JPH06337485A - Method of manufacturing silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To provide a method of manufacturing a sliver halide photographic emulsion which is excellent in stability in aging effect for an applicator liquid until it is applied to a substrate after preparation of the emulsion. CONSTITUTION:In a silver halide emulsion composed of planar particles having an aspect ratio of higher than 3 but less than 10, including more than 10 of transition lines per one particle, which occupy more than 60% but less than 100% of a projecting area given by all silver halide particles, a sensitizing pigment is added at a temperature which is higher than 35deg. but lower than 50deg., and is spectrally sensitized through a thermal aging at a temperature at a temperature which is higher than the added temperature by higher than 5deg.C but lower than 50deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it shows high sensitivity and stability of a coating solution with time after preparation of a silver halide photographic emulsion until coating on a support. Regarding improvement.

[0002]

2. Description of the Related Art In recent years, demands for silver halide photographic emulsions are becoming more and more stringent, and not only photographic characteristics such as high sensitivity and high image quality but also performance quality in the same manufacturing unit at the time of manufacturing photographic light-sensitive materials are required. Making it even more stable is an important issue. Among them, as a technique for improving sensitivity and image quality, it is already known to use tabular silver halide grains containing parallel twin planes (hereinafter referred to as "tabular grains") in U.S. Pat. No. 4,434,434. No. 226,
No. 4,433,048 and the like disclose its manufacturing method and use technique. Further, Japanese Patent Application Laid-Open No. 63-220238 discloses a technique for controlling and introducing dislocations into tabular silver halide grains.

The tabular grains have the following photographic characteristics: (1) ratio of surface area to volume (hereinafter referred to as "specific surface area").
Since it can adsorb a large amount of sensitizing dye on the surface, it has high sensitivity in the spectral sensitization region. (2) When an emulsion containing tabular grains is coated and dried,
Since the grains are arranged in parallel with the surface of the support, the scattering of incident light by the emulsion grains is small and the sharpness is good. And so on. In addition, tabular grains having poor monodispersity cannot be expected to have (a) a characteristic curve having a high contrast (so-called high gamma). (B) When chemical sensitization is performed on an emulsion in which large grains and small grains are mixed, the optimum conditions for chemical sensitization are different between large grains and small grains, so it is difficult to perform optimum chemical sensitization for both. is there. Therefore, it is preferable to use tabular grains having good monodispersion because of the drawbacks such as the above.

However, while such tabular grains increase the adsorption amount of the sensitizing dye, the sensitivity in the spectral sensitization region increases, while a silver halide photographic emulsion is prepared at the time of producing a photographic light-sensitive material. The inventor of the present invention later found that a new problem arises in that the photographic performance is greatly deteriorated during storage of the coating solution until it is coated on the support. On the other hand, as a technique for improving the temporal stability of a coating solution by a method of adding a dye, there are disclosed in JP-A-59-48756 and 59-148.
No. 050 discloses a technique in which sensitizing dyes having different chemical structures are divided and added into "at the time of chemical ripening" and "at the time of chemical ripening-before coating of a support", which is completely different from the addition method of the present invention. . The tabular silver halide grains are an indispensable technology in pursuit of higher sensitivity and higher image quality, and the amount of sensitizing dye to be adsorbed in the form of silver halide grains tends to further increase. Therefore, an emulsion having high sensitivity and high image quality, and excellent in stability with dissolution over time has been desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a silver halide emulsion which is excellent in the stability of a coating solution with time after the emulsion is prepared and before it is coated on a support.

[0006]

As a result of earnest research, the object of the present invention could be achieved by the following means. (1) In a silver halide emulsion in which tabular grains containing 10 or more dislocation lines per grain and having an aspect ratio of 3 or more and 100 or less comprise 60% or more of the projected area of all silver halide grains, a sensitizing dye is added. A method for producing a silver halide photographic emulsion, which comprises spectral sensitization through a step of thermally ripening at a temperature of 5 ° C. or more and 50 ° C. or less higher than the addition temperature after adding at 35 ° C. or more and 50 ° C. or less. (2) The method for producing a silver halide photographic emulsion according to (1), wherein in the silver halide emulsion, the silver iodide content on the grain surface is 2 mol% or more and 15 mol% or less. (3) The method for producing a silver halide photographic emulsion according to (1), wherein in the silver halide emulsion, the variation coefficient of the grain size of all silver halide grains is 20% or less.

The present invention will be described in more detail below. First, the tabular silver halide grains used in the present invention will be described in detail. Here, the tabular grains are a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane means the (111) plane when ions at all lattice points on both sides of the (111) plane have a mirror image relationship. In the tabular silver halide grains, the aspect ratio means the ratio of the diameter to the thickness of the silver halide grains. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter means the diameter of a circle having an area equal to the projected area of the grain when the silver halide grain is observed with a microscope or an electron microscope. Therefore, the aspect ratio of 3 or more means that the diameter of this circle is 3 times or more the thickness of the particles.

As an example of the method for measuring the aspect ratio, there is a method of taking a transmission electron microscope photograph by the replica method and obtaining the equivalent circle diameter and thickness of each particle. In this case, the thickness is calculated from the length of the shadow of the replica. In the emulsion used in the present invention, 60 to 100% of the projected area of all silver halide grains are tabular grains having an aspect ratio of 3.0 or more and 100 or less, and more preferably 5.0 or more and 10 or less.
It is a tabular grain of 0 or less, more preferably 8.0 or more and 100 or less. The tabular grains have a diameter of about 0.2-5.
0 μm is preferable, but 0.3 to 4.0 is more preferable.
μm, and more preferably 0.4 μm to 3.0 μm
Is. The thickness of the tabular grains is preferably less than about 0.5 μm, more preferably 0.05 to 0.5 μm, still more preferably 0.08 to 0.3 μm.

The grain size variation coefficient means a quotient obtained by dividing the standard deviation of all silver halide grain diameters by the average silver halide grain diameter. The coefficient of variation of particle size in the present invention is preferably 20% or less, more preferably 17% or less, still more preferably 15% or less. The lower limit of the coefficient of variation is preferably 2%. The emulsion used in the present invention is a tabular grain having dislocations.
Dislocations of tabular grains are described in, for example, JF Hamilton, Phot.Sc
i.Eng., 11, 57, (1967) and T. Shiozawa, JS
It can be observed by a direct method using a transmission electron microscope at low temperature, as described in oc. Phot. Sci. Japan, 35, 213 (1972).

That is, the silver halide grains taken out from the emulsion should be placed on a mesh for observation with an electron microscope, taking care not to apply a pressure such that dislocations occur in the grains, and damage (for example, printout) due to an electron beam may be caused. Observation is performed by a transmission method while the sample is cooled so as to prevent it. In this case, since the electron beam is more difficult to penetrate as the thickness of the particles is larger, the high pressure type (200 μm for particles having a thickness of 0.25 μm is used).
It is possible to observe more clearly by using an electron microscope of kV or more). From the photograph of the grain obtained by such a method, the position of dislocation in each grain when viewed from the direction perpendicular to the principal plane can be determined. Note that dislocation lines may or may not be visible depending on the tilt angle of the sample with respect to the electron beam.
It is necessary to determine the existence position of dislocation lines by observing the particle photographs of the same particle at as many sample tilt angles as possible.

In the present invention, five types of grain photographs are taken by changing the tilt angle of the same grain in 5 ° steps using a high-voltage electron microscope, and the existence positions and the number of dislocation lines are determined. The tabular grains which account for 60% or more of all grains in the emulsion used in the present invention have 10 or more dislocation lines per grain in the grain fringe portion, preferably 30 or more, particularly preferably 50. It has the above dislocation lines.

When the dislocation lines are densely present, or when the dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in such a case, about 10
It can be counted as a book, 20, or 30. The upper limit of the number of dislocation lines is difficult to count accurately as described above, but it may reach several hundreds. The fringe portion means a flat plate-shaped outer periphery, and more specifically,
In the distribution of silver iodide on the line from the side of the tabular grain to the center, the point where the silver iodide content at a certain point for the first time from the side exceeds or falls below the average silver iodide content of the entire grain. Means the area outside.

In the present invention, when determining the proportion of grains containing dislocations and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains. It is more preferable to observe 200 particles or more, and particularly 300 particles or more. The tabular silver halide emulsion grains used in the present invention are preferably silver iodobromide or silver iodochlorobromide.

The tabular silver halide emulsion grains used in the present invention may have a layered structure consisting of at least two layers having substantially different halogen compositions, or may have a uniform composition. It is preferable to have one or more layered structures. The silver iodide content of the high silver iodide portion in the grain is preferably 3 mol% or more and 6 mol% or less, and more preferably 4 mol% or more and 5 mol% or less.

When the silver iodide content increases, the intrinsic sensitivity upon blue exposure increases, and when spectrally sensitized, the cyanine dye adsorbing power increases and the sensitizing dye coverage increases. Are known. Next, the silver iodide content on the grain surface in the present invention will be described in detail.

More specifically, the "surface" in the present invention refers to a region which can be measured by the XPS method described later, and usually up to 50A. The silver iodide content on the grain surface can be measured by the XPS method (X-ray Photoelectron Spectroscopy).
py: X-ray photoelectron spectroscopy). The principle of the XPS method is described in detail, for example, in “Electron Spectroscopy” by Soichi Aihara (Kyoritsu Library 16: Kyoritsu Publishing, 1978).

The standard measurement method of XPS uses Mg-Kα as excitation X-ray, and the photoelectron intensities of iodine (I) and silver (Ag) emitted from silver halide grains in a suitable sample form. Is a method of observing. To determine the iodine content, a calibration curve of the intensity ratio (intensity (I) / intensity (Ag)) of the photoelectrons of iodine (I) and silver (Ag) using several kinds of standard samples with known iodine contents. Can be created and determined from this calibration curve. In the case of silver halide emulsions, gelatin adsorbed on the surface of silver halide grains must be decomposed with a proteolytic enzyme and removed, and then XPS must be measured. The grains of the present invention have a silver iodide content of 2 mol% or more and 15 mol% or less on the grain surface measured by XPS method,
It is more preferably 3 mol% or more and 12 mol% or less.

Next, a method for producing tabular grains will be described. In the present invention, the tabular grains are formed by a nucleation / Ostwald ripening / growth process. As a method of forming nuclei, a so-called single jet method in which only a silver nitrate aqueous solution is added to a halide salt solution and a double jet method in which a silver nitrate aqueous solution and a halide salt aqueous solution are simultaneously added are known. The preferable nucleation condition in the present invention requires that the occurrence probability of twin nuclei is high,
It is a double jet method that has a high degree of supersaturation without a stirrer and is liable to generate nuclei. Nucleation can be performed at a reaction solution temperature of about 20 ° C. to 60 ° C., but the probability of generation of twin nuclei is high, and in consideration of suitability for production, 30 ° C.-6 °
It is preferable to carry out at 0 ° C.

After the nucleation, the temperature is further raised to adjust the pAg to 7.6 to.
After adjusting to 10.0, grains other than tabular grains are extinguished with a silver halide solvent. Thus, after obtaining only the tabular grain group, tabular grains having a desired size are obtained by the grain growth process. In the grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. The aspect ratio of the resulting emulsion grains can be appropriately controlled by, for example, selecting the temperature during the grain growth process, pAg, and the addition rate of the aqueous silver nitrate solution and the aqueous halide solution to be added. Further, as described in JP-A-62-99751, a method of supplying a part or all of silver added in the grain growth process as fine grains of silver halide can also be used.

In the present invention, the emulsion is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The washing temperature can be selected according to the purpose, but it is 5 to 50 ° C.
It is preferable to set in. The pH at the time of washing with water can be selected according to the purpose, but it is preferably set within the range of 2 to 10.
More preferably, it is in the range of 3-8. PAg when washed with water
Can be selected according to the purpose, but it is preferably set in the range of 5 to 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, for example, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, and a method using a gelatin derivative can be selected.

In the present invention, the presence of a metal ion salt during the preparation of an emulsion, for example, during grain formation, desalting step, chemical sensitization, and before coating is preferred depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Specific examples of the metal species include Mg, Ca, Sr, Ba, Al, Sc, Y and LaC.
r, Mn, Fe, Co, Ni, Cu, Zn, Ga, R
u, Rh, Pd, Re, Os, Ir, Pt, Au, C
Examples thereof include d, Hg, Tl, In, Sn, Pb and Bi. These metals are added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. it can. For example, CdBr ₂ , CdCl
₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ C
OO) ₂ , K ₃ Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
_{N) 6], K 3 IrCl} 6, (NH 4) 3 RhCl 6, K 4
Ru (CN) ₆ is an example. Examples of the ligand of the coordination compound include halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These metal compounds may be used alone, or two or more kinds may be used in combination.

The metal compound is water or methanol,
It is preferably added by dissolving in a suitable solvent such as acetone. Aqueous hydrogen halide solution (eg HCl, HBr) or alkali halide (eg KCl, NaCl, KBr, NaBr) to stabilize the solution.
Can be added. If necessary, for example, acid / alkali may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (for example, AgNO ₃ ) or an aqueous alkali halide solution (for example, NaCl,
KBr, KI) and continuously during the formation of silver halide grains. Furthermore, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at an appropriate time during grain formation. In addition, it is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In this case, S, Se,
In addition to Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

At least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization, noble metal sensitization, and reduction sensitization is used in the silver halide grains used in the present invention in a process for producing a silver halide emulsion. Can be applied in any step. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared by appropriately selecting the step of chemical sensitization. For example, it is possible to prepare an emulsion of a type in which chemically sensitized nuclei are embedded in a grain, a type in which a chemically sensitized nucleus is embedded in a grain surface at a shallow position, or a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion used in the present invention, the location of the chemically sensitized nuclei in the grains can be selected according to the purpose, but it is generally preferable to form at least one type of chemically sensitized nuclei near the grain surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization alone or in combination. This chemical sensitization is by James (TH James),
The Photographic Process, 4th Edition, published by Macmillan, 1977, (THJames, The Theory of th
e Photographic Process, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67-76. Research Disclosure, 120 volumes, April 1974, 1208; Research Disclosure, 34 volumes, June 1975, 1
3452, U.S. Pat. Nos. 2,642,361 and 3,2.
97,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755, p.
It can be carried out using Ag, 5 to 10, pH 5 to 8 and temperature of 30 to 80 ° C., with sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and gold sensitization, palladium sensitization and a combination of both are particularly preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used.

The palladium compound is a divalent palladium salt.
Or a tetravalent salt, which is a preferred palladium compound
Is R₂PdX₆Or R₂PdX_FourIt is represented by. This
Where R is a hydrogen atom, an alkali metal atom or ammonium
Represents a group. X represents a halogen atom, chlorine, bromine
Or represents an iodine atom. Specifically, K₂PdCl
_Four, (NH_Four)₂PdCl₆, Na₂PdCl_Four, (NH
_Four)₂PdCl_Four, Li₂PdCl_Four, Na₂PdCl₆
Or K₂PdBr_FourIs preferred. Gold compounds and para
The thiocyanate or selenocyanic acid compound
It is preferably used in combination with a salt.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
7,711, 4,266,018 and 4,0
The sulfur-containing compounds described in No. 54,457 can be used.

It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Further, examples of the chemical sensitization aid modifier are described in US Pat. No. 2,131,03.
No. 8, No. 3,411, 914, No. 3,554, 757
JP-A-58-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

As described above, it is preferable to use gold sensitization together with the emulsion used in the present invention. The preferable amount of the gold sensitizer is 1 × 10 ⁻⁴ to 1 × 10 per mol of silver halide.
^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10
^-7 mol.

The preferred amount range of the palladium compound is 1 × 10 ^-3 to 5 × 10 ^-7 . The preferred amount range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 .

In the present invention, the preferable amount of the sulfur sensitizer used for the silver halide grains is 1 g of the silver halide.
It is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol.

In the present invention, the preferred sensitizing method for the emulsion is selenium sensitization. In the selenium sensitization, known unstable selenium compounds are used, and specifically, colloidal metal selenium and selenoureas (for example, N,
Selenium compounds such as N-dimethylselenourea, N, N-diethylselenourea), selenoketones, and selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

In the present invention, the silver halide emulsion is used during grain formation, after grain formation and before chemical sensitization or during chemical sensitization.
Alternatively, it is preferable to carry out reduction sensitization after chemical sensitization.

The reduction sensitization is carried out by adding a reduction sensitizer to a silver halide emulsion, pAg called silver ripening.
Either a method of growing or aging the particles in an atmosphere of low pAg of 1 to 7 or a method of growing or aging the particles in an atmosphere of high pH of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

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

Examples of reduction sensitizers that can be used here include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives,
Formamidinesulfinic acid, silane compounds and borane compounds are known. In the reduction sensitization applicable in the present invention, these known reduction sensitizers can be selected and used, or two or more compounds can be used in combination. Particularly preferred compounds as reduction sensitizers are stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives. The addition amount of the reduction sensitizer needs to be appropriately selected depending on the emulsion production conditions,
A suitable range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is water or alcohol,
It is dissolved in a solvent such as glycols, ketones, esters and amides and then added during grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during grain growth. Further, the reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

In the present invention, it is preferable to use an oxidizing agent for silver during the emulsion manufacturing process. The oxidizing agent for silver means a compound that acts on metallic silver to convert it into silver ions. In particular, a compound capable of converting extremely fine silver grains, which are a by-product in the silver halide grain formation process and the chemical sensitization process, into silver ions is effective. The silver ions generated here may form a sparingly soluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a water-soluble silver salt such as silver nitrate. Good.

Even if the oxidizing agent for silver is an inorganic substance,
It may be an organic substance.

As the inorganic oxidant, ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ .H ₂ O _2. )
3H ₂ O, 2NaCO ₃ · 3H ₂ O ₂ , Na ₄ P ₂ O ₇
・ 2H ₂ O ₂ , 2Na ₂ SO ₄・ H ₂ O ₂・ 2H
₂ O), peroxyacid salts (eg K ₂ S ₂ O ₈ , K _{2
C 2 O 6, K 2 P} 2 O 8), peroxy complex compounds _{(e.g., K 2 Ti (O 2)} C 2 O 4 · 3H 2 O, 4K 2 SO 4
・ Ti (O ₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ VO (O
_{2) (C 2 H 4)} 2 · 6H 2 O), permanganate (e.g., KMnO _4), chromates (e.g., K ₂ Cr ₂ O ₇₎
Oxygenates such as, halogen elements such as iodine and bromine,
Perhalogenates (eg potassium periodate) High valent metal salts (eg potassium hexacyanoferrate)
And thiosulfonate.

As the organic oxidant, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B) are mentioned as examples.

In the present invention, preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents and quinone type organic oxidizing agents. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected and applied from a method of using an oxidant and then reduction sensitization, a method in which the order is reversed, or a method of coexisting both. These methods can be selectively used in both the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinthione; azaindenes, For example, triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers can be added, such as 3,3a, 7) chitraazaindenes), pentaazaindenes. Specifically, US Pat. Nos. 3,954,474 and 3,982,
Those described in No. 947 and Japanese Patent Publication No. 52-28660 can be used. One of the preferred compounds is the compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. It is added during emulsion preparation to exert the original antifoggant and stabilizing effects, and also controls the crystal wall of grains, reduces grain size, reduces solubility of grains, and controls chemical sensitization. , It can be used for various purposes such as controlling the arrangement of dyes.

Next, the process of spectral sensitization used in the present invention will be described. Although the sensitivity of the emulsion spectrally sensitized using the above tabular silver halide grains was improved, it was revealed that unexpectedly a problem occurs in the stability of the emulsion coating solution over time.
The present inventor, when carrying out the spectral sensitization of the tabular silver halide grains, added a sensitizing dye to the tabular emulsion grains dissolved at 50 ° C. or lower to cause adsorption, and then the emulsion temperature was adjusted. ,
It was found that the temperature stability of the emulsion coating solution was improved while maintaining high sensitivity by raising the temperature to 5 ° C or more higher than the temperature of the dye-added emulsion and further performing thermal ripening. Achieved the purpose. The temperature for adding the sensitizing dye is preferably 35 ° C. or higher and 50 ° C. or lower, more preferably 45 ° C. or lower, and further preferably 40 ° C. or lower.
After the sensitizing dye is added, the temperature for raising the temperature for heat aging is 5 ° C.
The temperature is preferably 50 ° C or higher and 50 ° C or lower, more preferably 10 ° C or higher and 40 ° C or lower, still more preferably 20 ° C or higher and 30 ° C or lower.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a dye belonging to the complex merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, for example, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus,
The benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-
A 5-6 membered heterocyclic nucleus such as a 2,4-dione nucleus, a rhodanine nucleus, or a thiobarbituric acid nucleus can be applied.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, and 3,617. 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301. , 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281.
No. 1,507,803, Japanese Patent Publication No. 43-4936
No. 53-12,375, JP-A No. 52-110,6.
18 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The above-mentioned spectral sensitization step may be carried out at any time after the formation of the tabular silver halide grains. That is, it may be a time after the completion of the chemical sensitization and before the application, or it may be performed before the chemical sensitization. The addition amount of the sensitizing dye cannot be unambiguously stated depending on the kind of the additive and the silver halide used,
The amount added may be approximately equal to or more than the amount added by the conventional method. That is, the preferable addition amount of the sensitizing dye is 0.001 to 100 per mol of silver halide.
mmol. The most preferable addition amount of the sensitizing dye in the present invention is 6 with respect to the saturated coating amount of silver halide emulsion grains.
It is 0% or more. The saturated coating amount of the sensitizing dye on the silver halide emulsion grains can be easily calculated by obtaining an adsorption isotherm of a normal sensitizing dye. The sensitizing dye can be added by any method.

Water or alcohols, glycols,
It can be added after being dissolved in a solvent such as ketones, esters and amides. Also a dispersant (surfactant)
To help disperse the dye in water, add the powder as it is or add it to a powder obtained by drying, or mix the dye and dispersant together with a binder such as gelatin in a homogeneous mixture (gel,
Paste form, slurry form, etc.), a method of adding granules obtained by drying the mixture, water without a dispersant (a binder such as gelatin can also be used) Among them, a method in which a pigment is pulverized into fine particles having a size of 1 μm or less and dispersed and then added can be used.

The silver halide color photographic light-sensitive material of the present invention comprises at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer on a support, and is required. The non-photosensitive layer may be provided according to the above, and there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. In that case, the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is formed according to JP-A-61-43748,
No. 59-113438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler and a DIR compound as described in the specification, and a color-mixing inhibitor as commonly used. May be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are preferably composed of West German Patent 1,121,
As described in 470 or British Patent No. 923,045, a two-layer constitution of a high sensitivity emulsion layer and a low sensitivity emulsion layer can be used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, for example, JP-A-57-112751, JP-A-57-12751
2-200350, 62-206541, 62-
As described in 206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

Specific examples of the arrangement of these photosensitive layers include:
From the side farthest from the support, for example, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH
The order of / BL / GH / GL / RL / RH is mentioned.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and 62-63936.
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification.

As another concrete example, Japanese Examined Patent Publication No. 49-1549
As described in Japanese Patent Publication No. 5, the upper layer is a silver halide emulsion layer having the highest photosensitivity, the middle layer is a silver halide emulsion layer having a lower photosensitivity, and the lower layer is a halogen having a lower photosensitivity than the middle layer. By arranging the silver halide emulsion layer, the sensitivities are gradually reduced toward the support.
An example is an array composed of layers. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-2
As described in the specification of No. 02464, in the same color-sensitive layer, a medium-speed emulsion layer /
It may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, in the above three-layer structure, the layers are arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Good. Also, in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, and BL, G described in the specification.
It is preferable to dispose a donor layer (CL) having a multilayer effect, such as L and RL, which has a spectral sensitivity distribution different from that of the main photosensitive layer, adjacent to or close to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide emulsions other than the tabular silver halide grain emulsion which can be used in the present invention will be described in detail below.

The preferable silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons. Having an irregular crystal shape such as spherical or plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsions other than the emulsion comprising tabular silver halide grains usable in the light-sensitive material of the present invention are, for example, Research Disclosure (RD).
No.17643 (Dec. 1978), pp. 22-23,
"I. Emulsion preparation and types"
, And No. 18716 (November 1979),
648, ibid. No. 307105 (November 1989),
Pp. 863-865, and "Graphics and Chemistry" by Graphide, published by Paul Montel (P.Glafkides, Chemie et.
Phisique Photographique, Paul Montel, 1967),
Duffin, Photographic Emulsion Chemistry (Focus Press)
al Press, 1966)), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikman e).
t al., Making and Coating Photographic Emulsion, F
ocal Press, 1964).

In the present invention, US Pat. No. 3,574,62
No. 8, 3,655,394 and US Pat. Nos. 1,4.
The monodisperse emulsion described in No. 13,748 is also preferable.

The crystal structure of the silver halide grains usable in the present invention may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halides such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The emulsion comprising silver halide grains may be a surface latent image type which forms a latent image mainly on the grain surface, an internal latent image type which is formed inside the grain, or has a latent image both on the surface and inside. Any of the types may be used, but it is necessary that the emulsion is a negative type. In the case of an internal latent image type, Japanese Patent Laid-Open No. Sho 6
The core / shell type internal latent image type emulsion described in 3-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell constituting this emulsion varies depending on the development processing, but is preferably about 3 × 40 nm,
0 nm is particularly preferred.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized.
Additives used in such a process are described in Research Disclosure Nos. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below.

In the light-sensitive material of the present invention, the grain size of the light-sensitive silver halide emulsion, grain size distribution, halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
A silver halide grain whose inside or surface is fogged means a silver halide grain (emulsion) that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. Say that. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,4.
98 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Here, the grain shape is not particularly limited, and it may be a regular grain or a polydisperse emulsion, but a monodisperse emulsion (the weight of silver halide grains or the number of grains is at least 9).
5% has a particle size within ± 40% of the average particle size).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The non-photosensitive fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide, preferably iodide. It contains 0.5 to 10 mol% of silver halide.

The non-photosensitive fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area) of 0.01 to
0.5 μm is preferable, and 0.02 to 0.2 μm is more preferable.

The non-photosensitive fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the non-photosensitive silver halide fine particles need not be optically sensitized and spectral sensitization is also unnecessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide.

The silver coating amount of the light-sensitive material of the present invention is 9.0 g.
/ M ² or less is preferable, and 6.0 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention 24 to 25 pages 649 right column 868 to 870 Agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter to page 650, left column, dye, ultraviolet absorber 7. Stain, page 25, right column, page 650, left column, page 872, inhibitor-right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener, page 26, page 651, left column, pages 874-875 10. Binder page 26 page 651 left column page 873-874 11. Plasticizer, page 27, page 650, right column, page 876, lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, immobilization by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention includes US Pat.
40,454, 4,788,132, JP-A-6
It is preferable to incorporate the mercapto compounds described in JP-A No. 2-18539 and JP-A No. 1-283551.

In the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing, JP-A-1-10605 is used.
It is preferable to contain a compound releasing a fog agent, a development accelerator, a silver halide solvent or a precursor thereof described in No. 2.

The light-sensitive material of the present invention includes the international publication WO88.
No. 04794, Dyes dispersed by the method described in JP-A-1-502912, or EP317, 308A
U.S. Pat. No. 4,420,555, JP-A-1-259.
It is preferable to incorporate the dye described in No. 358.

Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof are Research Disclosure No. 17643, VII-C, mentioned above.
G, and the patents described in No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in EP 249,473A are preferred.

Examples of magenta couplers include 5-
Pyrazolone-based and pyrazoloazole-based compounds are used and are disclosed in US Pat. Nos. 4,310,619 and 4,35.
1,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984).
June 60), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 6
0-35730, 55-118034, 60-
185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in International Publication WO88 / 04795 are particularly preferable.

Phenol-type and naphthol-type couplers are used as the cyan coupler. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2,895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent Nos. 121,365A and 249,453A
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole-based couplers described in US Pat. No. 4,818,672 and the imidazole-based couplers described in US Pat. No. 4,818,672 can also be used.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

As a colored coupler for correcting unnecessary absorption of a color forming dye, Research Disclosure No. 17643, Item VII-G and No. 307105, can be used.
Section VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

In the light-sensitive material of the present invention, compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR releasing a development inhibitor
As the coupler, the patents described in the above-mentioned RD17643, VII-F section and No. 307105, VII-F sections, JP-A-57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
No. 63-37350, U.S. Pat. No. 4,248,96.
Those described in No. 2 and No. 4,782, 012 are preferable.

For example, R. D. No. 11449, 242
41, the bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective in shortening the processing time having a bleaching ability. In particular, the effect is great when added to the light-sensitive material using the above-mentioned tabular silver halide grains. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, there is disclosed in British Patent 2,097,1.
40, No. 2,131,188, JP-A-59-15.
Those described in 7638 and 59-170840 are preferable. Moreover, JP-A-60-107029 and JP-A-60-
252340, JP-A-1-44940, and 1-45.
Compounds releasing a fogging agent, a development accelerator, and a silver halide solvent by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,13.
Competitive couplers described in US Pat. No. 4,427, US Pat. No. 4,2.
No. 83,472, No. 4,338,393, No. 4,
Multi-equivalent couplers described in JP-A No. 310,618, JP-A-60
-185950, JP-A-62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313, 313. No. 308A, a coupler that releases a dye that recolors after separation, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and a leuco dye-releasing coupler described in JP-A-63-75747. Examples thereof include couplers that release a fluorescent dye described in Japanese Patent No. 4,774,181.

In the present invention, the coupler can be introduced into the photographic material by various known dispersion methods. Examples thereof include an oil-in-water dispersion method and a latex dispersion method.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate,
Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t
-Amylphenyl) phthalate, bis (2,4-di-t
-Amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); esters of phosphoric acid or phosphonic acid (eg triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri- 2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate); benzoic acid esters (for example, 2
-Ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (e.g., N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols ( For example, isostearyl alcohol, 2,4-di-tert
-Amylphenol); aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (for example, N, N-dibutyl-) 2-butoxy-5-tert-octylaniline); hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat.
199,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

In the color light-sensitive material of the present invention, for example, phenethyl alcohol, 1,2-benzisothiazoline-3-as described in JP-A Nos. 63-257747, 62-272248 and 1-80941. On-,
It is possible to add various preservatives or fungicides such as n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. preferable.

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

Suitable supports which can be used in the present invention are, for example, RD. No. 17643, page 28, No. 187 mentioned above.
16, page 647, right column to page 648, left column, and No. 30 of the same.
7105, p. 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. Here, the film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days). The film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photog
r.Sci.Eng.), Vol. 19, No. 2, pages 124 to 129. Further, T _1/2 is a color developing solution at 30 ° C.,
90% of the maximum swollen film thickness reached when processed for 3 minutes and 15 seconds
Is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. Here, the swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. . The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention is described in the above-mentioned RD. No. 17643, pages 28-29, 187.
No. 651, left column to right column, and No. 307105, pages 880 to 881 can be used for development processing.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used. As typical examples thereof, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-elch-β-methoxyethylaniline and their sulfates, nitrates or p-toluenesulfone Examples thereof include acid salts. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate,
It generally contains a development inhibitor such as a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound, or an antifoggant. Further, the color developing solution may contain various kinds of hydrazines such as hydroxylamine, diethylhydroxylamine, sulfite, N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, and catecholsulfonic acid, if necessary. Preservative,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-
Auxiliary developing agents such as 3-pyrazolidone, tackifiers,
Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid may be contained. Among these, examples of the chelating agent include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And salts thereof.

When the reversal process is applied to the light-sensitive material of the present invention, black and white development is usually carried out before color development. The black-and-white developing solution is represented by, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol. The black-and-white developing agents can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12.

The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 m 2 of the light-sensitive material, and the bromide ion concentration in the replenishing solution should be reduced. It is possible to make it less than 500 ml. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a means for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, Japanese Patent Laid-Open No.
The method using a movable lid described in 82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. The means to reduce the aperture ratio is
It is preferable to apply not only to both the color development step and the black and white development step but also to the subsequent steps, for example, all steps including bleaching, bleach-fixing, fixing, washing with water and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents, organic complex salts of iron (III), for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
Complex salts of iron (III) with aminopolycarboxylic acids such as methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of iron (III) with citric acid, tartaric acid or malic acid. Can be used. Of these, aminopolycarboxylic acid iron (II) complex salts including ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt
I) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8,
It is also possible to process at a lower pH for speeding up the process.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators include US Pat.
93,858, West German Patents 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53-37418, 53-.
No. 72623, No. 53-95630, No. 53-956
No. 31, No. 53-104232, No. 53-12442
No. 4, No. 53-141623, No. 53-28426.
No. 17129 (July 1978), compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A No. 50-140129; JP-B-45-8506.
No. 52-20832 and 53-32735.
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, JP-A-58.
-16,235, the iodide salt; West German Patent 966.
Nos. 410 and 2,748,430, polyoxyethylene compounds described in JP-B-45-8836; other JP-A-49-40,943,
49-59,644, 53-94,927, 54-35,727, 55-26,506, 5
8-163,940 compound; bromide ion is mentioned. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95,630. Compounds described in US Pat. Further, US Pat. No. 4,55
The compounds described in No. 2,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is a compound of 2 to 5, and specifically, for example, acetic acid,
Propionic acid and hydroxyacetic acid are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, the use of thiosulfates is common, with ammonium thiosulfate being the most widely used. Also, with thiosulfate, for example, thiocyanate,
Combination use with a compound such as a thioether compound or thiourea is also preferable. As a preservative for fixers and bleach-fixers,
Preferred are sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, a compound having a pKa of 6.0 to 9.0 for adjusting the pH of the fixing solution or the bleach-fixing solution, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering step in the development processing step is preferably as short as possible so long as no desilvering failure occurs.
The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing can be effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete means for strengthening the stirring, for example, the following method can be mentioned. That is, a method described in JP-A-62-183460, in which a jet of a processing liquid is made to collide with the emulsion surface of a light-sensitive material; JP-A-62-183.
No. 461, a method for improving the stirring effect by using a rotating means; the photosensitive material is moved while the wiper blade provided in the liquid is in contact with the emulsion surface, and the emulsion surface is turbulently stirred. A method of further improving the effect; a method of increasing the circulation flow rate of the entire processing liquid. Such a method of intensifying stirring is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the strengthening of stirring accelerates the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering rate. Further, the above-mentioned stirring intensifying means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibitory effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
No. 8 and No. 60-191259 are preferably provided with the photosensitive material transporting means.

As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, which is a great measure for preventing the deterioration of the performance of the treatment liquid. Produce an effect. Such an effect is
It is particularly effective for shortening the processing time in each step and reducing the replenishment amount of the processing liquid.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, the material used for the coupler), application, temperature of rinsing water, number of rinsing tanks (number of stages), replenishment method such as countercurrent or forward flow, and various other conditions. Can be set to. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion P
icture and Television Engineers Vol. 64, p. 24
8 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but bacteria multiply due to an increase in the residence time of water in the tank, and the problem that the suspended matter produced adheres to the photosensitive material Occurs.
In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 is extremely effectively used in order to solve such a problem. it can. Also,
Isothiazolone compounds described in JP-A-57-8,542, chlorine-based bactericides such as siabendazoles and chlorinated sodium isocyanurate, and others such as benzotriazole by Hiroshi Horiguchi, "Antibacterial and Antifungal Agent Chemistry "
(1986) Sankyo Publishing, edited by Hygiene Engineering Society, "Sterilization, sterilization and antifungal technology of microorganisms" (1982) Industrial Technology Association, edited by the Japan Society for Antibacterial and Antifungal "Dictionary for Antifungal Agents" (1986) The disinfectants described can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set according to the characteristics and application of the light-sensitive material, but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
It is preferably selected at 25 to 40 ° C. for 30 seconds to 5 minutes. Furthermore, the light-sensitive material of the present invention, instead of the above washing with water,
It is also possible to treat directly with the stabilizing solution. In such stabilizing treatment, JP-A-57-8543 and JP-A-5-543 have been used.
All known methods described in JP-A-8-14834 and JP-A-60-220345 can be used.

In addition, after the water washing treatment, a stabilizing treatment may be further performed. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic processor, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention comprises
A color developing agent may be incorporated for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, the Schiff base type compounds described in U.S. Pat. No. 3,342,597, indoaniline compounds, No. 3,342,599, Research Disclosure Nos. 14,850 and No. 15,159, Examples thereof include aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.

The silver halide color photographic light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development.
Typical compounds are disclosed in JP-A Nos. 56-64339 and 57-57.
-144547 and 58-115438.

Various processing solutions for the light-sensitive material of the present invention are
Used at 10 ° C to 50 ° C. Normally 33 ° C-3
Although a temperature of 8 ° C is standard, set a higher temperature to accelerate the processing to shorten the processing time, and conversely set a lower temperature to improve the image quality and improve the stability of the processing liquid. You can

The silver halide color photographic light-sensitive material of the present invention is described in, for example, US Pat. No. 4,500,626, JP-A-60-133449 and JP-A-59-218443.
61-238056, EP 210,660A.
It can also be applied to the photothermographic material described in No. 2.

The photographic product containing a light-sensitive material of the present invention, that is, a photographic product containing the above-described silver halide color photographic light-sensitive material and further having an exposure function is well known and is known, for example, in JP-A-4. No. 159542, JP-A 4-1
No. 57459.

[0125]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Emulsion Em-A: Comparative Emulsion) While keeping the pAg at 9.8 in the gelatin aqueous solution containing the alkali halide, the ammoniacal silver nitrate aqueous solution and the alkali halide aqueous solution were prepared by the control double jet mixing method. 5 at 50 ° C
Add and mix over 0 minutes, average particle equivalent diameter 0.8 μm,
An octahedral silver iodobromide emulsion having a coefficient of variation of 18% was obtained. The silver iodide content on the surface measured by XPS was 4.0 mol%. (Preparation of emulsion Em-B: comparative emulsion) The average iodine content is 2
0 mol%, seeded with twin twin particles having an average equivalent spherical diameter of 0.5 μm, the core: shell ratio was 1: 2 and the iodine content of the gel was 3.5 mol% by a control double jet method in a gelatin aqueous solution. The average equivalent spherical diameter is 0.8 μm
The slab-like particles composed of twin crystals of

(Preparation of emulsions Em-C to H) Thickness 0.15
Tabular grains of silver bromide having a diameter of 0.5 μm and a circle-equivalent diameter of 0.5 μm were prepared as seed crystals. Seed crystals containing 18 g of silver were dissolved in 1 liter of distilled water, pAg was adjusted to 8.2 and pH was adjusted to 5.
The mixture was kept warm at 75 ° C and stirred vigorously. Subsequently, particles were formed by the following procedure.

1) A silver nitrate (141 g) aqueous solution and a potassium bromide aqueous solution were added while keeping the pAg at 8.4. 2) The temperature was lowered to 55 ° C., and a potassium iodide (4.5 g) aqueous solution was added at a constant flow rate. 3) Add an aqueous solution of silver nitrate (63g) and an aqueous solution of potassium bromide.
Addition was carried out while maintaining Ag at 8.9.

The mixture was cooled to 35 ° C., washed with water by an ordinary flocculation method, added with 50 g of gelatin and redispersed to obtain pH.
It was adjusted to 6.0 and pAg 8.2. Average sphere equivalent diameter 0.8
An emulsion having an average aspect ratio of 2.4, a coefficient of variation of 30%, and a dislocation number of 3 per grain was obtained. Em-
Let be C. Em-D to H listed in Table 1 were prepared by appropriately adjusting the preparation conditions for Em-C.
All of Em-C to H were tabular grains having an average equivalent spherical diameter of 0.8 μm. The emulsions of Em-A to H were heated to 64 ° C., sodium thiosulfate, chloroauric acid, potassium thiocyanate, and N, N-dimethylselenourea were sequentially added, and each emulsion was ripened for 90 minutes. The optimum chemical sensitization was performed. The term "optimally" used here means
1/100 second It means the condition that the sensitivity becomes the highest. The obtained emulsions are designated Em-1 to Em-8, respectively.

[0130]

[Table 1]

The resulting emulsions Em-1 to Em-8 were dissolved at the addition temperatures shown in Table 4, added with the sensitizing dye amounts shown in Table 2 and held for 30 minutes, and then heat ripened shown in Table 4. It heated up to temperature and hold | maintained for 30 minutes. At this time, the amount of the sensitizing dye added was 85% of the saturated coating amount for each emulsion.

[0132]

[Table 2]

(Preparation of Coating Sample) The emulsions 101 to 128 thus obtained were dissolved at 40 ° C., and after agitation for 30 minutes, the cellulose triacetate film support provided with an undercoat layer was supported. It was applied onto the body together with the protective layer in the application amount shown in Table 3. Emulsions 101 to 128 obtained in the same manner
Was dissolved at 40 ° C., and after stirring for 12 hours,
The same coating was applied on the support.

Emulsion coating conditions (1) Emulsion layer-Emulsion ... Em-101 to 128, 201-209 (silver 2.1 × 10 ^-2 mol / m ² ) -Coupler (1.5 × 10 ^-3 mol / m ² ). ² )

[0135]

[Chemical 1]

Tricresyl phosphate (1.10 g / m ² ), gelatin (2.30 g / m ² ).

(2) Protective Layer ・ 2,4-Dichloro-6-hydroxy-s-triazine sodium salt (0.08 g / m ² ) ・ Gelatin (1.80 g / m ² ) These samples were subjected to relative temperature test at 40 ° C. 14 under humidity of 70%
After being left for a time, it was exposed for 1/100 seconds through a continuous wedge and a yellow filter, and the following color development processing was performed.

The density of the treated sample was measured with a green filter. Process Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C Bleach fixing 3 minutes 00 seconds 40 ° C Washing with water (1) 20 seconds 35 ° C Washing with water (2) 20 seconds 35 ° C Stability 20 seconds 35 ° C Drying 50 seconds 65 ° C Next, the composition of the treatment liquid is shown. (Color developer) (Unit g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 water was added to 1.0 liter pH 10.05 (bleach-fixing solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleach Accelerator 0.01 mol (3-mercapto-1,2,4-triazole) Add water 1.0 liter pH 6.0

(Washing liquid) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH type anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by isocyanuric dichloride. Sodium 20 mg / liter and sodium sulfate 1.5 g / liter were added. The pH of this solution is in the range 6.5-7.5. (Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to the mixture 1. 0 liter pH 5.0-8.0

The performance examined is as follows. (1) Sensitivity Sensitivity is represented by the relative value of the reciprocal of the exposure amount that gives a density of fog + 0.2. The larger the value, the higher the sensitivity. (2) Gamma It is a characteristic value with respect to gradation and is represented by the density difference between the density point of fog +0.2 and the point on the characteristic curve corresponding to the exposure amount corresponding to 10 times the exposure amount at this point. The gamma ratios shown in Table 2 are the ratios of the gamma values of the sample coated with the emulsion which was melted at 40 ° C. and aged for 12 hours, and the gamma value of the sample which was coated with the emulsion melted at 40 ° C. and aged for 30 minutes. Indicated by. If the gradation does not change with the lapse of dissolution, the gamma ratio will be 1.

The above results are summarized in Table 3.

[0142]

[Table 3]

From the results shown in Table 3, emulsion grains having a smaller specific surface area than tabular grains such as Em-101 to 106 have a small amount of sensitizing dye that can be adsorbed and have low sensitivity, and deterioration in photographic performance due to dissolution aging. Although not accompanied, tabular emulsion grains with a high specific surface area surprisingly show that when the amount of sensitizing dye that can be adsorbed increases, the photographic sensitivity is low when the addition temperature of the sensitizing dye is low, and when the addition temperature of the sensitizing dye is high, dissolution occurs. It can be seen that deterioration of photographic performance occurs over time. However, in such tabular emulsion grains, Em-119 to 120, 124 to 1
By adding the sensitizing dyes shown in Nos. 25, 127 to 128, high-sensitivity silver halide photographic sensitization without deterioration of photographic performance even after a long time until the coating after the emulsion is dissolved. It can be seen that the material is obtained.

Example 2 The emulsions Em-C, F, and H prepared in Example 1 were dissolved at the addition temperatures shown in Table 5, and the sensitizing dyes shown in Table 4 were added and adsorbed for 30 minutes. The temperature was raised to the heat aging temperature shown in 5 and held for 30 minutes. At this time, the amount of the sensitizing dye added was 85% of the saturated coating amount of each emulsion.

[0145]

[Table 4]

[0146]

[Table 5]

The emulsion thus obtained was heated to 64 ° C., and sodium thiosulfate, chloroauric acid, potassium thiocyanate and N, N-dimethylselenourea were sequentially added,
The emulsion was ripened for 90 minutes to optimally perform chemical sensitization on each emulsion. Preparation of Samples 210 to 209 The resulting emulsion was subjected to the same dissolution and aging as in Example 1 above, and then, the same coating was performed on the support. The obtained coated sample was exposed and developed in the same manner as in Example 1 to obtain the results shown in Table 5. As is clear from Table 5, the sample of the present invention can provide a highly sensitive silver halide photographic light-sensitive material without deterioration in photographic performance even after a long lapse of time after the emulsion is dissolved and before coating.

Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample as a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20

Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV- 3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ⁻⁵ ExS-3 3 .1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS- 1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS- 1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁴ ExS-3 3.4 × 10 ⁻⁴ ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Interlayer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ⁻⁵ ExS-5 2.1 × 10 ⁻⁴ ExS-6 8.0 × 10 ⁻⁴ ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ⁻⁵ ExS-5 2.2 × 10 ⁻⁴ ExS-6 8.4 × 10 ⁻⁴ ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 3.2 × 10 ⁻⁴ ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY− 4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Medium Sensitivity Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ⁻⁴ ExC-7 7.0 × 10 ⁻³ ExY-2 0.050 ExY-30 .10 HBS-1 0.050 gelatin 0.78

Thirteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0 .86

Fourteenth Layer (First Protective Layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0.10 B-30 .10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0165]

[Table 6]

In Table 6, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0167]

[Chemical 2]

[0168]

[Chemical 3]

[0169]

[Chemical 4]

[0170]

[Chemical 5]

[0171]

[Chemical 6]

[0172]

[Chemical 7]

[0173]

[Chemical 8]

[0174]

[Chemical 9]

[0175]

[Chemical 10]

[0176]

[Chemical 11]

[0177]

[Chemical 12]

[0178]

[Chemical 13]

[0179]

[Chemical 14]

[0180]

[Chemical 15]

[0181]

[Chemical 16]

Good results were obtained by using an emulsion corresponding to the sample name Em-209 of Example-2 in the fifth high-sensitivity red-sensitive emulsion layer.

Claims (3)

[Claims] 1. A silver halide emulsion in which tabular grains having an aspect ratio of 3 or more and 100 or less and containing 10 or more dislocation lines per grain consist of 60% or more and 100% or less of the projected area of all silver halide grains. , After adding the sensitizing dye at 35 ℃ to 50 ℃, 5 ℃ to 50 ℃ from the addition temperature
A method for producing a silver halide photographic emulsion, which is spectrally sensitized through the following heat ripening step. 2. The method for producing a silver halide photographic emulsion according to claim 1, wherein the silver iodide content on the grain surface of the silver halide emulsion is 2 mol% or more and 15 mol% or less. 3. The method for producing a silver halide photographic emulsion according to claim 1, wherein in the silver halide emulsion, the variation coefficient of the grain size of all silver halide grains is 20% or less.