by R, R ¹ and R ² has at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, and 3 to 15 carbon atoms having at least one carbon atom.
A 3-membered ring, preferably a 3- to 6-membered ring,
For example, pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole,
Examples include benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadiazole ring.

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), hydroxy Groups, halogen atoms (eg, fluorine, chlorine, bromine, iodine), aryloxy groups (eg, phenoxy), alkylthio groups (eg, methylthio, butylthio), arylthio groups (eg, phenylthio), acyl groups (eg, acetyl, propionyl, Butyryl, valeryl),
Sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy group (eg, acetoxy, benzoxy), carboxyl Group, cyano group, sulfo group, amino group, -SO ₂ MS group, (M represents a monovalent cation) -SO ₂ R ¹
Group.

The divalent linking group represented by L is an atom or an atomic group containing at least one selected from C, N, S and O. Specifically, an alkylene group, an alkenylene group,
Alkynylene group, arylene group, -O-, -S-, -NH
-, - CO -, - SO 2 - is made of a single or combination of such.

L is preferably a divalent aliphatic group or a divalent aromatic group. The divalent aliphatic group of L for example _{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 a phenylene group and a naphthylene group.

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

M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (ammonium, tetramethylammonium, tetrabutylammonium, etc.), a phosphonium ion (tetraphenylphosphonium), and a guanidyl group.

When the general formulas (I) to (III) are polymers,
Examples of the repeating unit include the following.

These polymers may be homopolymers or copolymers with other copolymerized monomers.

Specific examples of the compound represented by the general formula [I], [II] or [III] are shown in Table A, but are not limited thereto.

Compounds of general formulas (I), (II) and (III) are disclosed in JP-A-54-1019; British Patent 972, 211; Journal of Organic Ch.
emistry (Journal of Organic Chemistry) 53, 396 (1988) and Chemical Abstracts
(Chemical Abstracts) Vol. 59, 9776e, or can be easily synthesized by the method described or cited.

The compound represented by the general formula [I], [II] or [III] is added in an amount of 10 ^-6 to 10 ^-2 mol per mol of silver halide, and more preferably 10 ^-5 to 10 ^-3 mol / mol Ag. The addition amount 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 general formula [I], [II] or [III] 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 a compound is added before or during reduction sensitization. Particularly preferred is a method of adding during the grain growth.

It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. The compounds [1] to [III] may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. It is also a preferable method to add the solutions of the compounds [I] to [III] in several portions along with the formation of the particles, or to add them continuously for a long time.

The general formula of the compound most preferable for the present invention is a compound represented by the general formula [I].

In the tabular silver halide emulsion sensitized in the presence of the thiosulfonic acid compound used in the present invention, the aspect ratio means the ratio of the diameter to the thickness of silver halide grains. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of a grain when the silver halide emulsion is observed with a microscope or an electron microscope. Therefore, that the aspect ratio is 3 or more means that the diameter of the circle is 3 times or more the thickness of the particle.

The average aspect ratio was determined by extracting 1,000 silver halide grains of the emulsion at random and measuring the aspect ratio of each grain. Tabular grains are selected and the arithmetic average of the aspect ratios of the individual grains in the tabular grains is calculated. The arithmetic average of the diameters or thicknesses of the individual grains of the tabular grains used for calculating the aspect ratio is defined as the average grain diameter or the average grain thickness, respectively.

As an example of the method of measuring the aspect ratio, there is a method of obtaining a circle equivalent diameter and thickness of each particle by taking a transmission electron micrograph by a replica method. In this case, the thickness is calculated from the length of the shadow of the replica.

In the tabular silver halide grains sensitized by reduction in the presence of the thiosulfonic acid compound used in the present invention,
The average aspect ratio is 3.0 times or more, preferably 3 times.
-20, more preferably 4-15, particularly preferably 5-10. The proportion of tabular silver halide grains in the projected area of all silver halide grains in one emulsion layer was 50%.
Or more, preferably 70% or more, particularly preferably 85% or more.
% Or more.

By using such an emulsion, a silver halide photographic material having excellent sharpness can be obtained. The sharpness is excellent because the light scattering by the emulsion layer using such an emulsion is extremely small as compared with the conventional emulsion layer. This can be easily confirmed by those skilled in the art using experimental methods that can be used on a daily basis. The reason why the light scattering of the emulsion layer using the tabular silver halide emulsion is small is not clear, but it is considered that the main surface of the tabular silver halide emulsion grains is oriented parallel to the support surface.

The average grain diameter of the tabular silver halide grains reduction-sensitized in the presence of the thiosulfonic acid compound used in the present invention is 0.2 to 10.0 μm, preferably 0.3 to 5.0 μm.
m, and particularly preferably 0.4 to 3.0 μm. The average particle thickness is preferably 0.5 μm or less. More preferably, the average grain diameter is 0.4 μm or more and 3.0 or less, the average grain thickness is 0.5 μm or less, the average aspect ratio is 5 or more and 10 or less, and 85% or more of the total projected area of all silver halide grains. This is the case of a silver halide photographic emulsion occupied by tabular grains.

Tabular silver halide grains sensitized in the presence of the thiosulfonic acid compound used in the present invention are silver chloride,
Any of silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide may be used, but silver bromide, silver iodobromide of 20 mol% or less of silver iodide, or silver chloride of 50 mol% or less is used. Silver chloroiodobromide and silver chlorobromide of 2 mol% or less of silver iodide are more preferable, and the composition distribution in the mixed silver halide may be uniform or localized.

The particle size distribution may be narrow or wide.

Tabular silver halide emulsions which can be subjected to reduction sensitization in the presence of the thiosulfonic acid compound used in the present invention are described in Cugnac (Cunyac), Chateau (Chateau), and by Duffin (Duffin). Photographic Emulsio
n Chemistry "(Focal Press, New York 1966) pp. 66-72, and APHTrivelli, WFSmith
(Smith) ed., “Phot. Journal” 80 (1940), p. 285, which is described in JP-A-58-113927 and JP-A-58-113927,
It can be easily prepared by referring to the method described in JP-A-58-127921.

For example, in an atmosphere having a relatively high pAg value of pBr of 1.3 or less, a tabular grain forms a seed crystal having a weight percentage of 40% or more. Obtained by growing crystals. In this grain growth process, it is desirable to add a silver and halogen solution so as not to generate new crystal nuclei.

The size of the tabular silver halide grains sensitized by reduction in the presence of the thiosulfonic acid compound used in the present invention can be controlled by controlling the temperature, selecting the type and quality of the solvent, the silver salt used during grain growth, and the halide. It can be adjusted by controlling the rate of addition of.

As the silver halide which can be used in combination in the light-sensitive material of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are silver iodobromide, silver bromide, and silver chlorobromide containing 30 mol% or less of silver iodide.

The silver halide grains that can be used in combination with the silver halide emulsion of the present invention can be either normal crystals containing no twin planes (regular),
Particles containing twin planes as described in the Photographic Society of Japan, Photographic Industry Basic Silver Halide Photography (P.163), for example, single twin containing one twin plane, parallel twin It can be selected from parallel multiple twins including two or more crystal planes and non-parallel multiple twins including two or more non-parallel twin planes according to the purpose. In the case of a normal crystal, a cube consisting of (100) planes, an octahedron consisting of (111) planes, Japanese Patent Publication No. 55-42737,
Japanese Patent Application Laid-Open No. 60-222842 discloses a (1)
Dihedral particles can be used. Further Journal of Im
(aging science) Vol. 30, page 247 (h11) plane particles represented by (211), (hh1) plane particles represented by (331), and (210) plane represented by 1986 as reported in 1986 ( hk
The (0k) plane particles and the (hk1) plane particles represented by the (321) plane also need to be devised in the preparation method, but can be selected and used according to the purpose. (100) plane and (111) plane coexist in one particle
Particles with two or many planes, such as tetrahedral particles, particles with (100) and (110) planes, or particles with (111) and (110) planes, are also selected according to the purpose. Can be used.

The grain size of these silver halide grains 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 broad distribution. May be.

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 are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. 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 Photographiqus Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemmistry)
(Focal Press, 1966), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VLZelikman et.
at, Making and Coating Photographic Emulsion, Focal
Press, 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.

Further, tabular grains having an average aspect ratio of 3 or more and not undergoing reduction sensitization in the presence of a thiosulfonic acid compound can also be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Practice.
(1930)), p. 131; Gatoff, Photographic Science and Engineering (Gutoff, Photograp
hic Science and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226 and 4,414,310;
4,433,048, 4,439,520 and British Patent 2,112,
It can be easily prepared by the method described in No. 157 or the like. The use of tabular grains has advantages such as improved sharpness, increased covering power, and increased color sensitization efficiency with a sensitizing dye.
No. 4,434,226.

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. Further, although the core portion is a clear regular particle, the shell-attached particle may have a slightly irregular shape or an irregular shape. 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 emulsions are useful for promoting 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 the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. And a peptizer may 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 represented by sulfur sensitization and gold sensitization. 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. The effect of the present invention is effective in any case, but particularly preferable is a case where a chemical sensitizing nucleus is formed near the surface. That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization was written by James (THJames), The Photographic Process, 4th Edition, published by Macmillan,
1977, (THJames, The Theory of the Photographic
Process, 4th ed, Macmillan, 1977) using active gelatin as described on pages 67-76;
Research Disclosure, Volume 120, April 1974
Mon, 12008; Research Disclosure, 34, 1975
June, 13452, U.S. Patent Nos. 2,642,361 and 3,297,446
No. 3,772,031, No. 3,857,711, No. 3,901,714,
Nos. 4,266,018 and 3,904,415, and British Patent No. 1,315,755, as described in pAg 5-10, pH 5-8.
And at a temperature of 30 to 80 ° C, sulfur, selenium,
It can be performed using gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound, and sulfur-containing compounds or hypo, thiourea-based compounds, rhodanine-based compounds described in U.S. Pat.Nos. 3,857,711, 4,266,018 and 4,054,457. And the like in the presence of a sulfur-containing compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. Compounds known to suppress fog and increase sensitivity in the course of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine, are used as the chemical sensitization aid. Examples of chemical sensitization aid modifiers are described in U.S. Pat.Nos. 2,131,038, 3,41
Nos. 1,914 and 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 methine dyes or the like. The dyes used include:
Cyanine dye, merocyanine dye, complex cyanine dye,
Complex merocyanine dyes, holopolar cyanine dyes, hemicyanine 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 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, 3,666,480, 3,672,898, 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
507,803, JP-B-43-4936 and JP-B-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-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630,
No. 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. 3,772,002, 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, EP 161,626A and the like.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

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 UK Patent Nos. 2,097,140 and 2,1
No. 31,189, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
-185950, DIR redox compounds or DIR coupler releasing couplers or DIR coupler releasing couplers or redox described in JP-A-62-24252, EP 173,30.
Coupler releasing a dye that recolors after detachment described in 2A,
RD Nos. 11449 and 24241, bleaching accelerator releasing couplers described in JP-A-61-201247 and the like, and ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like.

The following Table B shows specific examples of the color coupler that can be used in the present invention, but the present invention is not limited thereto.

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 high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl Phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, phosphoric acid or phosphonic acid Esters (e.g., trifel phosphate, tricresyl phosphate, 2
-Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
Di-2-ethylhexylphenylphosphonate), benzoates (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoates), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,
4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, N , N-dibutyl-2-
Butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary bath agent, 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. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, -Ethoxyethyl acetate, dimethylformamide and the like.

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-59-58147,
JP-A-59-60437, JP-A-60-227256, JP-A-61-4
Nos. 043, JP-A-61-43743, JP-A-61-42657, etc., in which the coupling speed and the diffusivity of the color coupler are combined with the layer constitution. JP-B-49-15495, U.S. Pat.No. 3,843,469 wherein the same color-sensitive layer is divided into two or more layers, JP-B-53-37017, JP-B-53-37018, and JP-A-51-49027. JP-A-52-143016, JP-A-53-974
No. 24, 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 fixing agents, 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, couplers such as sodium boron hydride, 1-
Auxiliary developing agents 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 typical 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 l 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, the evaporation area of the solution is reduced by reducing the contact area of the processing tank with air.
Preferably, air oxidation is prevented. 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 (III), 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, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. 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 the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831, JP-A-53-37,
No. 418, No. 53-72,623, No. 53-95,630, No. 53-95, 63
No. 1, 53-10,4232, 53-124,424, 53-141,6
No. 23, No. 53-28,426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17,129 (July 1978);
No. 129 thiazolidine derivative; JP-B-45-8,506
No., JP-A-52-20832, JP-A-53-32,735, U.S. Pat.
Thiourea derivatives described in 3,706,561; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836: Other No. 49-42,434, No. 49-59,644, No.
No. 53-94,927, No. 54-35,727, No. 55-26,506, No. 58
Compounds described in -163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West Patent No. 1,290,812, and
Compounds described in No. 95,630 are preferred. In addition, U.S. Pat.
The compounds described in 4,552,834 are also preferred. 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
elevision Engineers Vol. 64, pp. 248-253 (5 May 1955)
Month) can be obtained.

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-58-14,83434 and JP-A-60-220,345 can all be used.

In some cases, a stabilization process may be performed after the water washing process. For example, the stabilization process is used as a final bath of a color photographic material for photography. Examples include a stabilizing bath containing formalin and a surfactant. 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.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Salt complexes and urethane compounds described in JP-A-53-135,628 can be mentioned.

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.

 Examples will be further described below with reference to examples.

Example 1 Double twin particles 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 1: 2 in an aqueous gelatin solution by a control double jet method, and the iodine content of the shell was obtained. Is equivalent to 2 mol%
An emulsion composed of twin grains of 1.2 μm was formed.

After the grains are formed, the emulsion is subjected to a normal desalting and washing step at 40 ° C.
It was redispersed under the conditions of pAg8.9 and pH6.3. The emulsion thus obtained is designated as Em-1. In contrast, one minute before the start of shell formation, the following thiosulfonic acid compounds 1-10, 1
-6, 1-2, 1-16, and 1-21 were added to the reaction pots shown in Table 1-1 to form emulsions.
2 to 6.

When particles are formed as in Em-1, shell formation starts 1
After 1 minute, the following reduction sensitizers 2-A, 2-B and 2-C were added to Table 1
Emulsions Em-7 to Em-15 were prepared by adding the amounts shown in -2.

(Reduction sensitizer) 2-A thiourea dioxide 2-B dimethylamine borane 2-C tin chloride Further, when forming particles similar to Em-1, thiosulfonic acid compound one minute before the start of shell formation 1-10, 1-
6, 1-2, 1-16, and 1-21 were added, and one minute after the start of shell formation, reduction sensitizers 2-A, 2-B, and 2-C were added in appropriate amounts, respectively, as shown in Table 1-3. Emulsion Em-16 of the present invention shown in
~ Em-30 was created.

The emulsions 16 to 30 of the present invention and the emulsions 1 to 15 of the comparative examples thus prepared were optimally gold-sulfur sensitized with sodium thiosulfate and chloroauric acid to prepare chemically sensitized emulsions. did.

The emulsion and the protective layer were coated on the triacetylcellulose film support provided with the undercoat layer in the coating amounts shown in Table 1-4.

Table 1-4 (1) Emulsion layer Emulsion: Emulsions 1 to 30 chemically sensitized (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 Table 1-5.

 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 Ammonium water (28% w / w) 25.0 ml 130 g of sodium ferric ethylenediamine-tetraacetate trihydrate
Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70% w / w) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 Exposure was carried out at 1 second and 1/100 second by ordinary wedge exposure.

A light source adjusted to a color temperature of 4800 ° K using a filter was used, and blue light was extracted using a blue filter (BPN42 manufactured by Fuji Photo Film Co., Ltd.). The sensitivity was compared at a point of 0.2 in optical density from fog. The sensitivity is indicated by a sensitivity of 10 for the sample using the emulsion Em-1.
It was expressed as relative sensitivity as 0. (Either 1/100 ", 1"
100) As is clear from Table 1-5, the emulsion of the present invention has reduced fog and high sensitivity (particularly low illuminance).

Example 2 According to the emulsion preparation method described in Example 1, reduction sensitizer 2-
B was added 1 minute after the start of shell formation, and thiosulfonic acid compounds 1-6 and 1-16 were added 1 minute before the start of shell formation, 10 minutes before the end of shell formation (after about 83% of the shell portion was formed), and Emulsions Em-31 to Em which were added immediately after the completion of formation and immediately before the start of chemical sensitization and optimally sensitized with gold and sulfur as shown in Table 2-1
-38 was formed.

(Addition time of thiosulfonic acid compound) a 1 minute before the start of shell formation b 10 minutes before the end of shell formation c immediately after the end of shell formation d immediately before the start of chemical sensitization These emulsions were coated in the same manner as in Example 1 and sensitometric evaluation was performed. The results shown in Table 2-2 were obtained. The sensitivity was evaluated in the same manner as in Example 1 in terms of relative sensitivity, where the sensitivity of Em-1, which was optimally subjected to gold / sulfur sensitization, was 100.

Here, Em-31 and Em-35 are substantially equal to Em-20 and Em-26, respectively.

As is apparent from Table 2-2, the emulsion sensitized by reduction in the presence of the thiosulfonic acid compound exhibits preferable photographic properties.

Example 3 The following dyes were added to the chemically sensitized emulsion prepared in Example 1 as shown in Table 3-1 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 Sensitive Dye) Sensitizing Dye VIII 2.2 × 10 ⁻⁴ mol / mol Ag The chemical structural formulas of the sensitizing dyes II to IX are shown in Table C below.

In the sensitometry experiment, the emulsion to which the red and green sensitizing dyes were added was exposed using a yellow filter (SC-52, manufactured by Fuji Photo Film Co., Ltd.) instead of the blue filter in Example 1, and exposed to blue. The dye-sensitized emulsion was exposed without using the above filter. Other conditions are the same as in the first embodiment.
Table 3-2 shows the sensitivity of each of Em-39, -40, and -41 for 1 second and
Em- is the relative sensitivity when 100 is set for 1/100 second exposure.
The sensitivity from 39 to Em-59 is shown.

Example 4 pH and pA during shell growth during particle formation in Example 1
Reduction sensitization was performed by changing g. At this time, one minute before the start of shell formation, a thiosulfonic acid compound was added. Table 4 shows the set pH, pAg and the amount of thiosulfonic acid compound added.
-1. The pH, pAg, and the like at the time of redispersion after the desalting and washing step are the same as those in Example 1.

Emulsions 60 to 71 thus prepared were optimally chemically sensitized in the same manner as in Example 1, coated samples were prepared in the same manner, and sensitometry experiments were performed. The results are shown in Table 4-2.

In the table, the sensitivity of Em-60 was set to 100 for both 1 second and 1/100 second, and described as relative sensitivity. As is clear from the table, it was confirmed that the present invention is also effective in reduction sensitization by controlling pH and pAg in the course of grain formation in the presence of gelatin.

Example 5 Samples 501, which are multilayer color photographic materials, were prepared by coating each layer having the following composition on a subbed cellulose triacetate film support.

(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.

(Sample 501) First layer: Antihalation layer Black colloidal silver: silver 0.18 Gelatin: 1.40 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 (Iodine) 6 mol% of silver halide, average grain size of 0.
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 (1st 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 VIII 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) Monodisperse silver iodobromide emulsion (silver iodide) 10 mol%, average particle size 0.
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 μm 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 above compound used for Sample 501 is shown in Table D below.

Silver iodobromide emulsion I of the fifth layer, silver iodobromide emulsion of the ninth layer
II, except that the silver iodobromide emulsion III of the 13th layer was changed.
Samples 502 to 505 were produced in the same manner as in 01.

These samples were exposed to sensitometry 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 5-1 shows the obtained results.
Shown in

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 501 was set to 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each 100.

Processing Method Color development was performed 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 4.5g Add water 1.0l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0 l 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 1.0l pH 6.6 Stabilizer Formalin (40%) 2.0ml Polyoxy Ethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g As is clear from Table 5-1, it can be seen that the emulsion of the present invention hardly increases fog and has an effect of sensitization.

Example 6 The sample 501 of the comparative example and the samples 502 to 505 of the present invention were exposed in the same manner as in Example 5, 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 1.0l pH 10.05 (Bleaching solution) (unit g) Ferric ammonium ethylenediaminetetraacetate dihydrate 120.0 Ethylenediaminetetraacetic acid Disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0ml Add water 1.0l pH 6.3 (Bleaching fixer) (g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0
Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thionitrate aqueous solution (70%) 240.0ml Ammonia water (27%) 6.0ml Add water 1.0l pH 7.2 (aqueous solution) Tap water is replaced with H-type strongly acidic cation exchange resin (ROHM Andhas Amberlite IR-120B) and OH type anion exchange resin (Amberlite IR-400) were packed in a mixed bed column filled with water to reduce the calcium and magnesium ion concentration 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 Add water 1.0l pH 5.0-8.0 The samples 502 to 505 of the invention can be used in Example 5 by this treatment.
The results were as good as.

Example 7 The sample 501 of the comparative example and the samples 502 to 505 of the present invention were exposed in the same manner as in Example 5, and then processed using an automatic developing machine in the following manner.

Processing method Processing time Processing temperature Color development 2 minutes 30 seconds 40 ° C Bleaching and fixing 3 minutes 00 seconds 40 ° C Rinse with water (1) 20 seconds 35 ° C Rinse with water (2) 20 seconds 35 ° C Stable 20 seconds 35 ° C Dry Next, the composition of the treatment liquid is 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 iodobromide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleaching / fixing solution) (Unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0 Ethylenediaminetetrahydrate Acetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thionitrate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleaching accelerator 0.01 mol Add water and add 1.0l pH 6.0 (washing solution) Tap water is converted to H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH-type anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to reduce the concentration of calcium and magnesium ions 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 Add water 1.0l pH 5.0-8.0 The samples 502 to 505 of the invention can be used in Example 5 by this treatment.
The results were as good as.

Example 8 A sample 601 as 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 shown in units of g / m ² . However, silver halide,
For colloidal silver, the amount was expressed in g / m ² of silver, and for the sensitizing dye, it was expressed in moles per mole of silver halide in the same layer.

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 (Equivalent sphere 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 sphere diameter 0.7μ, spherical) Coefficient of variation of equivalent diameter 14%, tetrahedral grains) Silver coating amount 0.15 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, sphere equivalent coefficient of variation 22%, tetrahedral particles) Silver coating amount 0.2 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 ExS-2 1.5 × 10 ^-4 ExS-3 0.4 × 10 ^-4 ExS-4 0.3 × 10 ^-4 ExC-1 0.33 ExC-2 0.009 ExC-3 0.023 ExC-6 0.14 Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, equivalent sphere diameter 1.
0Myu, sphere variation coefficient of 25% equivalent diameter, the plate-like particles, diameter / thickness ratio 4.0) silver coverage 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 (Internal high AgI type, sphere equivalent diameter 1.2μ, sphere) Coefficient of variation of 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 Sixth layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter 0.7 μm, equivalent sphere) Coefficient of variation of diameter 14%, tetrahedral grains) Silver coating amount 0.2 Silver iodobromide 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 0.1 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 emulsion 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-1 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 Structural formula of compound used for sample 601 The results are shown in Table E below.

5th layer silver iodobromide emulsion I, 10th layer silver iodobromide emulsion
Sample 601 except that silver iodobromide emulsion III of the 16th layer was changed.
In the same manner as in the above, samples 602 to 605 were produced.

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours, and then subjected to sensitometric exposure.
The same color development processing was performed.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 6-1 shows the obtained results.
Shown in

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 601 was set to 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each.

As is clear from Table 6-1, the emulsion of the present invention hardly increases fog and has an effect of sensitization.

Example 9 On an undercoated cellulose triacetate film support, a sample 701, which was a multilayer color photographic material composed of layers having the following compositions, was prepared.

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,
ExS; sensitizing dye, ExC; cyan coupler, ExM; magenta coupler, ExY; yellow coupler, Cpd; additive First 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 0.4 µm) Coefficient of variation of equivalent sphere diameter 37%, plate-like particle diameter / thickness ratio 3.0) 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 x 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 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: 0.9 Gelatin: 0.8 ExS-1: 1.6 × 10 ^-4 ExS-2: 1.6 × 10 ^-4 ExS-5: 1.6 × 10 ^-4 ExS-7: 6 × 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.
Sphere equivalent 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-3 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 7th layer (medium speed green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, standard height of core-shell ratio 1: 1)
AgI type, sphere equivalent type, sphere equivalent diameter 0.5μ, variation coefficient of sphere equivalent diameter
20%, plate-like particles, 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 iodobromide emulsion II (core-shell ratio 1: 2; internal high AgI Mold, equivalent ball diameter 0.75μ, coefficient of variation of equivalent ball diameter 25%
0.7 Gelatin… 0.8 ExS-4… 5.2 × 10 ^-4 ExS-5… 1 × 10 ^-4 ExS-8… 0.3 × 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-4 ... 0.04 Polyethyl acrylate latex ... 0.12 Solv-1 ... 0.02 10th layer (donor layer of multilayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 internal high AgI type, sphere equivalent diameter 0.7μ, equivalent to sphere) Coefficient of variation in diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount: 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform type, variation coefficient of equivalent spherical diameter 37%, plate-like grains, diameter / Thickness ratio 3.0) Silver coating amount 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) Equivalent diameter variation coefficient 25%) Coating amount: 0.5 Gelatin: 0.5 ExS-6: 1 x ^10-4 ExY-9: 0.01 ExY-11: 0.20 ExC-1: 0.02 Solv-1: 0.10 15th layer (1st layer) Protective layer) Fine-grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07 μ) 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) Coating amount of silver ... 0.36 Gelatin ... 0.55 polymer Chill acrylate particles diameter 1.5μ 0.2 H-1 0.17 In each layer, 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.

The structural formula of the compound used for Sample 701 is shown in Table F below.

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.

Emulsions 202 to 207 were prepared by adding thiosulfonic acid compounds and reduction sensitizers to Em-201 in the same manner as described in Example 1 in the amounts shown in Table 7-1.

Inventive emulsions 202 to 207 thus produced and Comparative Example 20
1 was optimally gold-sulfur sensitized in each emulsion using sodium thiosulfate and chloroauric acid.

Silver iodobromide emulsion I of the fourth layer, silver iodobromide emulsion of the eighth layer
Sample 701 except that the silver iodobromide emulsion III in the 14th layer was changed.
Samples 702 to 707 were produced in the same manner as in.

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours, and then subjected to sensitometric exposure.
The same color development processing as described above was performed.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 7-2 shows the obtained results.
Shown in

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 701 was set to 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each 100.

As is evident from Table 7-2, the emulsion of the present invention hardly increases fog and has an effect of sensitization.

Example 10 30 g of inert gelatin and 6 g of potassium bromide were added to distilled water 1
Stir the aqueous solution dissolved in
After adding 35 cc of an aqueous solution in which 5.0 g was dissolved and 3.2 g of potassium bromide and 35 cc of an aqueous solution in which 0.98 g of potassium iodide were dissolved at a flow rate of 70 cc / min for 30 seconds, the pAg was raised to 10 and aged for 30 minutes. A seed emulsion was prepared.

Subsequently, a predetermined amount of an aqueous solution 1 in which 145 g of silver nitrate was dissolved and an aqueous solution of a mixture of potassium bromide and potassium iodide were added in equimolar amounts at a predetermined temperature and a predetermined pAg at an addition rate near the critical growth rate, and the plate was added. A core emulsion was prepared. Subsequently, the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in the preparation of the core emulsion were added in equimolar amounts at an addition rate near the critical growth rate to coat the core. A core / shell type silver iodobromide tabular emulsion Em-101 to 104 was prepared.

Aspect ratio adjustment is based on pAg during core and shell preparation.
Was obtained by selecting. The results are shown in Table 8-1.
The average equivalent sphere diameter was 1.2 μm. Also, Em-101
In Nos. To 104, 85% or more of the projected area of all grains were tabular grains.

Average aspect ratio: Measure the aspect ratio of each grain of 1000 randomly extracted emulsion grains, select the grains with the largest aspect ratio in the order of 50% of the total projected area in descending order of the aspect ratio, and determine the aspect ratio of those grains. Arithmetic mean.

In Em-101 to 104, the emulsions obtained by adding the thiosulfonic acid compound 1-2 to the reaction vessel one minute before the start of the shell formation in the amount shown in Table 8-2 to form the emulsions, respectively. 105 to 108. Emulsions prepared by using 1-16 instead of the thiosulfonic acid compound 1-2 in Em-105 to 108 are referred to as Em-109 to 112, respectively.

When grains were formed in the same manner as in Em 101 to 104, thiourea dioxide was used as a reduction sensitizer one minute after the start of shell formation, as shown in Table 8-3.
And Em-113 to 116 were prepared. Em-11
Emulsions Em-117 to 120 and Em-121 to 124 were prepared by adding dimethylamine borane or tin chloride in place of thiourea dioxide as the reduction sensitizer in Examples 3 to 116, and adding them.

When grains are formed in the same manner as in Em-101 to 104, a thiosulfonic acid-based compound is added as shown in Table 8-4 one minute before the start of shell formation, and a reduction sensitizer is added one minute after the start of shell formation. As in Example 4, Em-125 to 148 were prepared.

Em-101 to 148 prepared in this manner were optimally gold-sulfur sensitized in each emulsion using sodium thiosulfate and chloroauric acid, and the following dye was added immediately before coating to obtain a spectrally sensitized emulsion. Created.

Dye group (green dye) The emulsion and the protective layer were coated on the triacetyl cellulose film support provided with the undercoat layer in the following coating amounts.

(1) Emulsion layer Emulsion: Emulsions spectrally sensitized and shown in Tables 8-1 to 8-4 Em-101 to Em-148 (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 Table 8-5.

 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 Salt 4.5g Add water 1 Bleaching solution Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-tetraferric sodium ferric sodium trihydrate 130g Glacial acetic acid 14ml Add water 1 Fixing solution Sodium rattrapolyphosphate 2.0g Sodium sulfite 4.0 g Ammonium thiosulfate (700 g / l) 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 second and 1/100 second in normal wedge exposure .

A light source adjusted to a color temperature of 4800 K using a filter was used, and a yellow filter (SC-52, manufactured by Fuji Photo Film Co., Ltd.) was used. The sensitivity was compared at a point of 0.2 in optical density from fog. Display of sensitivity is Emulsion E
The sensitivity of the sample using m-101 was expressed as a relative sensitivity, taking the sensitivity as 100. The pressure characteristics of the samples were evaluated as follows.
The sample is wrapped around a cylindrical rod having a diameter of 6 mmφ so that the emulsion side of the sample is on the inside, and held for 10 seconds. Thereafter, wedge exposure was performed for 1/100 second under the same exposure conditions as described above, and the same development processing and density measurement were performed. The results of sensitivity and fogging at this time are shown in Table 8-5. Those having little desensitization due to pressure and little fog change are preferable.

As is clear from Table 8-5, the emulsion subjected to reduction sensitization in the presence of the thiosulfonic acid compound 1-2 or 1-16 during grain formation has a high sensitivity, particularly at low illuminance exposure. It can be seen that the fog is high and the fog is low, and the degree of desensitization and increase in fog after bending are also small.

In Em-101 to 104, when the average aspect ratio is large, the deterioration of the photographic characteristics after bending is large, but Em-125 to 148
In the figure, it was found that the deterioration of the pressure property when the average aspect ratio was increased was considerably suppressed, and furthermore, Em-12
From 5 to 148, it can be seen that the emulsion of the present invention (average aspect ratio of 3 or more) has slightly higher sensitivity.

Therefore, the emulsion of the present invention has, firstly, high sensitivity, and secondly, a high aspect ratio and excellent pressure property (equivalent to a low aspect ratio).

Example 11 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multi-layered manner to prepare a sample 1201 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 and colloidal silver, the coating amount is expressed 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: ultraviolet absorber, HBS: high boiling point organic solvent, EX: coupler, S: additive (Sample 1201) 1st layer; antihalation layer Black colloidal silver ... silver 0.18 gelatin ... 1.40 2nd layer; intermediate layer 2,5 -Di-t-pentane Decylhydroquinone ... 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) Monodispersed 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 0.
7μ, average aspect ratio 5.5, average thickness 0.2μ) ... 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 XI… Silver 1.60 Sensitizing dye IX… 5.4 × 10 ^-5 sensitizing dye II ... 1.4 x 10 ^-5 sensitizing dye III ... 2.4 x 10 ^-4 sensitizing dye IV ... 3.1 x 10 ^-5 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) Tabular silver iodobromide emulsion (silver iodide 6 mol%) , Average particle 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 Ninth layer (third green-sensitive emulsion layer) Silver iodobromide emulsion XI ... Silver 1.2 Sensitizing dye V ... 3.5 × 10 ^-5 sensitizing dye VI… 8.0 × 10 ^-5 sensitizing dye VII… 3.0 × 10 ^-4 EX-6… 0.065 EX-11… 0.030 EX-1… 0.025 HBS-1… 0.25 HBS-2… 0.10 Gelatin ... 1.74 10th layer (yellow filter layer) Yellow colloidal silver ... silver 0.05 EX-5 ... 0.08 HBS-3 ... 0.03 Gelatin ... 0.95 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (iodine) 6 mol% silver halide, average grain
6μ, average aspect ratio 5.7, average thickness 0.15μ) ... silver 0.24
Sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.85 EX-8 0.12 HBS-1 0.28 Gelatin 1.28 12th layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide) 10 mol%, average particle size 0.
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 XI ... silver 0.77 Sensitizing dye VIII ... 2.2 x 10 ^-4 EX-9 ... 0.20 HBS-1 ... 0.07 Gelatin ... 0.69 14th layer (first protective layer) Silver iodobromide emulsion (iodide) 1 mol% silver, average particle size 0.07μ)
... 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 formulas of the compounds used are shown in Table D below.

Samples 1202-1208 were prepared in the same manner as Sample 1201, except that the silver iodobromide emulsion XI of the fifth, ninth and thirteenth layers was changed. The emulsion used was the gold-sulfur sensitized emulsion of Example 1.

Exposure to these samples for sensitometry (1/100 second)
And the following color development processing was performed.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 9-1 shows the obtained results.
Shown in

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 1201 was set to 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each.

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 developer 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 l pH 10.0 Bleaching solution Ferric ammonium salt of ethylenediaminetetraacetic acid 100.0 g Disodium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water 1.0 l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 l pH 6.6 Stable Liquid Formalin (40%) 2.0 ml Polyoxyethylene-p-monononyl phenylate Ter (Average degree of polymerization: 10) 0.3 g Water was added and the pressure was evaluated as follows: 1.0 l Evaluation was conducted in the same manner as in Example 10 by bending and then applying the above-described sensitometric exposure, followed by (3 minutes 15 seconds) After performing the color developing treatment of (1), the density was measured with a blue filter, and the fog and sensitivity of the blue-sensitive layer were examined.
The sensitivity was shown as a relative sensitivity with the sensitivity of sample 1201 taken as 100.

For evaluation of sharpness, the MTP of the red-sensitive layer was measured. The MTF value was measured according to the method described in The Theory of Photographic Process 3rd edd. (Published by Macmillan). The exposure was processed by providing white light, and the red color density was measured for cyan color density. 25 cycles / at cyan color density of 1.0
The MTF value for the spatial frequency of mm is shown as a representative value. M
The larger the TF value, the better.

As is clear from Table 9-1, the color photographic light-sensitive material of the present invention has high sensitivity and very excellent sharpness and pressure property.

Example 12 A multilayer color light-sensitive material, Sample 1301, comprising the following layers was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The coating amount was expressed in g / m ² . However, silver halide,
For colloidal silver and colloidal silver, the amount is expressed in g / m ² unit. For sensitizing dye, silver halide 1 in the same layer was used.
It was shown in moles per mole. 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 point organic solvent, W: coating aid, H: hardener, ExS: sensitizing dye, ExC: cyan coupler, Ex
M: Magenta coupler, ExY: Yellow coupler, Cpd: Additive 1st 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 grain 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 0.7μ, coefficient of variation of equivalent spherical diameter 14%, tetrahedral grains) Silver coating amount 0.26 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 0.2 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 0.3 × 10 ^-4 mol ExC-1 0.33 ExC-2 0.009 ExC-3 0.023 ExC-6 0.14 Fourth layer: second 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 XI (Internal high AgI type, equivalent sphere diameter 1.2μ) 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 Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter 0.7 μm, coefficient of variation of equivalent spherical diameter 14%, 14 Silver coating amount 0.2 Silver iodobromide 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 0.1 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 XI (Internal high AgI type, equivalent sphere diameter 1.2 μm) 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 equivalent spherical diameter 14) %, Tetrahedral particles) Silver coating amount 0.1 Silver iodobromide emulsion (AgI 4.0 mol%, internal high iodine type, equivalent spherical diameter 0.4μ, variation coefficient of equivalent spherical diameter 22%, tetrahedral 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, equivalent coefficient of sphere variation 16%, Silver coating 0.19 Gelatin 0.3 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0.1)
3μ) Silver coating amount 0.2 Gelatin 0.36 16th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion XI (Internal high AgI type, equivalent sphere diameter 1.2μ) 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 grain silver iodobromide (equivalent to sphere) 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 The structural formula of the above compound used in sample 1301 is shown in Table E below. Show.

Samples 1302-1308 were prepared in the same manner as Sample 1301, except that the silver iodobromide emulsion XI of the fifth, tenth, and sixteenth layers was changed. The emulsion used was the gold-sulfur sensitized emulsion of Example 1.

These samples were exposed to sensitometry exposure and subjected to the same color development processing as in Example 11.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 10-1 shows the obtained results.
Shown in

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 1301 was set to 100, where the sensitivities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer were each 100.

Evaluation of pressure property and sharpness was performed in the same manner as described in Example 11. The MTF value is a value for a spatial frequency of 25 cycles / mm when the cyan color density is 1.2.
These results are shown in Table 10-1.

As is clear from Table 10-1, the color photographic light-sensitive material of the present invention has high sensitivity, and is excellent in sharpness and pressure.

Example 13 A sample 1401 as a multilayer color photosensitive material comprising the following layers 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,
ExS; sensitizing dye, ExC; cyan coupler, ExM; magenta coupler, ExY; yellow coupler, Cpd; additive First 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 0.4 µm) Coefficient of variation of equivalent sphere diameter 37%, plate-like particle diameter / thickness ratio 3.0) 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 x 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 Internal high AgI ratio of 2: 1, equivalent sphere diameter 0.65μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount: 0.65 silver iodobromide emulsion (4 mol% AgI, uniform) AgI type, ball equivalent diameter 0.
4μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter / thickness ratio 3.0) Coating amount of silver: 0.1 gelatin: 1.0 ExS-1: 2 × 10 ^-4 ExS-2: 1.2 × 10 ^-4 ExS-5 ... 2 × 10 ^-4 ExS-7 ... 7 × 10 ^-6 ExC-1 ... 0.31 ExC-2 ... 0.01 ExC-3 ... 0.06 Fourth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion XI (internal high AgI type, equivalent sphere diameter 1.2μ) 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 ... 6x 10 ^-4 ExC-1 ... 0.07 ExC-4 ... 0.05 Solv-1 ... 0.07 Solv-2 ... 0.20 Cpd-7 ... 4.6 × 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.
Coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter / thickness ratio 2.
0) Silver coating amount ... 0.18 Gelatin ... 0.4 ExS-3 ... 2 x ^10-4 ExS-4 ... 7 x ^10-4 ExS-5 ... 1 x ^10-4 ExM-5 ... 0.11 ExM-7 ... 0.03 ExY-8 ... 0.01 Solv-1 ... 0.09 Solv-4 ... 0.01 7th layer (medium-speed green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface-high AgI type with 1: 1 core-shell ratio, equivalent sphere diameter 0.5μ) , The coefficient of variation of the equivalent sphere diameter 20%, plate-like particles, 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 iodobromide emulsion XI (internal high AgI type, sphere equivalent diameter 1.2μ) Silver coating amount… 0.7 Gelatin… 0.8 ExS-4… 5.2 × 10 ^-4 ExS-5… 1 × 10 ^-4 ExS-8… 0.3 × 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- ... 1 × 10 ^-4 ninth layer (intermediate layer) Gelatin ... 0.6 Cpd-1 ... 0.04 polyethyl acrylate latex ... 0.12 Solv-1 ... 0.02 10th layer (donor layer of interlayer effect for the red sensitive layer) Silver iodobromide Emulsion (AgI 6 mol%, internal high AgI type having a core-shell ratio of 2: 1, sphere equivalent diameter 0.7 μ, coefficient of variation of sphere equivalent diameter 25%, plate-like grains, diameter / thickness ratio 2.0) Silver coating amount: 0.68 Silver halide emulsion (AgI 4 mol%, uniform type, variation coefficient of equivalent sphere diameter 37%, plate-like grains, diameter / thickness ratio 3.0) Silver coating amount 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 12 layers (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent sphere diameter)
0.7μ, sphere equivalent diameter variation coefficient 15%, plate-like grains, diameter / thickness ratio 7.0) Silver coating amount: 0.3 silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 0.
3μ, coefficient of variation of sphere equivalent diameter 30%, plate-like particles, diameter / thickness ratio 7.0) Coating amount of silver… 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 13th layer (intermediate layer) Gelatin ... 0.7 ExY-12 ... 0.20 Solv-1 ... 0.34 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion XI (Internal high AgI type, sphere equivalent diameter 1.2μ) 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 15 layers (first 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 Sixteenth layer (second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07μ) Silver coated Amount: 0.36 gelatin ... 0.55 polymethyl acrylate particles (diameter 1.5μ) ... 0.2 H-1 ... 0.17 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0.07 g / m ² ) Surfactant Cpd-4 (0.03 g / m ² ) was added as a coating aid. The structural formulas of the compounds used are shown in Table F below.

Samples 1402-1408 were prepared in the same manner as Sample 1401, except that the silver iodobromide emulsion XI of the fourth, eighth and fourteenth layers was changed. The emulsion used was the gold-sulfur sensitized emulsion of Example 10.

These samples were exposed to sensitometry exposure and subjected to the same color development processing as in Example 11.

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 11-1 shows the obtained results.
Shown in

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 sensitivity of the sample 1401 was set to 100.

The evaluation of the pressure property and the sharpness were performed in the same manner as described in Example 11. The MTF values are for a spatial frequency of 25 cycles / mm at a cyan color density of 1.3. These results are also shown in Table 11-1.

As is clear from Table 11-1, the color photographic light-sensitive material of the present invention has high sensitivity and excellent sharpness and pressure property.

Example 14 An emulsion was prepared in exactly the same manner as in Em-130 of the present invention except that the compound (2-9) or (3-8) was used instead of the thiosulfonic acid compound (1-2), respectively.
Two kinds of test samples were prepared. Next, fog and sensitivity were determined by the same test as in Example 10.
The effect of suppressing fog and increasing the sensitivity was also observed in the species samples.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiji Yamashita 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fujisha Shin Film Co., Ltd. (72) Inventor Shigeru Shibayama 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fujisha Shin Film Co., Ltd. 72) Inventor Shigeo Hirano 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Inside Fujisha Shin Film Co., Ltd.

Claims (7)

(57) [Claims] In a process for producing a silver halide emulsion, at least one compound selected from compounds represented by the general formulas [I], [II] and [III] is added during the growth of silver halide grains. A silver halide emulsion produced by a method of reduction sensitization in the presence of 10 ^-6 to 10 ^-2 mol per mol of silver halide. [I] in _{R-SO 2 S-M [} II] R-SO 2 S-R 1 [III] R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is 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 [I] to [III] may be polymers containing as a repeating unit a divalent group derived from the structure represented by any one of [I] to [III]. When possible, R, R ¹ , R ² , and L may combine with each other to form a ring. 2. The method according to claim 1, wherein said production comprises at least one compound selected from the compounds represented by formulas [I], [II] and [III].
2. The silver halide emulsion according to claim 1, wherein the two compounds are present in the presence of 10 ^-6 to 10 ^-2 mol per mol of silver halide, reduction sensitized, washed with water and chemically sensitized. 3. The method according to claim 1, wherein said production comprises at least one compound selected from the compounds represented by formulas [I], [II] and [III].
2. The silver halide according to claim 1, wherein the two compounds are present in a concentration of 10 ^{< -6} > to 10 ^<-2 > mol per mol of silver halide, subjected to reduction sensitization, washed with water, chemically sensitized and spectrally sensitized. emulsion. 4. The silver halide emulsion according to claim 1, wherein the tabular grains having an aspect ratio of 3 to 8 account for 50% or more of the total projected area of all silver halide grains. 5. In a process for producing a silver halide emulsion, during the growth of silver halide grains, at least one compound selected from compounds represented by the general formulas [I], [II] and [III] is halogenated. At least 10 ^-6 to 10 ^-2 mol per mol of silver halide and at least the total projected area of all silver halide grains of one emulsion layer containing the silver halide emulsion produced by the method of reduction sensitization. Tabular silver halide grains occupying 50%, and the tabular silver halide grains occupying 50% have an average aspect ratio of 3.0 or more; and having at least one silver halide emulsion layer on a support. Characteristic silver halide color photographic material. [I] in _{R-SO 2 S-M [} II] R-SO 2 S-R 1 [III] R-SO 2 S-Lm-SSO 2 -R 2 Formula, R, R ^1, also R ² is 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 [I] to [III] may be polymers containing as a repeating unit a divalent group derived from the structure represented by any one of [I] to [III]. When possible, R, R ¹ , R ² , and L may combine with each other to form a ring. 6. A silver halide color photographic material according to claim 5, wherein said tabular silver halide grains have an average aspect ratio of 3 to 20. 7. A silver halide color photographic light-sensitive material according to claim 5, wherein the tabular silver halide grains having an average aspect ratio of 3 to 20 account for 50% or more of the total projected area of all silver halide grains.