JPH0695280A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material high in sensitivity and yet small in dependency on rapid processing conditions and strong in resistance to pressure, such as scratching, by using an emulsion high in silver chloride content and superior in rapid processing aptitude. CONSTITUTION:The silver halide photographic sensitive material is obtained by forming on a support at least one emulsion layer containing silver halide grains prepared by adding bromide to substantially cubic silver halide host grains composed of >=95mol% silver chloride in an amount of <=5mol% of the silver halide to form a bromide-localized phase near the vertex of each cubic grin, and then, adding silver chloride to each host grain with the localized- bromide phase in an amount of <=5mol% of the silver halide to deposit it to the host grain.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material having high sensitivity and capable of rapid processing, and a silver halide emulsion used therefor. And a silver halide photographic light-sensitive material capable of rapid processing.

[0002]

2. Description of the Related Art With the spread of color photographic materials, color processing has become simpler and faster, and on the other hand, high quality images and uniform finish quality are required. In general,
A silver iodobromide emulsion containing 4 to 20 mol% of silver iodide is used for a color light-sensitive material for photographing, and a silver chlorobromide emulsion is used for a light-sensitive material for color print. It is known that it is more advantageous than the silver iodobromide emulsion for speeding up development processing. A high silver chloride emulsion having a silver chloride content of 95 mol% or more is particularly advantageous for rapid processing, but has low sensitivity and is difficult to undergo chemical sensitization or spectral sensitization, and the obtained sensitivity is unstable. It had a defect that fogging was also likely to occur.

Several methods have been proposed for solving this problem. For example, as described in JP-A-48-51627 and JP-B-49-46932, a method of adding a water-soluble bromine ion or iodine ion after adding a sensitizing dye to a silver halide emulsion, Kaisho 58-1085
No. 33, No. 60-222845, etc., a bromine ion and a silver ion are simultaneously added to a silver halide grain having a high silver chloride content, and a silver bromide content of 60 mol is added to the surface of the grain. % Or 10 to 50 mol% of a high silver bromide layer, JP-B Nos. 50-36978 and 58-240772, and U.S. Pat. No. 4,471,050.
No. 2, DE 329,999, and the like, to a silver halide having a high silver chloride content, by adding a bromine ion or simultaneously adding a bromine ion and a silver ion, a double structure or bonding of a core and a shell A method for producing grains having a multi-phase structure such as structured grains, as described in JP-A-58-95736, the use of triple-structure grains having a layer mainly consisting of silver bromide inside high silver chloride grains. Method,
As described in JP-A-60-222844, those having a phase mainly composed of silver bromide or a phase having a silver bromide content of 50 mol% or more inside a high silver chloride grain; No. 26837 proposes various methods such as using a silver halide grain having a silver bromide rich region near the apex of the grain and having an average silver bromide content on the surface of 15 mol% or less. However, none of the methods is sufficient to satisfy the rapid processability while maintaining high sensitivity. Also, when trying to increase the sensitivity, when the surface of the photosensitive material before exposure is scratched or rubbed by something,
There is a drawback that the concentration tends to decrease in the portion where the pressure is applied.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to use a high silver chloride silver halide emulsion excellent in rapid processing suitability, maintain high sensitivity, have a small dependency on rapid processing conditions, and prevent scratching. The object of the present invention is to develop a silver halide emulsion having a strong resistance to pressure and provide a silver halide photographic light-sensitive material using the same.

[0005]

As a result of intensive studies, the present inventors have found that the above objects can be solved by the following means. (1) To a cubic silver halide host grain having a silver chloride content of 95 mol% or more, bromide of 5 mol% or less with respect to the silver amount is added to add odor to the vicinity of the apex of the cubic grain. After forming the silver bromide localized phase, it was adjusted by further supplying 5 mol% or less of silver chloride with respect to the silver amount of the host grain having the silver bromide localized phase, and depositing the silver chloride on the host grains. A silver halide photographic light-sensitive material having at least one emulsion layer containing a silver halide emulsion on a support. (2) The silver halide photographic light-sensitive material described in the above item, wherein the silver halide emulsion is chemically sensitized with sulfur, selenium, gold or a combination thereof.

In the silver halide emulsion of the present invention, 5 mol% or less of bromide is added to substantially cubic host grains having a silver chloride content of 95 mol% or more in the vicinity of the apex of the cubic grains. It is produced by forming a localized silver bromide phase and further supplying 5 mol% or less of silver chloride to deposit the silver chloride on host grains. The silver bromide localized phase can be formed by adding a bromide ion, a bromine or a bromide ion sustained-release agent, or a high silver bromide fine grain emulsion to substantially cubic host grains having a silver chloride content of 95 mol% or more. . The method described in JP-A-64-26837 can be used for the method of forming the silver bromide localized phase. Further, regarding the use of bromine or bromide ion releasing agent, JP-A-1-
It is preferable to use the compound represented by the general formula [S] described in No. 285942. CR when forming this localized phase
Preference is given to using compounds. As the CR compound, those described on pages 4 to 5 of JP-A No. 64-26837 can be used. The CR compound has an effect of suppressing a reaction of a new phase richer in silver bromide content than that of the host grain so as to repeat recrystallization and cover the whole grain with a uniform new phase.

The silver bromide localized phase thus obtained is formed near the apexes of cubic grains. Here, the "vicinity of the apex" is defined as one side of the diameter of a circle having the same area as the projected cube or the area of a particle conforming to the cube, and the apex of the particle (a particle considered as a cube or a particle Means the inside of a square that shares with the host particle its one corner. The length is preferably 1/5. The halogen composition of the localized silver bromide phase has a silver bromide ratio of 50.
It is preferably not more than 10% by mol. After the localized silver bromide phase is formed in this way, 5 mol% or less of silver chloride is supplied and deposited on the host grains. In this case, silver chloride may be substantially supplied with silver chloride, for example, chlorine ions and silver ions may be added simultaneously or alternately, or by mixing silver halide grains having a high silver chloride content. May be aged. Also, small amounts of bromine ions and iodine ions can be used together with chlorine ions within a range that does not impair the effects of the present invention. Specifically, the total amount of bromine ions and iodine ions is 3 with respect to silver ions added together with chlorine ions.
It is used in an amount of 0 mol% or less, preferably 10 mol% or less, and particularly preferably 5 mol% or less.

As the silver halide host emulsion used in the present invention, those composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less.
The halogen composition of the emulsion may be different or the same between the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to homogenize the properties of each grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, the silver chloride content is preferably 95 mol% or more, more preferably 98 mol% or more. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μ to 2 μ. Is preferred. The particle size distribution is preferably so-called monodisperse with a coefficient of variation (standard deviation of the particle size distribution excluding the average particle size) of 20% or less, preferably 15% or less. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The silver chloride or silver chlorobromide emulsion used in the present invention is described by P. Glafkides C
himie etPhisique Photographique (published by Paul Montel,
1967), Photog-raphic Emulsion Chem by GF Duffin
istry (Focal Press, 1966), VLZalikman et
al by Making and Coating Photographic Emuldion (Foca
l Press, 1964) and the like. That is, any of the acidic method, the neutral method, the ammonia method, etc. may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method,
Any method such as a simultaneous mixing method and a combination thereof may be used. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed 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 substantially uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can.
In particular, the above Group VIII elements can be preferably used.
The amount of these compounds added may vary over a wide range depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide. The silver halide emulsion used in the present invention is usually chemically and spectrally sensitized. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-21527.
Those described in the lower right column of page 18 to the upper right column of page 22 of the specification of Japanese Patent Publication No. 2 are preferably used. Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength region 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-spectral sensitizing dye that absorbs light in the wavelength range corresponding to the desired spectral sensitivity. The spectral sensitizing dye used at this time is, for example,
By FM Harmer Hete-rocyclic compounds−Cyanine dyes
and related compounds (John Wiley & Sons New York,
Listed in London, 1964). Further, it is also preferable to select and use from the compounds listed as the CR compounds in the above-mentioned JP-A No. 64-26837.

The spectral sensitizing dyes used in the present invention may be used alone or in combination of two or more kinds. Among the sensitizing dyes preferably used in the present invention, the cyanine dye is specifically described in JP-A-2-129628.
(V-1) to (V-3) described on pages 13 to 13
6) can be mentioned. Along with the spectral sensitizing dye, a dye that does not have a spectral sensitizing effect by itself, or a supersensitizer that does not substantially absorb in the visible region but enhances the sensitizing effect of the spectral sensitizing dye is included. Good. In the present invention, an aminostilbene compound substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721) has the above oxazole nucleus. Reduction of residual color of carbocyanine dyes we have,
It is useful for improving the color sensitizing property of a dicarbocyanine dye having a benzothiazole nucleus, and it is particularly preferably used in combination.

The aminostilbene compound preferably used in the present invention is 4,4'-bis (s-triazinylamino) stilbene-2,2'-disulfonic acid or 4,4'-bis (pyrimidinylamino) stilbene. −
2,2'-disulfonic acid and alkali metal salts thereof and the like can be mentioned. In these compounds, the s-triazine ring or the pyrimidine ring is a substituted or unsubstituted arylamino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkyloxy group or It is more preferable that one or two sites are substituted with a hydroxyl group or an amino group.
In order to reduce the residual color, it is more preferable that this portion be substituted with a highly water-soluble substituent. The highly water-soluble substituent is, for example, a substituent containing a sulfonic acid group or a hydroxyl group. These compounds are represented by the following general formula (A).

[0012]

[Chemical 1]

In the formula, D represents a divalent aromatic residue,
R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group and an alkyl group. It represents an amino group, a cyclohexylamino group, an arylamino group, a heterocyclylamino group, an aralkylamino group or an aryl group. Q ₁ and Q ₂ each represent -N = or -C =. However, at least one of Q ₁ and Q ₂ is -N =. Examples of compounds that are particularly preferably used in the invention include (F-1) to (F-24) described on pages 15 to 18 of JP-A-2-129628.

The silver halide emulsion of the present invention can prevent fog from occurring during the production process of a photographic light-sensitive material, during storage until development processing, or during development processing, and enhance the stability of photographic performance. The following compounds may be added and contained for the purpose of That is, first of all, heterocyclic mercapto compounds, such as mercaptothiadiazoles, mercaptotetrazoles, mercaptobenzimidazoles, mercaptobenzothiazoles, mercaptopyrimidines, mercaptothiazoles, etc. Heterocyclic mercapto compounds having a functional group, thirdly azoles, for example, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro-substituted or halogen-substituted), Fourth, cytoketo compounds such as oxazolidinethione, and fifth, azaindenes, such as tetraazaindenes, more specifically hydroxyazaindenes, aminoazaindenes, especially 4-hydroxy-6-methyiene. -
Many compounds known as antifoggants or stabilizers such as 1,3,3a, 7-tetraazaindene and the like, and further benzenthiosulfinic acids and benzensulfinic acids can be added and contained. Particularly, the heterocyclic mercapto compound and azaindene are preferably used in the present invention.

In the present invention, it is particularly preferably used for the purpose of preventing fog and improving processing dependence after addition of silver halide grains during or after grain formation, during chemical sensitization or after finish, or during emulsion coating. The mercaptotetrazole compound can be selected from the compounds represented by the following general formula (Ia).

[0016]

[Chemical 2]

In the formula, R represents an alkyl group, an alkenyl group or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. The alkali metal atom is, for example, a sodium atom or a potassium atom, and the ammonium group is, for example, a trimethylammonium chloride group or a dimethylbenzylammonium chloride group. The precursor is a group which can be X = H or an alkali metal under alkaline conditions, and is, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group or the like.

Of the above R, the alkyl group and the alkenyl group include a non-substituted group and a substituted group, and further include an alicyclic group.
Examples of the substituent of the substituted alkyl group include a halogen atom, an alkoxy group, an aryl group, an acylamino group, an alkoxycarbonylamino group, a ureido group, a hydroxy group, an amino group, a heterocyclic group, an acyl group, a sulfamoyl group, a sulfonamide group and a thioureido group. Groups, carbamoyl groups, and further carboxylic acid groups, sulfonic acid groups or salts thereof,
Etc. can be mentioned. The above ureido group, thioureido group, sulfamoyl group, carbamoyl group and amino group are each unsubstituted, N-alkyl substituted, N
-Including aryl-substituted. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and a substituent of the alkyl group listed above. The preferred mercaptothiadiazole compound can be selected from the compounds represented by the following general formula (IIa).

[0019]

[Chemical 3]

In the formula, L represents a divalent linking group, and R represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. The alkyl group, alkenyl group and X of R are the same as those in formula (Ia). Specific examples of the divalent linking group represented by L above include:

[0021]

[Chemical 4]

The following can be mentioned. n represents 0 or 1, and R ₀ , R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an aralkyl group. Besides these compounds,
Mercaptobenzimidazoles can also be preferably used in the present invention. Preferred specific examples of these compounds are shown below.

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

The silver halide photographic light-sensitive material of the present invention is a color light-sensitive material containing a cyan coupler, a magenta coupler and a yellow coupler, respectively, and having on a support three kinds of silver halide emulsion layers having different color sensitivities. That
It is particularly preferable in achieving the object of the present invention. In the light-sensitive material according to the present invention, a hydrophilic colloid layer is added in order to improve image sharpness and the like, European Patent EP 0,337,
490A2, pages 27 to 76, dyes which can be decolorized by treatment (among others, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which chemically bonds with the oxidant of the group amine color developing agent to form a chemically inactive and substantially colorless compound, simultaneously or alone, is effective in, for example, storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant. Further, in the light-sensitive material according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-271247 is used.
It is preferable to add an antifungal agent as described in No.

As the support used in the light-sensitive material according to the present invention, a white polyester support or a layer containing a white pigment for a display is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8. The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Also, upon exposure, U.S. Pat. No. 4,880,72
It is preferable to use the band stop filter described in No. 6. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The exposed color light-sensitive material is preferably subjected to bleach-fixing processing after color development for the purpose of rapid processing. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing this light-sensitive material. As additives, the following patent publications, especially European patent EP
No. 0,355,660 A2 (JP-A-2-139544)
No.) are preferably used. The color development processing method applied to the light-sensitive material of the present invention includes:
The methods described in JP-A-2-207250, page 27, upper left column to page 34, upper right column are preferable.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in 33144, European Patent EP 0,333,185A2
3-Hydroxypyridine cyan couplers (especially couplers (42) listed as specific examples, which have been converted into 2-equivalent by attaching a chlorine-leaving group to couplers (6) and (9)) Is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used.

[0037]

【Example】

Example 1 An emulsion for a light-sensitive silver halide emulsion layer containing a cyan coupler was prepared as follows. Lime treated gelatin 30g
Was added to 1000 ml of distilled water, dissolved at 40 ° C., the pH was adjusted to 3.8 with sulfuric acid, and 5.5 g of sodium chloride and 0.05 N, N′-dimethylimidazolidine-2-thione were added.
2 g were added and the temperature was raised to 52.5 ° C. A solution prepared by dissolving 62.5 g of silver nitrate in 750 ml of distilled water and a solution prepared by dissolving 21.5 g of sodium chloride in 500 ml of distilled water were mixed.
The solution was added and mixed for 40 minutes while maintaining the temperature at 2.5 ° C. Further, a solution prepared by dissolving 62.5 g of silver nitrate in 500 ml of distilled water and a solution prepared by dissolving 21.5 g of sodium chloride in 300 ml of distilled water were added and mixed at 52.5 ° C. for 20 minutes.

When the obtained emulsion was observed with an electron microscope, it was an emulsion consisting of cubic grains having an average side length of about 0.46 μ and a coefficient of variation of grain size distribution of 0.09. After washing this emulsion with demineralized water, 0.2 g of nucleic acid and red sensitizing dye (V-6) 1 × 10 ⁻⁴ mol / 50 ° C.
A monodisperse silver bromide emulsion having a mol Ag of 0.05 μm and an average grain size of 0.05 μm was added in an amount of 0.6 mol% with silver halide, and optimally chemically sensitized with triethylthiourea. Further, the exemplified compound (I-8) was added at 7 × 10 ⁻⁴ mol / mol Ag to prepare an emulsion Em-1A. Further, the following compounds were added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0039]

[Chemical 9]

A green photosensitive emulsion for a magenta coupler-containing silver halide emulsion layer was prepared as follows. Add 30 g of lime-processed gelatin to 1000 ml of distilled water and add 40 ° C.
After dissolution in, the temperature was raised to 50 ° C. by adding 5.5 g of sodium chloride and 0.02 g of N, N′-dimethylimidazolidine-2-thione. A solution prepared by dissolving 62.5 g of silver nitrate in 750 ml of distilled water and a solution prepared by dissolving 21.5 g of sodium chloride in 500 ml of distilled water at 40 ° C while maintaining a temperature of 50 ° C.
The above solution was added and mixed in minutes. Further silver nitrate 62.5g
A solution obtained by dissolving 500 ml of distilled water in sodium chloride and sodium chloride.
A solution prepared by dissolving 5 g in 300 ml of distilled water was added and mixed at 50 ° C. for 20 minutes. Observation of the obtained emulsion with an electron microscope revealed that the average side length was about 0.44 μm.
The emulsion consisted of cubic grains having a value of 0.08 as the coefficient of variation of the grain size distribution.

After washing this emulsion with demineralized water, 0.2 g of nucleic acid, 5 × 10 ⁻⁴ mol / mol Ag of the exemplified compound (V-41) and monodispersed bromide having an average particle size of 0.05 μm were added at 50 ° C. A silver halide was added in an amount of 0.4 mol% corresponding to silver halide and optimally chemically sensitized with triethylthiourea. Further, the exemplified compound (I-8) was added in an amount of 1.1 × 10 ⁻³ mol / mol Ag to prepare a green photosensitive emulsion Em-2A for a magenta coupler-containing silver halide emulsion layer. This emulsion was used as a low-sensitivity green light-sensitive emulsion for a silver halide emulsion layer containing a magenta coupler.

A blue-sensitive emulsion for a silver halide emulsion layer containing a yellow coupler was prepared as follows. Add 30 g of lime-processed gelatin to 1000 ml of distilled water and add 40 ° C.
After dissolution in, the pH was adjusted to 3.8 with sulfuric acid, 5.5 g of sodium chloride and N, N'-dimethylimidazolidine-2.
-0.03 g of thione was added to raise the temperature to 75 ° C. A solution prepared by dissolving 12.5 g of silver nitrate in 150 ml of distilled water and a solution prepared by dissolving 4.3 g of sodium chloride in 100 ml of distilled water were added to and mixed with the above solution for 30 minutes while maintaining the temperature at 75 ° C. Further, a solution prepared by dissolving 112.5 g of silver nitrate in 1100 ml of distilled water and 38.7 g of sodium chloride were added to 650 ml of distilled water.
The solution dissolved in was added and mixed at 75 ° C. for 40 minutes. When the obtained emulsion was observed with an electron microscope, it was an emulsion composed of cubic grains having an average side length of about 0.82 μ and a value of 0.11 as a variation coefficient of grain size distribution. After washing this emulsion with demineralized water, 0.2 g of nucleic acid and blue sensitizing dye (V-34) 2 × 10 ⁻⁴ mol / 58 at 58 ° C.
Mol Ag and (V-36) 2 × 10 ⁻⁴ mol / mol Ag, 0.3 mol% of silver halide was added to a monodispersed silver bromide emulsion having an average grain size of 0.05 μ, and optimum with triethylthiourea Chemically sensitized. Further exemplified compound (I-8)
Of 9 × 10 ⁻⁴ mol / mol Ag to give a high-sensitivity blue-sensitive emulsion Em- for a silver halide emulsion layer containing a yellow coupler.
3A.

The halogen composition and its distribution of the green-sensitive silver halide emulsion for the magenta coupler-containing layer and the blue-sensitive silver halide emulsion for the yellow coupler-containing layer were observed by X-ray diffraction.
70% to 65% silver chloride in addition to the main peak corresponding to mol%
A broad diffraction pattern having a center in the vicinity of mol% and having a tail in the vicinity of 60 mol% of silver chloride could be slightly observed. After the corona discharge treatment is applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecyl benzene sulfonate is provided, and various photographic constituent layers are further coated to form a multilayer structure as shown below. A color photographic paper was prepared and used as a sample 101. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-)
7) 0.7 g of ethyl acetate 27.2 cc and solvent (So
lv-3) and (Solv-7) (4.1 g) were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate (8 cc) in 10% gelatin aqueous solution 185.
Emulsified dispersion A was prepared by emulsifying and dispersing in cc. Emulsion Em
-3A and the above emulsified dispersion A were mixed and dissolved to prepare a first coating liquid having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer (the cyan coupler was also used as the color image stabilizer (Cp in the fifth layer).
d-7) and the like were dissolved in ethyl acetate and then emulsified and dispersed). 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Further, Cpd-10 and Cpd-11 were added to each layer so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively. Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the yellow coupler-containing emulsion layer, the magenta coupler-containing emulsion layer and the cyan coupler-containing emulsion layer, respectively, at 8.5 × 10 ⁻⁶ per mol of silver halide. Mole, 7.7 × 10 ^-4 mole, 2.5 × 1
^0-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazainde was added to the yellow coupler-containing emulsion layer and the magenta coupler-containing emulsion layer, respectively, in an amount of 1 × 10 ^-4 mol and 2 per mol of silver halide.
× 10 ⁻⁴ mol was added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0045]

[Chemical 10]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper (polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)) First layer (blue sensitive emulsion layer) Emulsion Em-3A 0.30 Gelatin 1. 86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0. 06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Green Sensitive Emulsion Layer) Emulsion Em-2A 0.11 Gelatin 1.24 Magenta Coupler (ExM) 0.23 Color Image Stabilizer (Cpd-2) 0.03 Color Image Stabilizer ( Cpd-3) 0.16 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 UV absorber (UV-1) 0.47 Color-mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive emulsion layer) Emulsion Em-1A 0. 23 Gelatin 1.34 Magenta coupler (ExM) 0.23 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer ( Cpd-6) 0.18 color image stabilizer Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0. 16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17%) 0.17 Flow Paraffin 0.03

Ten minutes after adding the silver bromide fine grain emulsion to each of the emulsions 1A, 2A and 3A, the silver chloride content was 98 mol%, the silver bromide content was 2 mol%, and the average diameter was 0.1 μm.
The silver chlorobromide fine grain emulsion of 1 was added in an amount corresponding to 1 mol% with respect to the silver amount of emulsions 1A, 2A and 3A and ripened for 20 minutes.
B and 3B were obtained. In sample 101, emulsions 1A, 2
Samples 102 were prepared by replacing 1A, 3B with 1B, 2B, and 3B respectively.

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Chemical 13]

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

First, the sample 101 was subjected to gray exposure so that the developed silver amount was 30% of the applied silver amount, and the solution having the following processing steps and processing solution composition was used, and the tank capacity for color development was set to 2%. Continuous processing (running test) was performed until double replenishment. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17L Bleach fixing 30-35 ℃ 45 seconds 215ml 17L Rinse 30-35 ℃ 20sec-10L Rinse 30-35 ℃ 20sec-10L Rinse 30-35 ℃ 20 seconds 350ml 10 liter Dry 70-80 ℃ 60 seconds ^* Replenishment amount per 1 m ² of light-sensitive material (Rinsing → 3 tanks countercurrent method) Composition of each processing solution is as follows. is there.

Color developing solution Tank solution Replenishing solution Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g -Potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water was added to 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water was added. 1000 ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 ppm each for calcium and magnesium)
Less than)

Then, gradation exposure for sensitometry was applied to samples 101 and 102 by FWK manufactured by Fuji Photo Film Co., Ltd.
Type sensitometer, 2500 Lux 1/10 second SP manufactured by the same company
Three color separation exposure was performed through 1, SP-2 and SP-3 filters. The exposed sample was processed by using the running processing solution while changing the developing time to 15 seconds, 45 seconds and 90 seconds. The density of the obtained sample was measured using a TCD type self-recording densitometer manufactured by Fuji Photo Film Co., Ltd., and changes in sensitivity and gradation were measured. The sensitivity was defined as the reciprocal of the exposure amount that gives a density of 0.8, and was expressed as a relative value with 100 being the sensitivity of Sample 101 in 45-second development. The gradation is represented by the logarithmic value of the exposure amount required to increase the density from 0.5 to 1.5. The results are shown in Table 1.

[0061]

[Table 6]

As is clear from the results shown in Table 1, the sample 102 of the present invention has a higher sensitivity than the comparative sample 101, and the change in the sensitivity and gradation when the developing time is changed is small. It can be seen that it is strong against changes in conditions. Also,
It can be seen that this tendency is particularly remarkable in the blue sensitive layer.

Example 2 Emulsions 1A, 2A, 3A, 1B, 2 prepared in Example 1
Emulsions were prepared which differed only in that gold and sulfur were optimally sensitized to B and 3B, respectively. These are emulsions 11A, 12A, 13A, 11B, 12B and 13B, respectively.
And The gold and sulfur sensitization was performed by adding chloroauric acid and triethylthiourea 20 minutes after the addition of the silver chlorobromide fine grain emulsion and ripening. Emulsions 11A, 12A, 13
Application samples 201 and 202 were prepared in the same manner as in Example 1 using A and 11B, 12B, and 13B, respectively.

Using a commercially available sponge-like scrubbing brush (trade name: Kykron: manufactured by Scotch Bright Co.), a constant load was applied to the emulsion-coated side of the sample thus prepared. I rubbed and rubbed it. After that, stepwise gray exposure was performed, development processing was performed using the running liquid used in Example 1, and changes in density due to pressure in the image area and the white background area were examined. As a result, comparative sample 2
With respect to No. 01, a small amount of dian color streaks was observed in the white background, and streaks of various colors due to the decrease in density were observed in the gray high density part. The quantitative results are shown in Table 2.

[0065]

[Table 7]

As is clear from the results in Table 2, the sample 202 of the present invention is superior to the comparative sample 201 in both the white background portion and the high density portion.

[0067]

According to the present invention, it is possible to obtain a light-sensitive material having high sensitivity, less dependency on development processing, and less likely to cause streaks due to pressure.

Claims (2)

[Claims] 1. A substantially cubic silver halide host grain having a silver chloride content of 95 mol% or more is added with bromide in an amount of 5 mol% or less with respect to the silver amount, and the vicinity of the apex of the cubic grain. After the silver bromide localized phase is formed on, the silver halide is supplied to the host grain in an amount of 5 mol% or less based on the silver amount of the host grain having the silver bromide localized phase, and the silver is deposited on the host grain. A silver halide photographic light-sensitive material, comprising at least one emulsion layer containing the prepared silver halide emulsion on a support. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion is chemically sensitized with sulfur, selenium, gold or a combination thereof.