JP2820154B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material having high sensitivity, low fog and high image density. The present invention also relates to a silver halide photographic light-sensitive material having less fluctuation in sensitivity and fog during the storage period of the photographic material.

(Prior art)

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 deterioration in graininess, it is most preferable to increase the efficiency of converting photoelectrons into a latent image, that is, to increase the quantum sensitivity. In order to increase the quantum sensitivity, it is necessary to remove inefficient processes such as recombination and latent image dispersion as much as possible. It is known that a reduction sensitization method in which small silver nuclei having no development activity are formed inside or on the surface of silver halide is effective for preventing recombination.

Attempts at reduction sensitization have long been considered. Carroll
(Carroll) reduced tin compounds in US Patent No. 2,487,850, Lowe et al. Reduced polyamine compounds in US Patent No. 2,512,925, and Fallens (Farence) reduced thiourea dioxide compounds in British Patent No. 789,823. It has been disclosed that it is useful as a sensitizer. Further Co
llier is Photographic Science and Engine
ering 23: 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She is dimethylamine borane, stannous chloride, hydrazine, high
A method of pH aging and low pAg aging was adopted. The method of reduction sensitization is further disclosed in U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930,867. Regarding not only the selection of reduction sensitizers, but also the invention of reduction sensitization methods, JP-B-57-33572 and JP-B-58-1410
No. Among these, conventionally known reduction sensitizers are listed, and ascorbic acid is described therein. However, compounds such as thiourea dioxide are considered to be preferred, and thiourea dioxide, silver ripened and hydrazine are shown in the examples. Therefore, favorable properties of the ascorbic acid compound as a reduction sensitizer have not been found. For further contrivance, see JP-A-57-17
No. 9835.

However, in order to put reduction sensitization into practical use, it is necessary to overcome the problem of the storage stability of the photosensitive material. A technique for improving the storage stability of the reduction-sensitized emulsion is also disclosed in JP-A-57-82831.
No. 60-178445, but the level of improvement is not yet sufficient. 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 described in Journal of Imaging Science Vol. 29, p. 233 (198
5) was reported by Moisar et al.
At the same time, improvements in the storability of light-sensitive materials containing reduction-sensitized emulsions have been desired.

[Problems to be solved by the invention]

In response to recent demands for higher sensitivity and higher image quality, conventional reduction sensitization techniques have been unsatisfactory. The first is that the sensitivity and fog of the photographic material containing the emulsion subjected to reduction sensitization greatly fluctuate when stored over time. Second, the range of increase in sensitivity due to reduction sensitization is insufficient.

An object of the present invention is to provide a photographic light-sensitive material having high sensitivity and low fog, and in particular, to provide a high-sensitivity photographic light-sensitive material with little change in sensitivity and fog during storage aging. Another object of the present invention is to provide a silver halide photographic material which provides a high maximum image density in addition to the above objects.

[Means for solving the problem]

The above object has been achieved by the following silver halide photographic materials described in (1) and (2).

(1) In the step of producing a silver halide emulsion, at least one emulsion layer containing a monodispersed silver halide emulsion sensitized by reduction with at least one of ascorbic acid or a derivative thereof during grain formation is provided on a support. Silver halide photographic light-sensitive material.

(2) The above-mentioned ((1), wherein the silver halide emulsion is a monodisperse silver halide emulsion which has been reduction-sensitized in the presence of at least one compound represented by the general formula [I], [II] or [III]. The silver halide photographic light-sensitive material according to 1).

[I] R-SO ₂ S-M [II] R-SO ₂ S-R ¹ [III] R-SO ₂ S-Lm-SSO ₂ -R ^{2 In the} formula, even if R, R ¹ and R ² are the same, It may be different and represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas [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].

(3) The silver halide according to the above (1) or (2), wherein the addition amount of ascorbic acid or a derivative thereof is in the range of 5 × 10 ^-5 mol to 1 × 10 ^-1 mol per mol of silver halide. Photosensitive material.

 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 sensitization by gold sensitization, sulfur or selenium sensitization, or a combination thereof. You may go after the feeling. 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 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,
This means that a method is also included in which a reduction sensitization is performed in a state where the growth is temporarily stopped during the growth and then the growth is further performed.

Specific examples of ascorbic acid and its derivatives (hereinafter, referred to as “ascorbic acid compound”) include the following.

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

It is desirable to use a large amount of the ascorbic acid compound used in the present invention as compared with the amount in which a reduction sensitizer is conventionally preferably used. For example, Japanese Patent Publication No. 57-33572 states that the amount of a reducing agent usually does not exceed 0.75 × 10 ^-2 milliequivalents per gram of silver ion (8 × 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (As ascorbic acid, 10 ^-7 to 10 ^-5
Mol / AgX mol) is often effective. (The converted value is based on the inventors). US-2,487,850
Describes "1.times.10.sup.- ^{7 to} 44.times.10.sup.- ⁶ mol as an addition amount in which a tin compound can be used as a reduction sensitizer". JP-A-57-179835 states that it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mole of silver halide, and about 0.01 mg to about 3 mg of stannous chloride. ing. The preferred amount of the ascorbic acid compound to be used in the present invention depends on factors such as the grain size of the emulsion, the halogen composition, the temperature for preparing the emulsion, pH and pAg, but is preferably from 5 × 10 ^-5 mol per mol of silver halide. 1 × 10 ^-1
It is desirable to select from the molar range. It is more preferable to select from the range of 5 × 10 ^-4 mol to 1 × 10 ^-2 mol. It is particularly preferable to select from the range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol.

The ascorbic acid compound of the present invention may be added at any stage of the emulsion production process, but a particularly preferred method is 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 preferable method to add the solution of the reduction sensitizer several times during the formation of the grains or to continuously add the solution for a long time.

The method of reduction sensitization using the ascorbic acid compound of the present invention is more sensitive than conventionally known reduction sensitization methods,
Although excellent in fog and stability over time, combination with other reduction sensitization methods is more preferable in some cases. However, it can be used only as an auxiliary means of reduction sensitization, and the main means of reduction sensitization is preferably performed with an ascorbic acid compound. A method of adding a known reducing agent to a silver halide emulsion as a method of combining,
A method of growing or ripening in an atmosphere with a low pAg of pAg 1 to 7 called silver ripening, pH 8 to 1 called high pH ripening
Either the method of growing in a high pH atmosphere or the method of ripening can be selected.

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,
Although silane compounds and borane compounds are known, ascorbic acid compounds give better results than these known reduction sensitizers.

The reduction sensitization of the present invention is characterized by performing reduction sensitization with an ascorbic acid compound in the production process of a silver halide emulsion, and is selected from compounds represented by general formulas (I), (II) and (III). The reduction sensitization is preferably performed in the presence of at least one compound.

[I] R-SO ₂ S-M [II] R-SO ₂ S-R ¹ [III] R-SO ₂ S-Lm-SSO ₂ -R ^{2 In the} formula, even if R, R ¹ and R ² are the same, It may be different and represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas (I), (II) and (III) will be described in more detail. When R, R ¹ and R ² are an aliphatic group, preferably an alkyl group having 1 to 22 carbon atoms, 2 to 22 alkenyl groups, alkynyl groups, which are
It may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

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

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

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

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group for L include CH _{2 n
(N = 1~12), -CH 2} -CH = CH-CH 2 -, -CH 2 C≡CCH 2 -, A xylylene group, and the like. Examples of the divalent aromatic group for L include phenylene and naphthylene.

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

M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. As an organic cation, an ammonium ion (for example, ammonium,
Tetramethylammonium, tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), guanidine group and the like.

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

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

The compound represented by the general formula [I], [II] or [III] is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. From 10 ^-6 to 10 ^-2 , especially from 10 ^-5
The addition amount of 10 ^-3 mol / mol Ag is preferable.

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 compounds are added before or during reduction sensitization, and these compounds coexist during reduction sensitization. Particularly preferred is a method of performing reduction sensitization in the coexistence during 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, the compounds [I] 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] several times at the same time as 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 present invention, a monodispersed silver halide emulsion is defined as a silver halide emulsion in which the weight of silver halide contained in a grain size range of ± 20% around the maximum grain size is 60% or more of the weight of all silver halide grains. And preferably 70% or more, particularly preferably 80%
% Or more.

Here, the pole large size, frequency n ¹ of particles having a particle size r ¹
And (r ^{1) 3} and the product n ¹ × (r ^{1) 3} is defined as the particle size r ¹ when a maximum, means a particle size which gives the maximum value of the volume frequency curve (three significant figures, the minimum Digits are rounded off to the nearest 5).

The particle size referred to here is the diameter of spherical silver halide grains, and the equivalent diameter of spheres of grains other than spherical.

The monodispersed silver halide emulsion of the present invention may have any halogen composition of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. The preferred silver halide composition is
Silver iodobromide or silver bromide or silver chlorobromide containing 30 mol% or less of silver iodide.

The grains in the monodispersed silver halide emulsion of the present invention may be normal crystals containing no twin planes, as described in the Photographic Society of Japan, Basic Silver Salt Photography of the Photographic Industry (Corona), page 163. Examples include single twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel multiple twins containing two or more non-parallel twin planes according to the purpose. You can select and use it. 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
(h11) plane particles represented by (211), (hh1) plane particles represented by (331), and (210) plane represented by (aging Science 30: 247 page 1986)
Plane particles and (hk1) plane particles represented by the (321) plane also need to be devised in the preparation method, but can be selected and used depending on the purpose. For example, tetradecahedral particles in which (100) and (111) planes coexist in one particle, particles in which (100) and (110) planes coexist, or particles in which (111) and (110) planes coexist. Particles in which one surface or many surfaces coexist can be selected and used depending on the purpose.

The grain size of the silver halide may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm.

In the present invention, two or more kinds of monodisperse silver halide emulsions having different maximum frequency diameters and having been subjected to reduction sensitization in the presence of the compound represented by the formula (I), (II) or (III) are mixed in the same layer. May be used as a mixture, or may be applied as a multi-layer coating on another layer. Further, two or more kinds of polydisperse silver halide emulsions or monodisperse emulsions other than those of the present invention can be used in a mixture of not more than half, preferably not more than 30% by weight based on the total weight of silver halide grains.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell) P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), “Digital Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VLZelikman et.
al, 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.

In the case of a silver halide emulsion containing core / shell type silver halide grains, the silver halide emulsion can be produced by using monodisperse silver halide grains as a core and coating the shell with the core. In order to produce monodispersed silver halide grains having a core portion, grains having a desired size can be obtained by a double jet method while keeping pAg constant.
In addition, highly monodisperse silver halide grains are added, for example, by adding an aqueous solution of potassium iodobromide-gelatin and an aqueous solution of ammoniacal silver nitrate to an aqueous gelatin solution containing silver halide seed particles by changing the addition rate as a function of time. It is manufactured by a method. At this time, the time function of the addition rate, pH, pAg,
By appropriately selecting the temperature and the like, highly monodisperse silver halide grains can be obtained. The shell covering the core can be formed by depositing a soluble halogen compound solution and a soluble silver salt solution on the core of monodisperse silver halide grains by a double jet method.

The method for producing the above-mentioned monodisperse silver halide grains is described in detail in, for example, Photographic Science.
And Engineering (Photographic Science and
Engineering, Volume 6, pp. 159-165 (1962); Journal of Photography Science (Journal of
Photographic Science), 12, 242-251 (1964),
It is described in U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

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

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

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. These emulsion grains are described in GB 1,027,146.
And U.S. Pat. Nos. 3,505,068 and 4,444,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

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

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

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

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, on the other hand, May have a low silver iodide content and a high shell portion. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa.

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

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

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

Silver halide solvents are useful to promote ripening.
For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, these ripening agents can be incorporated in their entirety in 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 typified by sulfur sensitization and gold sensitization, and a remarkable effect is obtained when chemical sensitization is performed. The location of chemical sensitization depends on the composition, structure, and shape of the emulsion grains, and on the intended use in which the emulsion is used. There is a case where a chemical sensitizing nucleus is embedded in the inside of a grain, a case where the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, or a case where a chemical sensitizing nucleus is formed on the surface. Although effective in the case of the effects of the present invention, etc., it is particularly preferable to form a chemical sensitizing nucleus near the surface.
That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

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

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioindole compounds such as oxadrine thione; azaindenes; for example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes, pentaazaindenes and the like); Many compounds known as such 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, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzene 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 from 4 × 10 ^-6 to 8 × 10 ⁶ per mol of silver halide.
^-3 mol, but more preferably about 5 × 10 ^-5 to 2 × when the silver halide grain size is 0.2 to 1.2 μm.
10 ^-3 mol is more effective.

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

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

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

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

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

Examples of cyan couplers include phenol-based and naphthol-based couplers, and are described in U.S. Patent 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 and EP 161,626A.

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

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

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

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

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

Other couplers that can be used in the light-sensitive material of the present invention include, for example, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,33
No. 8,393, multi-equivalent coupler described in 4,310,618 and the like,
DIR redox compounds or DIR coupler releasing couplers or DIRs described in JP-A-60-185950 and JP-A-62-24252.
Coupler emitting coupler or redox, European Patent No.
No. 173,302A, couplers releasing dyes that recolor after release, for example, RD Nos. 11449 and 24241, JP-A-61-20124
The bleaching accelerator releasing couplers described in No. 7, etc., such as the ligand releasing couplers described in U.S. Pat. No. 4,553,477, and the like.

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

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

Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate), phosphorus Acid or phosphonic acid esters (e.g., trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl) Benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenol (E.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g., bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, tris Octyl citrate), aniline derivatives (eg, N, N
-Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like.
Further, as an auxiliary solvent, the boiling point is about 30 ℃ or more, preferably
An organic solvent having a temperature of 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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

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

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

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

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

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

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

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

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

The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amounts of these developers are
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 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. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858 and the like. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

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

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

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

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

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.

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

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

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

〔Example〕

 Hereinafter, the present invention will be further described with reference to examples.

Example 1 In a stainless steel reaction vessel having a capacity of 4 l, 60 g of gelatin and 900 ml of water were added, and an equal amount of an aqueous solution of silver nitrate and an aqueous solution of a mixture of potassium bromide and potassium iodide were added while maintaining the temperature at 60 ° C. A silver iodobromide emulsion as a core was prepared by the method. Subsequently, the core was coated with silver bromide by adding an equal amount of an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to prepare a core / shell type silver iodobromide emulsion.

 Table 1-1 shows the addition time and the concentration of the addition solution.

The pAg during the addition was 8.6 for the first 10 minutes, 8.3 for the next 80 minutes,
The last 20 minutes were kept at 7.3.

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. The resulting emulsion has a maximum particle size of 0.6
μm, the average AgI content (prescription value) is 5 mol%, and the weight of silver halide contained within a particle size range of ± 20% around the maximum particle size is as follows:
It was 75% of the total silver halide grain weight.

When particles are formed as in Em-1, shell formation starts 1
Minutes later, the aforementioned reduction sensitizer A-1 (L-ascorbic acid)
And tin chloride were added in the amounts shown in Table 1-2 to obtain emulsions Em-2 to Em.
-3 was prepared.

Further, when forming particles in the same manner as in Em-1, one minute before the start of shell formation, the thiosulfonic acid compound 1-2, 1-6, 1
-16, and 1 minute after the start of shell formation, reduction sensitizer L
-Emulsions of the present invention and comparative emulsions Em-4 to Em-9 shown in Table 1-3 were prepared by adding ascorbic acid and tin chloride in optimal amounts.

In the Em-1 particle preparation method, the stirring speed after 50 minutes was set to 50.
Em-10 was prepared in the same manner as Em-1, except that the speed was reduced to 0 rpm. The resulting emulsion had a maximum grain size of 0.6 μm, an average AgI content (prescription value) of 5 mol%, and a silver halide weight within ± 20% of the grain size centered on the maximum grain size. 65% of the weight.

Em-4 to Em-9 when forming particles similar to Em-10
In the same manner as in the above, emulsions of the present invention and comparative emulsions Em-11 to Em-16 shown in Table 1-4 were prepared by adding an optimum amount of a thiosulfonic acid compound and a reduction sensitizer, respectively.

A comparative emulsion was prepared as follows. At the time of core formation in the preparation method of Em-1, these aqueous solutions are added so that the addition amounts of silver nitrate and potassium halide are constant per unit time, and the particle size is adjusted so that Em-1 and the maximum particle size match. except
Em-17 was obtained in the same manner as in Em-1. The resulting emulsion had a maximum grain size of 0.6 μm, an average AgI content (prescription value) of 5 mol%, and a silver halide weight within ± 20% of the grain size centered on the maximum grain size. 55% of the weight.

Em-4 to Em-9 when forming particles similar to Em-17
In the same manner as described above, the present invention and emulsion comparative examples Emulsions Em-18 to Em-23 shown in Table 1-5 were prepared by adding optimal amounts of the thiosulfonic acid compound and the reduction sensitizer, respectively.

The emulsion of the present invention thus prepared and the emulsion of Comparative Example Em-
Emulsions 1 to Em-23 were optimally sensitized with gold and sulfur using sodium thiosulfate and chloroauric acid to prepare emulsions.

Samples 1 to 23 were prepared by applying the emulsion and the protective layer to the triacetyl cellulose film support provided with the undercoat layer in the coating amounts shown in Table 1-6.

Table 1-6 (1) Emulsion layer Emulsion: The above-mentioned emulsion Em-1 to Em-23 (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 1-7.

 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 4.5 g Add water 1 Bleaching solution Ethylenediaminetetraacetic acid sodium ferric sodium trihydrate 100 g Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediaminetetraacetic acid sodium salt 10.0 g Glacial acetic acid 14 ml Add water 1 Fixing solution Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1 Stabilizer Formalin 8.0 ml Add water 1 Exposure for 10 seconds and 1/100 A normal wedge exposure was performed in seconds.

The light source was adjusted to a color temperature of 4800 ° K using a filter, and blue light was extracted using a blue filter (BPM42, 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 the sensitivity of sample 1 using emulsion Em-1.
Expressed as relative sensitivity with 100 (1/100 sec, 10 sec both
100 was set. The fog value was a value for a non-exposed part, and was the same value for 1/100 seconds and 10 seconds. ). At the same time, the maximum concentration _Dmax of Sample 1 using Em-1 was also determined.
_It was expressed as a relative concentration with _max being 100.

As is clear from Table 1-7, the emulsion of the present invention has reduced fog, high sensitivity (especially low illuminance), and increased _Dmax .

Samples 1 to 23 coated with the emulsions Em-1 to Em-23 were aged for 12 months in an environment at a temperature of 25 ° C. and a humidity of 60%, and the same sensitometry experiment was performed. Table 1-8 shows the results of relative sensitivities assuming that the sensitivity of Sample 1 before the lapse of time was 100.

The coated sample of the emulsion of the present invention shows that both the decrease in sensitivity after aging and the increase in fog are small, indicating excellent storage stability.

When the same experiment was performed for each of the ascorbic acid compounds A-2 to A-10, the same effect was confirmed.

Example 2 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 multilayer color photosensitive material 101.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in units of g / m ² ). For silver halide and colloidal silver, the coating amount is expressed in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.2 gelatin 2.6 Cpd-3 0.2 Solv-1 0.02 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07 μm) 0.15 Gelatin 1.0 Third layer (low sensitivity red) Sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 5.5 mol%, maximum grain size 0.3μ)
m, variation coefficient related to particle size (hereinafter simply referred to as variation coefficient) 19
%) 1.5 Gelatin 3.0 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 0.3 × 10 ^-4 ExC-1 0.7 ExC-2 0.1 ExC-3 0.02 Cpd-1 0.01 Solv-1 0.8 Solv -2 0.2 Solv-4 0.1 4th layer (high-sensitivity red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion I 1.2 Gelatin 2.5 ExS-1 3.0 × 10 ^-4 ExS-2 1.5 × 10 ^-4 ExS-3 0.45 × 10 ^-4 ExC-4 0.15 ExC-5 0.05 ExC-2 0.03 ExC-3 0.01 Solv-1 0.05 Solv-2 0.3 5th layer (intermediate layer) Gelatin 0.8 Cpd-2 0.05 Solv-3 0.01 6th layer (low sensitivity) Green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 5 mol%, maximum particle size 0.3 μm)
m, coefficient of variation 19%) 0.4 Monodispersed silver iodobromide emulsion (7 mol% silver iodide, maximum particle size 0.5 μm)
0.8 Gelatin 3.0 ExS-4 1 × 10 ^-4 ExS-5 4 × 10 ^-4 ExS-6 1 × 10 ^-4 ExM-6 0.2 ExM-7 0.4 ExM-8 0.16 ExC-9 0.05 Solv-2 1.2 Solv-4 0.05 Solv-5 0.01 7th layer (high-sensitivity green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion II 0.9 Gelatin 1.6 ExS-4 0.7 × 10 ^-4 ExS-5 2.8 × 10 ^-4 ExS-6 0.7 × 10 ^-4 ExM-7 0.05 ExM-8 0.04 ExC-9 0.01 Solv-1 0.08 Solv-2 0.3 Solv-4 0.03 8th layer (yellow filter layer) Yellow colloidal silver 0.2 Gelatin 0.9 Cpd-2 0.2 Solv-2 0.1 Ninth layer (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, maximum particle size 0.3 μm)
m, coefficient of variation 20%) 0.4 Monodispersed silver iodobromide emulsion (5 mol% silver iodide, maximum grain size 0.6μ)
0.4, gelatin 2.9 ExS-7 1 × 10 ^-4 ExS-8 1 × 10 ^-4 ExY-10 1.2 ExC-3 0.05 Solv-2 0.4 Solv-4 0.1 10th layer (high sensitivity blue feeling) Emulsion layer) Monodispersed silver iodobromide emulsion III 0.5 Gelatin 2.2 ExS-7 5 × 10 ^-5 ExS-8 5 × 10 ^-5 ExY-10 0.4 ExC-3 0.02 Solv-2 0.1 11th layer (first protective layer) ) Gelatin 1.0 Cpd-3 0.1 Cpd-4 0.1 Cpd-5 0.1 Cpd-6 0.1 Solv-1 0.1 Solv-4 0.1 12th layer (second protective layer) Fine grain silver bromide emulsion (average particle size 0.07 μm) 0.25 gelatin 1.0 Polymethyl methacrylate particles (1.5 μm in diameter) 0.2 Cpd-8 0.5 In addition, surfactant Cpd-7 and hardener H-1 were added. Table B shows the structural formulas of the compounds used.

The monodisperse silver iodobromide emulsion I of the fourth layer was prepared by appropriately changing the iodine content and the silver content of the shell portion at the time of forming the core grains of Em-1.
(3.5 mol% silver iodide, maximum grain size 0.7 μm), monodispersed silver iodobromide emulsion II of the seventh layer (3.5 mol% silver iodide, maximum grain size 0.8 μm)
m), a monodisperse silver iodobromide emulsion III of the 10th layer (silver iodide 6 mol%, maximum particle size 1.4 μm) was prepared, and it was set as sample 101. Emulsion I was 73%; Emulsion II was 70%; Emulsion III was 66%, by weight of the particles falling within ± 20% of the maximum particle size. Emulsions I-III
Each emulsion is optimally sensitized with gold and sulfur using sodium thiosulfate and chloroauric acid.

Samples 102 to 104 were prepared in the same manner as Sample 101 except that each emulsion was replaced with an emulsion containing a thiosulfonic acid compound and a reduction sensitizer L-ascorbic acid as in Em4-6 during grain formation. Table 2-1 (A)).

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

The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 2-1 shows the obtained results.
It is shown in (B).

The results of the photographic performance were described as relative sensitivities when the sensitivity of the sample 101 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 The color development processing was performed at 38 ° C. according to the following processing steps (the washing step was 24 ° C.).

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%) 2.0ml Polyoxyethylene-p-monononylphenyl ace Ter (Average degree of polymerization 10) 0.3 g Disodium ethylenediaminetetraacetate 0.05 g Add water 1.0 l As is clear from Table 2-1 (B), the emulsion of the present invention has an effect of sensitization with almost no increase in fog.

When the photographic performance after aging was examined in the same manner as in Example 1, it was found that the sample using the emulsion of the present invention exhibited good storage stability.

Example 3 Samples 101 to 104 of the present invention and Comparative Example were exposed in the same manner as in Example 2, and then processed by an automatic developing machine according to the method described below.

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 / fixing solution) (unit: g) Ferric ammonium ammonium diaminetetraacetate dihydrate 50.0 Disodium ethylenediaminetetraacetic acid 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution ( 70%) 240.0ml Ammonia water (27%) 6.0ml Add water 1.0l pH 7.2 (Washing solution) Tap water is replaced with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH Water through a mixed bed column filled with an anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by 20 mg / l of sodium diisocyanurate sodium 1.5 g / L of sodium sulfate was 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 Samples 102 to 104 of the present invention can be used in Example 2 by this treatment.
The results were as good as.

Example 4 Samples 101 to 104 of the present invention and comparative examples were exposed in the same manner as in Example 2, and then processed by an automatic developing machine according to the method described below.

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

(Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleaching and fixing solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetrahydrate Acetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleaching accelerator 0.01 mol 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 Samples 102 to 104 of the present invention can be used in Example 2 by this treatment.
The results were as good as.

Example 5 A sample 201, which is a multilayer color light-sensitive material comprising the following layers, was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The coating amount is g / g for silver halide and colloidal silver.
The amount of silver expressed in m ² units, the amount expressed in g / m ² for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes Indicated by

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 0.07 μm) Silver coating amount 0.15 Gelatin 1.0 ExC-4 0.03 Cpd-2 0.2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter)
1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter)
0.4 μm, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.33 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol Mol ExC-1 0.40 ExC-2 0.11 ExC-3 0.009 ExC-4 0.023 Solv-1 0.24 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter)
1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.55 Gelatin 0.7 ExS-1 3 × 10 ^-4 ExS-2 1 × 10 ^-4 ExS-3 0.3 × 10 ^-4 ExC-1 0.10 ExC-2 0.05 ExC-4 0.025 Solv-1 0.20 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, equivalent spherical diameter 1.4 μm, coefficient of variation of equivalent spherical diameter 28%, plate-like grains, diameter / thickness ratio 6.0 ) Silver coating amount 1.29 Gelatin 0.6 ExS-1 2 × 10 ^-4 mol ExS-2 0.6 × 10 ^-4 mol ExS-3 0.2 × 10 ^-4 mol ExC-2 0.08 ExC-4 0.01 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 6th layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Solv-1 0.1 7th layer: 1st green sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter)
1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter)
0.7 μm, coefficient of variation of sphere equivalent diameter 38%, plate-like particles, diameter /
Thickness ratio 2.0) Silver coating amount 1.0 Gelatin 1.2 ExS-5 5 × 10 ^-4 mol ExS-6 2 × 10 ^-4 mol ExS-7 1 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 0.03 Solv -1 0.2 Solv-4 0.03 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high iodine type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 25%, plate Particles, diameter / thickness ratio 3.0) Silver coating amount 0.47 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 mol ExS-6 1.4 × 10 ^-4 mol ExS-7 0.7 × 10 ^-4 mol ExM-1 0.12 ExM-3 0.01 Solv-1 0.15 Solv-4 0.03 Ninth layer: Intermediate layer Gelatin 0.5 Tenth layer: Third green-sensitive emulsion layer Monodispersed silver iodobromide emulsion III of Example 2 Silver coating amount 1.3 Gelatin 0.8 ExS-5 2 × 10 ^-4 mol ExS-6 0.8 × 10 ^-4 mol ExS-7 0.8 × 10 ^-4 mol ExM-3 0.01 ExM-4 0.04 ExC-4 0.005 Cpd-5 0.01 Solv-1 0.2 11th layer: 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 μm, coefficient of variation of equivalent spherical diameter 14%, 14 faces Silver coating amount 0.1 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent sphere diameter)
0.4 μm, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.05 Gelatin 1.0 ExS-9 3 × 10 ^-4 ExY-1 0.6 ExY-2 0.02 Solv-1 0.15 14th layer: 2nd layer Blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 16%, tetradecahedral grains) Silver coating amount 0.19 Gelatin 0.3 ExS-9 2 × 10 ^-4 mol ExY-1 0.22 Solv-1 0.07 Fifteenth layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0.13)
Silver coating amount 0.2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, equivalent spherical diameter 1.7 μm, coefficient of variation of equivalent spherical diameter 28%, plate Particles, diameter / thickness ratio 5.0) Silver coating amount 1.4 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 grain silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.7 Polymethacrylate particles (1.5 μm diameter) 0.2 W-1 0.02 H-1 0.4 Cpd- 6 1.0 In addition to the above, B-1 (total 0.20 g / m ² ), 1,2-
Benzisothiazolin-3-one (about 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 10,000 ppm) were added. Table C shows the structural formulas of the compounds used.

Samples 202 to 204 were prepared in the same manner as in Sample 201 except that the emulsion of the tenth layer was replaced with an emulsion to which a thiosulfonate compound and a reduction sensitizer L-ascorbic acid were added in the same manner as in Em4 to 6 during grain formation. .

These samples were subjected to sensitometric exposure in the same manner as in Example 2, and subjected to color development processing.

The density of the treated sample was measured with a green filter. Table 3-1 shows the obtained results.

For the photographic performance results, the sensitivity of the green sensitive layer
The relative sensitivity when the sensitivity of 1 was set to 100 was described.

As is clear from Table 3-1, the emulsion of the present invention has an effect of sensitization with almost no increase in fog. Further, when this sample was stored over time in the same manner as in Example 1, the photographic performance was compared. As a result, the fog of Sample 201 was significantly increased and the sensitivity was lowered. On the other hand, it was found that Samples 202 to 204 of the present invention exhibited better photographic performance than Comparative Example 201.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-280243 (JP, A) JP-A-48-87825 (JP, A) JP-A-50-3619 (JP, A) JP-A 63-280243 304253 (JP, A) JP-A-54-1019 (JP, A) US Patent 3047393 (US, A)

Claims (3)

(57) [Claims] In a process for producing a silver halide emulsion, at least one emulsion layer containing a monodispersed silver halide emulsion which has been reduced and sensitized with at least one of ascorbic acid or a derivative thereof during grain formation is supported. A silver halide photographic material as described above. 2. The method according to claim 1, wherein the silver halide emulsion has the general formula [I] or [I]
A monodisperse silver halide emulsion which has been reduction-sensitized in the presence of at least one compound represented by the formula [I] or [III],
The silver halide photographic material according to claim 1. [I] R-SO ₂ S-M [II] R-SO ₂ S-R ¹ [III] R-SO ₂ S-Lm-SSO ₂ -R ^{2 In the} formula, even if R, R ¹ and R ² are the same, It may be different and represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas [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]. 3. The method according to claim 1, wherein the amount of ascorbic acid or a derivative thereof is in the range of 5 × 10 ^-5 mol to 1 × 10 ^-1 mol per mol of silver halide. Silver halide photographic material.