JP2611847B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic material, which is suitable for rapid processing, has high sensitivity, high contrast, and is excellent in safelight safety. Further, the present invention relates to a silver halide photographic material having a good latent image preservability for a long time.

(Prior Art) Currently, commercially available silver halide photographic light-sensitive materials and image forming methods using the same are widely used in various fields. The halogen composition of silver halide emulsions used in many of these light-sensitive materials is often silver iodobromide mainly containing silver bromide for the purpose of achieving high sensitivity, particularly in the case of photographic light-sensitive materials. .

On the other hand, in products used in markets where there is a strong demand for finishing large quantities of prints in a short delivery time, such as photosensitive materials for color photographic paper, bromide containing substantially no silver iodide is required due to the need to increase the development speed. Silver or silver chlorobromide is used.

In recent years, there has been an increasing demand for rapid processing performance improvement of color photographic paper, and much research has been conducted. It is known that increasing the silver chloride content of the silver halide emulsion used results in a dramatic improvement in development speed.

However, a silver halide emulsion having a high silver chloride content has a disadvantage that it is difficult to obtain a high-sensitivity and hard gradation, and furthermore, there is a drawback that reciprocity failure, that is, a change in sensitivity and gradation due to a change in exposure illuminance is large. It is known.

Various techniques have been disclosed to overcome the above-mentioned disadvantages of silver halide emulsions having a high silver chloride content.

JP-A-64-26837 discloses that a high silver chloride emulsion having a silver bromide-rich region near the apex of a grain provides high sensitivity, high contrast, and safe performance. JP 1
-105940 shows that a high silver chloride emulsion having a silver bromide-rich region selectively doped with iridium can provide an emulsion with excellent reciprocity characteristics without impairing the latent image stability for several hours after exposure. Is disclosed.

The present inventors have continued intensive studies thereafter to further improve the performance of the high silver chloride emulsion. As a result, when the high silver chloride emulsion prepared as described above is used as a light-sensitive material, the gradation is softened when the light-sensitive material is exposed to safelight light before printing, and further several days after printing. It has become clear that the latent image stability over a long period of time is not always satisfactory. When such a situation occurs, not only the handling of the photosensitive material in the laboratory is lacked, but also the finished quality of the print may be deteriorated.

The present inventors have found that by performing gold sensitization of a high silver chloride emulsion, the latent sensitization stability over a long period of time is considerably improved. However, gold sensitization may cause soft gradation in some applications, or may degrade the stability of the emulsion or photosensitive material over time before coating. It could not be used.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a halogenated compound which is suitable for rapid processing, has high sensitivity, high contrast, is excellent in safelight safety, and has good latent image preservability for a long time. It relates to a silver photographic light-sensitive material.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, wherein the silver halide emulsion contained in the emulsion layer is cubic or 14 mm thick. The surface of the silver halide grains is mixed by mixing the silver halide host grains with silver halide fine grains having a smaller average grain size than the silver halide host grains and having a high silver bromide content, followed by ripening. A salt substantially free of silver iodide containing 95% or more silver chloride obtained by chemically sensitizing the surface after forming a localized phase having a silver bromide content of at least 10 mol% in the vicinity. It is a silver bromide emulsion and has a pH between the start of the formation of the localized phase and the end of chemical sensitization on the surface.
This was achieved by a silver halide photographic light-sensitive material characterized in that the emulsion was matured under an atmosphere of 6.5 or more.

The halogen composition of the silver halide grains of the present invention must be composed of substantially no silver iodide-free silver chlorobromide in which 95 mol% or more of the total silver halide constituting the silver halide grains is silver chloride. is there. Here, the phrase "contains substantially no silver iodide" means
The silver iodide content is 1.0 mol% or less. A preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, wherein 98 mol% or more of all silver halide constituting the silver halide grains is silver chloride.

The silver halide grains of the present invention need to have a localized phase having a silver bromide content exceeding at least 10 mol%. The arrangement of such a localized phase having a high silver bromide content is required to be in the vicinity of the grain surface in order to exhibit the effect of the present invention, and further from the viewpoint of pressure property, processing solution composition dependency, and the like.
Here, “near the grain surface” means a position within 1/5 of the grain size of the silver halide grains used, measured from the outermost surface. The position is preferably within 1/10 of the grain size of the silver halide grains to be used, as measured from the outermost surface. The most preferable arrangement of the localized phase having a high silver bromide content is such that a localized phase having a silver bromide content of at least 10 mol% or more is epitaxially grown at corners of cubic or tetradecahedral silver chloride grains.

Localized phase with high silver bromide content has a silver bromide content of 10 mol%
However, if the silver bromide content is too high, desensitization may occur when pressure is applied to the photosensitive material,
Variations in the composition of the processing solution may impart undesired characteristics to the photographic material, such as a significant change in sensitivity and gradation. Taking these points into consideration, the silver bromide content of the localized phase having a high silver bromide content is 10
Is preferably in the range of from 20 to 60 mol%, most preferably in the range of from 20 to 50 mol%. The silver bromide content of the localized phase having a high silver bromide content can be determined by an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) and the like. Can be used to analyze. The localized phase having a high silver bromide content is 0.1% of the total silver constituting the silver halide grains of the present invention.
Preferably comprised of 1 to 20% silver, 0.5
More preferably, it is composed of silver of from 7 to 7%.

The interface between the localized phase having a high silver bromide content and other phases may have a clear phase boundary, or may have a transition region in which the halogen composition changes gradually. Good.

Various methods can be used to form such a localized phase having a high silver bromide content. For example, a localized phase can be formed by reacting a potential silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Further, a localized phase can be formed by using a conversion method for converting already formed silver halide grains into silver halide having a lower solubility product. However, cubic or tetradecahedral silver halide host grains are mixed with silver halide fine grains having an average grain size smaller than that of the silver halide host grains and having a high silver bromide content, followed by ripening. The formation of a localized phase with a high silver content is
It is most preferable to exhibit the effects of the present invention.

The formation of the localized phase having a high silver bromide content is preferably performed in the presence of an iridium compound. Here, the formation of the localized phase in the presence of the iridium compound means that the iridium compound is supplied simultaneously with, immediately before, or immediately after the supply of silver or halogen for forming the localized phase. Say. After mixing silver halide fine grains having a smaller average grain size than silver halide host grains and having a high silver bromide content and then ripening to form a localized phase having a high silver bromide content, It is most preferable that an iridium compound is previously contained in silver halide fine grains having a high silver bromide content. The iridium compound may be present during the phase formation other than the formation of the localized phase having a high silver bromide content, but the localized phase having a high silver bromide content is formed together with at least 50% of the total iridium added. Is preferred. Most preferably, it is formed with at least 80% of the total iridium added.

In the present invention, it is necessary to chemically sensitize the surface after forming a localized phase having a high silver bromide content. As the chemical sensitization, sulfur sensitization is preferably performed, but it is also preferable to use gold sensitization, reduction sensitization and the like in combination.

The chemical sensitization with sulfur used in the present invention is performed using a compound containing sulfur which can react with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanines). These examples are described in U.S. Pat.
Nos. 1,574,944, 2,278,947, 2,410,689, 2,728,668, and 3,656,955.

In the present invention, it is necessary to ripen in an atmosphere of pH 6.5 or more from the start of the formation of the localized phase having a high silver bromide content to the end of the chemical sensitization of the surface. If the pH is too high, it can cause unintended fogging
9.0 or less is preferable. As the effect of the present invention, the pH is more preferably in the range of 6.8 to 8.0, and most preferably in the range of 7.0 to 7.7. The ripening in an atmosphere of pH 6.5 or more may be performed only when a localized phase having a high silver bromide content is formed, or only when the surface is chemically sensitized. Further, ripening may be performed under an atmosphere of pH 6.5 or more for a part of time during the formation of a localized phase having a high silver bromide content or the chemical sensitization of the surface, or it may be divided into several portions. You may do it. However, in order to make the effect of the present invention more remarkable, it is preferable to maintain the localized phase having a high silver bromide content and the chemical sensitization of the surface in an atmosphere of pH 6.5 or more.

The silver halide grains of the present invention may have a (100) face, an (111) face, or both of them on the outer surface. Although a beam may include a higher-order plane, a cube mainly composed of a (100) plane or a tetrahedron is preferable.

The size of the silver halide grains of the present invention may be within the range usually used, but the average grain size is 0.1 μm to 1.5 μm.
m is preferred. The particle size distribution may be polydisperse or monodisperse, but is preferably monodisperse. The particle size distribution, which represents the degree of monodispersion, is the ratio (s / d) between the statistical standard deviation (s) and the average particle size (d).
Is preferably 0.2 or less, more preferably 0.15 or less. It is also preferable to use a mixture of two or more monodisperse emulsions.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). Specific examples of compounds and spectral sensitization methods described in JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material is coupled with an oxidized form of an aromatic amine-based color developing agent to form a yellow coupler, a magenta coupler, and a cyan coupler which respectively form yellow, magenta, and cyan. Is usually used.

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following formulas (C-I), (C-II), (M-I), (M-II) and (Y).

General formula (C-I) General formula (C-II) General formula (MI) General formula (M-II) General formula (Y) In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a coloring dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamido ballast group as described in JP-A No. 226,849 and pyrroloazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in European Patent Publication Nos. 226,849 and 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂
And the substituents of R ₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom. And a nitrogen atom-elimination type is particularly preferable.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color relationship to light to be exposed--yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, it is possible to carry out color reproduction by the corrosion-reduction method. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
A high-boiling organic solvent having a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound (wherein W ₁ , W ₂ and W ₃ are each a substituted or unsubstituted alkyl group, cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, W ₄ represents W _1, OW ₁ or S-W _1, n is 1 to 5 integer, and when n is 2 or more W ₄ May be the same or different from each other, and in the general formula (E), W ₁ and
W ₂ may form a fused ring).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
52-6623, etc., gallic acid derivatives, methylenedioxybenzenes and aminoferols are described in U.S. Pat.
Nos. 3,457,079, 4,332,886 and JP-B-56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, a benzoxazole compound (for example, US Patent No.
Nos. 3,406,070 and 3,677,672 and 4,271,307) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used.
These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

In addition, it is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The use of a compound (G) which chemically binds to the oxidized form of an aromatic amine color developing agent to form a chemically inert and substantially colorless compound is used simultaneously or independently, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of from 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with p-anisidine. It is a compound that reacts. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) _n -X General formula (F II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a ring.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilicity “Cll ₃ I value (RGPea
rson, et al., J. Am. Chem. Soc., 90 , 319 (1968)), or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid or any one treated with an acid may be used. For details on the method of producing gelatin, see The Macromolecular Chemistry of Gelatin (Academic
Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing, and washing (or stabilization). Bleaching and fixing may be performed separately, instead of in a single bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is 4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline (Exemplary compound D-6).

Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, p-toluenesulfonates and the like may be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, substantially not containing, preferably 2 ml / or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml / or less, and most preferably, no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63-63
No. 44657, No. 63-44656, U.S. Pat.
2,494,903, JP-A-52-143020, and JP-B-48-30496.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrozides)
Are particularly preferred, and for details, see Japanese Patent Application No. 62-2552.
No. 70, No. 63-9713, No. 63-9714, No. 63-11300 and the like.

Further, it is more preferable to use the hydraxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines disclosed in Japanese Patent Application No. 63-9713. 63
Other amines described in -11300 can be mentioned.

In the present invention, 3.5 × 1 chloride ion in the color developer
The content is preferably 0 ^{-2 to} 1.5 × 10 ^-1 mol / mol. Particularly preferably, it is 4 × 10 ^-2 to 1 × 10 ^-1 mol /. When the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / mol, it has a disadvantage of delaying the development, and is not preferable for achieving the object of the present invention of rapid and high maximum concentration. Further, if it is less than 3.5 × 10 ⁻² mol / mol, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
The content is preferably from × 10 ⁻⁵ mol / to 1.0 × 10 ⁻³ mol /. More preferably, 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol /
It is. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / mol, the development is delayed, the maximum density and the sensitivity are lowered, and
If the amount is less than ^10-5 mol / m, fogging cannot be sufficiently prevented.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to the color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with the preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are soluble and have a high pH of 9.0 or more.
It is excellent in the buffering capacity in the H region, has no adverse effects on photographic performance (such as fog) even when added to a color developer, and has the advantages of being inexpensive, and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1 , 2-Diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'- Bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like can be mentioned.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-43429 and the like, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Nos. 546, 2,596,926 and 3,582,346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-B-42-2388.
No. 3, US Pat. No. 3,532,501, etc., polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1 g-4 /.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer applicable to the present invention is 20 to
The temperature is 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although the replenishment amount is preferably small, it is suitably 20 to 600 ml, preferably 50 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably 60ml-200m
l, most preferably from 60 ml to 150 ml.

Next, the desilvering step applicable to the present invention will be described. As the desilvering step, generally, any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.
An iron ion complex salt may be formed. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylate iron complexes are preferred, and the amount added is 0.01 to 1.0 mol /, preferably
0.05 to 0.50 mol /.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
Compounds having a mercapto group or a disulfide bond described in 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July, 1978), JP-B-45-8506, JP-A-52-50 -20832, 53-327
No. 35, U.S. Pat. No. 3,706,561, and the like, thiourea-based compounds or halides such as iodine and bromine ions are preferred because of their excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). One or more inorganic salts having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary; Organic salts and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

Fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid Thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas, which can be used alone or in combination of two or more. . Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per one is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, It preferably contains a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions
The content is preferably 0.02 to 0.05 mol / mol, more preferably 0.04 to 0.40 mol /.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed.

The amount of rinsing water in the rinsing process can vary widely depending on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set. Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journa
l of the Society of Motion Picture and Television
Engineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 to 1 or less per 1 m ^{2 of the} photosensitive material is possible, and the effect of the present invention is remarkable. Problems occur. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, 61-12
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A No. 145, benzotriazole described in JP-A-61-26761, copper ions and others, written by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) And the bactericides described in (1) and (2).

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution, for example, an aldehyde compound represented by formalin, or a film suitable for stabilizing a dye.
Examples include a buffer for adjusting the pH, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
Known methods described in JP-A Nos. 8543, 58-14834, 60-220345, etc. can all be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

The preferred pH of the washing step or the stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably
15 seconds to 1 minute and 45 seconds, more preferably 30 seconds to 1 minute and 30 seconds.
It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like.

Example 1 32 g of lime-processed gelatin was added to 1000 cc of distilled water,
After dissolving in, 3.3 g of sodium chloride is added and the temperature is raised to 60 ° C.
Was raised. 1.8 cc of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added to this solution.
Subsequently, a solution prepared by dissolving 32.0 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 11.0 g of sodium chloride in 200 cc of distilled water were added to the above solution over 14 minutes while maintaining the temperature at 60 ° C. Further, a solution in which 128.0 g of silver nitrate was dissolved in 560 cc of distilled water and a solution in which 44.0 g of sodium chloride were dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 60 ° C. After subjecting to desalting and washing at 40 ° C., 90.0 g of lime-processed gelatin was added, and pAg was further increased to 7.5 with sodium chloride and sodium hydroxide.
The pH was adjusted to 6.2. Subsequently, a red-sensitive sensitizing dye (S-
After 1) was added in an amount of 8 × 10 ⁻⁵ mol per mol of silver halide, sulfur sensitization was optimally performed at 50 ° C. using triethylthiourea. The silver chloride emulsion thus obtained was named Emulsion A.

After adjusting the pH to 7.2 before sulfur sensitization from emulsion A, a silver chloride emulsion was prepared which was different only in that sensitization was optimized.

Emulsion A was added to a silver bromide ultrafine grain emulsion (particle size: 0.05 μm) containing 0.8 mol of silver bromide with respect to silver chloride at 50 ° C. before sulfur sensitization, followed by ripening for 15 minutes. A silver bromide emulsion was prepared which was different only in that the sensitization was optimized.

The emulsion was adjusted to pH 6.7 before adding ultrafine silver bromide particles to the emulsion C, and then a silver chlorobromide emulsion was prepared which was different from the emulsion C only in that the sensitization was optimized.

The emulsion was adjusted to pH 7.2 before the addition of ultrafine silver bromide particles, and a silver chlorobromide emulsion was prepared, which was different from the emulsion D only in that sensitization was optimized.

After adjusting the pH to 7.8 before adding the ultrafine silver bromide particles to the emulsion E, a silver chlorobromide emulsion was prepared which was different from the emulsion E only in that the sensitization was optimized.

With respect to the six kinds of emulsions A to F thus prepared, the shape, the grain size, and the grain size distribution of the grains were determined from electron micrographs. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size. The six types of emulsions A to F were cubic grains having a grain size of 0.56 μm and a grain size distribution of 0.09.

Electron micrographs of Emulsions C, D, E and F to which ultrafine silver bromide particles were added showed that the cubes had sharper corners than Emulsions A and B to which no ultrafine silver bromide particles were added. Was. X of emulsions C, D, E and F
The line diffraction showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol% to 50 mol%. From the above, it can be said that the emulsions C, D, E, and F are obtained by epitaxially growing a localized phase having a silver bromide content of 10 mol% to 50 mol% at the corners of cubic silver chloride grains.

On a paper support laminated on both sides with polyethylene, a multilayer color photographic paper having the following layer constitution was produced. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) were added to 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7) and dissolved, and the resulting solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, silver chlorobromide emulsion (cubic, 3: 7 mixture of 0.88μm and 0.70μm average grain size (silver mole ratio). Coefficient of variation of grain size distribution is 0.08 and 0.10, each emulsion is silver bromide) 0.
2 mol% is localized on the grain surface), and 2.0 × 10 ^-4 mol of the following blue-sensitive sensitizing dye is added per mol of silver to the large-size emulsion, and , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-4 for small size emulsion
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average and 0.39 μm emulsion (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion is AgBr
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv) -5) 0.24 Fifth layer (red-sensitive layer) Silver chloride emulsion A 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree
17%) 0.17 Liquid paraffin 0.03 The photosensitive material obtained as described above is designated as A. The photosensitive material A was prepared by replacing only the emulsion of the fifth layer (red-sensitive layer) as shown in Table 1, and these were designated as photosensitive materials B, C, D, E and F.

In order to examine the sensitivity and gradation of the six types of photosensitive materials thus obtained, exposure was performed for 0.1 second through an optical wedge and a red filter, and one hour later, color development was performed using the following processing steps and processing solutions. Was.

In order to investigate the safelight safety of light-sensitive materials, use the Fujifilm's Safelight Filter 10 for color photographic paper.
10 at 1m distance from 10W tungsten lamp through 3A
After exposing the light-sensitive material for 1 minute, a wedge exposure of 0.1 second was performed, and the same processing as described above was performed.

To examine the latent image stability of the light-sensitive material, the same processing as described above was performed 72 hours after giving a 0.1-second wedge exposure.

 Processing time Temperature Color development 35 ° C 45 seconds Bleaching and fixing 30-35 ° C 45 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Dry 70-80 ° C 60 seconds Is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-N- (β-methane Sulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g N, N-bis (carboxymethyl) hydrazine 5.5 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g Add water and 1000 ml pH (25 ° C) 10.05 Bleach-fix solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water to 1000 ml pH (25 C) 6.0 Rinse liquid Ion-exchanged water (3 ppm or less for calcium and magnesium, respectively) The reflection density of the treated sample thus prepared was measured to obtain a characteristic curve. Sensitivity (S) is more than fog density
The reciprocal of the exposure required to give 0.5 higher density, expressed as a relative value with the sensitivity of photosensitive material A being 100. Gradation (G)
Is expressed as the difference between the density at which the sensitivity was calculated and the density for the exposure that was increased by 0.5 logE from the exposure.

As an evaluation of safelight safety, a density change ΔD (S) when a safelight was irradiated at an exposure amount that gave a density of 0.5 to a sample not irradiated with the safelight was read. As an evaluation of the latent image stability, a density change ΔD (L) in the case of processing after 72 hours of exposure at an exposure amount giving a density of 0.5 to the sample processed after 1 hour of exposure was read.

 The results are shown in Table 1.

As is evident from the results in Table 1, Emulsions A and B having no localized phase having a high silver bromide content are excellent in safelight safety and latent image preservability, but are low in sensitivity and soft. Further, even if the pH at the time of chemical sensitization is set high, the change is slight. Emulsion C, which has a localized phase having a high silver bromide content, has higher sensitivity than Emulsion A, but is extremely poor in safelight safety and latent image storability. Emulsions D, E and F, in which the formation of a localized phase having a high silver bromide content and the chemical sensitization of the surface were performed at a relatively high pH, the safelight safety and latent image preservability were dramatically improved, Further, high sensitivity and high contrast were achieved.

With respect to the above-mentioned emulsion, a drastic improvement of the latent image preservability according to the present invention was also confirmed in the emulsion in which the temperature at the time of adding silver bromide fine grains and sulfur sensitization was changed to 56 ° C.

Example 2 Lime-treated gelatin (32 g) was added to distilled water (1000 cc) at 40 ° C.
After dissolving in, 3.3 g of sodium chloride was added, and the pH was set to 6.2 with sodium hydroxide, and then the temperature was raised to 50 ° C. To this solution, 2.7 cc of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added. Subsequently, a solution prepared by dissolving 32.0 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 11.0 g of sodium chloride in 200 cc of distilled water were added to the above solution over 14 minutes while maintaining the temperature at 50 ° C. Silver nitrate
A solution in which 1.6 g was dissolved in 60 cc of distilled water and a solution in which 1.12 g of potassium bromide was dissolved in 60 cc of distilled water were added and mixed over 10 minutes while maintaining 50 ° C. Furthermore, 128.0 g of silver nitrate is distilled water 560 cc
And a solution of 44.0 g of sodium chloride dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining 50 ° C. Subsequently, 8 × 10 ⁻⁵ mol of a red-sensitive sensitizing dye (S-1) was added per 1 mol of silver halide. After subjecting to desalting and washing at 40 ° C., 90.0 g of lime-processed gelatin was added, and pAg was further increased to 7.5 with sodium chloride and sodium hydroxide.
The pH was adjusted to 6.2. Thereafter, sulfur sensitization was optimally performed at 50 ° C. using triethylthiourea. Silver chlorobromide emulsion thus obtained (containing 1 mol% of silver bromide)
Was used as Emulsion G.

Emulsion G was adjusted to pH 7.2 before sulfur sensitization, and then a silver chlorobromide emulsion was prepared which was different only in that sensitization was optimized.

Add 32 g of lime-processed gelatin to 1000 cc of distilled water, and add
After dissolving in, 3.3 g of sodium chloride was added, and the pH was set to 6.2 with sodium hydroxide, and then the temperature was raised to 50 ° C. N, N'-dimethylimidazolidin-
2.7 cc of 2-thione (1% aqueous solution) was added. Next, sodium chloride and sodium chloride dissolved in 200 cc of distilled water with 32.0 g of silver nitrate
A solution prepared by dissolving 11.0 g in 200 cc of distilled water was added to the above solution over 14 minutes while maintaining the temperature at 50 ° C., and mixed. Further silver nitrate 12
8.0g dissolved in 560cc of distilled water and 44.0g of sodium chloride
Is dissolved in 560 cc of distilled water.
The mixture was added over a period of minutes. Subsequently, a red-sensitive sensitizing dye (S-
1) was added in an amount of 8.times.10.sup.- ⁵ mol per mol of silver halide.
Further, a solution prepared by dissolving 1.6 g of silver nitrate in 60 cc of distilled water and a solution prepared by dissolving 1.12 g of potassium bromide in 60 cc of distilled water were added and mixed over 10 minutes while maintaining the temperature at 50 ° C. After desalting and washing at 40 ° C, 90.0 g of lime-processed gelatin was added, and the pAg was further increased to 7.5 with sodium chloride and sodium hydroxide.
The pH was adjusted to 6.2. Thereafter, sulfur sensitization was optimally performed at 50 ° C. using triethylthiourea. The silver chlorobromide emulsion (containing 1 mol% of silver bromide) thus obtained was designated as Emulsion I.

After adjusting the pH to 7.2 before sulfur sensitization from Emulsion I, a silver chlorobromide emulsion was prepared which was different only in that the sensitization was optimized.

Add 32 g of lime-processed gelatin to 1000 cc of distilled water, and add
After dissolving in, 3.3 g of sodium chloride was added, and the pH was set to 6.2 with sodium hydroxide, and then the temperature was raised to 50 ° C. To this solution, 2.7 cc of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added. Subsequently, a solution prepared by dissolving 32.0 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 11.0 g of sodium chloride in 200 cc of distilled water were added to the above solution over 14 minutes while maintaining the temperature at 50 ° C. Silver nitrate
A solution prepared by dissolving 128.0 g in 560 cc of distilled water and sodium chloride 44.
0 was dissolved in 560 cc of distilled water.
The mixture was added over a period of minutes. Subsequently, a red-sensitive sensitizing dye (S-
1) was added in an amount of 8.times.10.sup.- ⁵ mol per mol of silver halide.
A silver bromide ultrafine grain emulsion (particle size 0.05 μm) was added in an amount containing 1.0 mol% of silver bromide with respect to silver chloride, ripened for 15 minutes, and then desalted and washed with water at 40 ° C. 90.0 g of lime-processed gelatin was added, and the pAg was adjusted to 7.5 and the pH was adjusted to 6.2 with sodium chloride and sodium hydroxide. Thereafter, sulfur sensitization was optimally performed at 50 ° C. using triethylthiourea. The silver chlorobromide emulsion (containing 1 mol% of silver bromide) thus obtained was designated as Emulsion K.

After adjusting the pH to 7.2 before sulfur sensitization from emulsion K, a silver chlorobromide emulsion was prepared which was different only in that the sensitization was optimized.

Each of the six types of emulsions from G to L has a grain size.
Cubic particles having a particle size distribution of 0.50 μm and a particle size distribution of 0.11 were obtained.

Electron micrographs of Emulsions I, J, K and L are shown in Emulsion G
And H, the corner of the cube had a sharper shape. Emulsions G, H, I, J, K and L
X-ray diffraction showed weak diffraction at a portion corresponding to a silver bromide content of 10 mol% to 50 mol%. From the above, emulsions G and H contain a localized phase having a silver bromide content of 10 mol% to 50 mol% inside the grains, and emulsions I, J, K and L show corner portions of cubic silver chloride grains. Has a silver bromide content of 10 mol%
To 50 mol% of the localized phase epitaxial growth.

The photosensitive material A of Example 1 was prepared by changing only the emulsion of the fifth layer (red-sensitive layer) as shown in Table 2 and preparing these photosensitive materials G, H, I, J, K and L.

The sensitivity, gradation, safelight safety and latent image stability of the six types of photosensitive materials thus obtained were determined in Example 1. Was evaluated in the same way as The results are shown in Table 2.

As is clear from the results in Table 2, when the emulsions G and H each containing a localized phase having a high silver bromide content inside the grains were compared, the sensitivity, gradation, safelight safety and latent image preservability were improved. The effect of pH during chemical sensitization is very slight. Comparing Emulsions I and J, and K and L, which have a localized phase having a high silver bromide content near the grain surface, the emulsions J and L, which were subjected to chemical sensitization at a relatively high pH, showed safelight safety. Further, the storage stability of the latent image has been dramatically improved, and higher sensitivity and higher contrast have been achieved. The effect is remarkable in the emulsion L in which a localized phase having a high silver bromide content is formed near the grain surface by adding ultrafine silver bromide particles.

Example 3 32 g of lime-processed gelatin was added to 1000 cc of distilled water,
After dissolving in, 1.6 g of sodium chloride is added, and the temperature is 54 ° C.
Was raised. 1.7 cc of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added to this solution.
Subsequently, a solution prepared by dissolving 32.0 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 11.0 g of sodium chloride in 200 cc of distilled water were added to the above solution over 14 minutes while maintaining the temperature at 54 ° C. Further, a solution in which 128.0 g of silver nitrate was dissolved in 560 cc of distilled water and a solution in which 44.0 g of sodium chloride were dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 54 ° C. After subjecting to desalting and washing at 40 ° C, 90.0 g of lime-processed gelatin was added, and the pAg was further increased to 8.1 with sodium chloride and sodium hydroxide.
The pH was adjusted to 6.0. After the temperature was raised to 46 ° C., 6 × 10 ^-5 mol of a red-sensitive sensitizing dye (S-1) was added per mol of silver halide. Subsequently, a silver bromide ultrafine grain emulsion (particle size 0.05
μm) was added in an amount containing 0.55 mol% of silver bromide with respect to silver chloride, and after aging for 25 minutes, triethylthiourea was used.
Optimum sulfur sensitization at 46 ° C. The silver chlorobromide emulsion (containing 0.55 mol% of silver bromide) thus obtained was designated as Emulsion M.

Emulsion M was prepared by adding a silver bromide ultrafine grain emulsion, ripening, adjusting the pH to 7.3 with sodium hydroxide before sulfur sensitization, and then preparing a silver chlorobromide emulsion that differs only in that sensitization was optimized. This was Emulsion N.

Emulsion M was adjusted to pH 7.3 with sodium hydroxide before adding the silver bromide ultrafine grain emulsion, and further adjusted to pH 6.0 with sulfuric acid immediately before the start of sulfur sensitization, and then sensitization was optimized. A silver chlorobromide emulsion different from the above was prepared.

Emulsion M was prepared by adjusting the pH to 7.3 with sodium hydroxide before adding the ultrafine silver bromide emulsion, and preparing a silver chlorobromide emulsion which was different only in that sensitization was optimized. .

Emulsion M is a silver bromide ultrafine grain emulsion to be added before sulfur sensitization, in which potassium hexachloroiridate (IV) was previously contained at 1.1 × 10 ^-5 mol per mol of silver bromide to optimize sensitization. A silver chlorobromide emulsion that differs only in that
This was Emulsion Q.

Emulsion P is a silver bromide ultrafine grain emulsion added before sulfur sensitization in which potassium hexachloroiridate (IV) was previously contained at 1.1 × 10 ^-5 mol per mol of silver bromide to optimize sensitization. A silver chlorobromide emulsion that differs only in that
This was Emulsion R.

Each of the six emulsions from M to R has a grain size
Cubic particles having a particle size distribution of 0.52 μm and a particle size distribution of 0.10.

Electron micrographs of Emulsions M, N, O, P, Q and R had a cubic shape with sharp corners. The X-ray diffraction of these emulsions showed weak diffraction at a portion corresponding to a silver bromide content of 10 mol% to 50 mol%. From the above, these emulsions were placed at the corners of cubic silver chloride grains,
It can be said that a localized phase having a silver bromide content of 10 mol% to 50 mol% was epitaxially grown.

The light-sensitive material A of Example 1 was prepared by changing only the emulsion of the fifth layer (red-sensitive layer) as shown in Table 3 and preparing these light-sensitive materials M, N, O, P, Q and R.

The sensitivity, gradation, safelight safety and latent image stability of the six types of photosensitive materials thus obtained were evaluated in the same manner as in Example 1. The results are shown in Table 3.

As is evident from the results in Table 3, ripening in an atmosphere of pH 6.5 or more is performed only when a localized phase having a high silver bromide content is formed or only when the surface is chemically sensitized. Although the effects of the present invention can be obtained, by maintaining both the formation of the localized phase having a high silver bromide content and the chemical imaging of the surface in an atmosphere of pH 6.5 or more, a particularly remarkable effect can be obtained. Is obtained. In addition, by forming a localized phase having a high silver bromide content in the presence of an iridium compound, a high-contrast emulsion can be obtained even in high-illumination exposure as in this experiment, but the safelight safety is significantly deteriorated. . It can be seen that the effect of the present invention is remarkable in the emulsion R of the present invention containing an iridium compound.

(Effects of the Invention) According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which is suitable for rapid processing, has high sensitivity, high contrast, is excellent in safelight safety, and has good latent image preservability for a long time. it can.

Claims (3)

(57) [Claims] 1. A silver halide photographic material having at least one light-sensitive emulsion layer on a support, wherein the silver halide emulsion contained in the emulsion layer is converted into a cubic or tetradecahedral silver halide host grain. After mixing silver halide fine particles having an average particle size smaller than that of the silver host grains and having a high silver bromide content, the mixture is aged and then ripened to have a silver bromide content of at least 10 mol in the vicinity of the surface of the silver halide grains. % Of a silver chlorobromide emulsion containing substantially no silver iodide, in which 95% by mole or more is obtained by chemically sensitizing the surface after forming a localized phase of more than 95%. A silver halide photographic material, which is an emulsion matured under an atmosphere of pH 6.5 or more from the start of phase formation to the end of surface chemical sensitization. 2. A silver halide photographic material according to claim 1, wherein said localized phase is formed in the presence of an iridium compound. 3. The emulsion according to claim 1, wherein said localized phase is an emulsion ripened in an atmosphere having a pH of 7.0 or more and 7.7 or less from the start of formation to the end of chemical sensitization on the surface. The silver halide photographic light-sensitive material according to item (1) or (2).