JPH05289269A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material superior in color developing performance and fastness of a color image and improved in color reproduction performance by making it contain a specified compound, CONSTITUTION:The silver halide color photographic sensitive material has on a support at least one silver halide emulsion layer and it is characterized by containing at least one kind f cyan coupler represented by the formula and in at least one of the silver halide emulsion layers, negative latent image type silver halide grains chemically sensitized from the surface of each grain to the depth of <=0.02mmu. In formula, R<1> is H or a substituent: R<2> is a substituent: X is H or a group to be released by coupling with the oxidation product of a color developing agent; and Z<1> is a nonmetallic atomic group necessary to form an N-containing 6-membered hetero ring.

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, to a negative internal latent image type emulsion having excellent color forming property, color image fastness, color reproducibility and good sensitivity. The present invention relates to a silver halide color photographic light-sensitive material contained.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is a reaction of a dye-forming coupler (hereinafter referred to as a yellow coupler, a magenta coupler and a cyan coupler, respectively) that develops yellow, magenta and cyan, respectively, with a color developing agent. The method of forming a color image using
Currently most widely used. Among them, in a silver halide photographic light-sensitive material, an internal latent image type emulsion has been developed to increase the storage stability of the emulsion and increase the sensitivity. Various attempts have been made to further increase the sensitivity of a light-sensitive material using this internal latent image type emulsion. For example, U.S. Pat. Nos. 2,696,436, 3,206,313, 3,917,485, 3,979,213, 4,623,612, and Japanese Patent Publication No. 43-29405. No. 45-13259, No. 45-13259, discloses that a silver halide emulsion coating sample is immersed in an AgNO ₃ solution or a silver halide solvent, or is soluble in Ostwald ripening or AgNO ₃ aqueous solution after chemical sensitization in the process of producing a silver halide emulsion. It is described that a silver halide photographic emulsion having a large internal sensitivity or a silver halide photographic light-sensitive material is prepared by adding an aqueous solution of a halogen salt, and that its photographic properties are good.

By the way, cyan couplers generally used in silver halide color photographic light-sensitive materials are phenol-type and naphthol-type couplers. On the other hand, in recent years, in order to improve the color developability (coupling activity and molecular extinction coefficient of the obtained dye) of these phenol-type and naphthol-type couplers, the fastness of the obtained color image, the absorption characteristics of the color image, etc. Proposed as a new cyan coupler. For example, 3-hydroxypyridine compounds described in European Patent No. 333,185, 3H-2-dicyanomethylidene thiazoles described in European Patent No. 362,808, and JP-A No. 64-32260. 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1,1-dioxides, JP-A-63-264
753 and the pyrazoloazoles described in U.S. Pat. No. 4,873,183, U.S. Pat. No. 4,818,672.
No. 4,921,783 and JP-A-3-48243.
And imidazoles described in Japanese Patent No. 30
4,001, 329,036, 374,781
And Pyrazolopyrimidones and Pyrazoloquinazolones described in JP-A No. 2-85851 and EP-A-342.
The condensed ring triazoles described in No. 637 can be mentioned. However, in a silver halide color photographic light-sensitive material using an internal latent image type emulsion, the performance of these proposed new cyan couplers cannot satisfy the above-mentioned color forming property, color image fastness and color reproducibility at the same time. However, further improvement was required for practical use. That is, the dyes produced from these couplers have unnecessary absorption in the blue and green regions, which is a major obstacle to improving color reproducibility. Further, the conventional cyan coupler has a problem that it causes an interaction with a silver halide emulsion and thus lowers the sensitivity of a light-sensitive material using an internal latent image type emulsion containing this coupler.

[0004]

SUMMARY OF THE INVENTION Therefore, the present invention provides a silver halide color photographic light-sensitive material which is excellent in cyan color image development and color image fastness, has improved color reproducibility, and exhibits good sensitivity. The purpose is to provide. A further object of the present invention is to provide a silver halide color photographic light-sensitive material using an internal latent image type emulsion, which does not cause deterioration in sensitivity even after storage.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies in order to overcome the drawbacks of the conventional silver halide color photographic light-sensitive materials, and as a result, have found that they have a novel nitrogen-containing 6-membered heterocyclic ring. A cyan coupler, and improves the color reproducibility by sensitizing a very shallow interior of the internal latent image type silver halide emulsion having a depth of less than 0.02 μm from the surface of the silver halide grain. At the same time, it was found that the decrease in sensitivity can be prevented and the above-mentioned object can be achieved, and the present invention has been completed based on this finding. That is, the present invention provides a photographic light-sensitive material having one or more silver halide emulsion layers on a support, the photographic light-sensitive material containing at least one cyan coupler compound represented by the following general formula (I): At least one of the silver halide emulsion layers contains negative internal latent image type silver halide grains chemically sensitized to a depth of less than 0.02 μm from the grain surface. A color photographic light-sensitive material is provided.

[0006]

[Chemical 2] (In the formula, R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidation product of a color developing agent, and Z ¹ represents Represents a group of non-metal atoms necessary for forming a nitrogen-containing 6-membered heterocycle, provided that the heterocycle has at least one dissociative group.)

Next, the above-mentioned general formula (I) used in the present invention is used.
The cyan coupler represented by will be described in detail. In formula (I), R ¹ represents a hydrogen atom or a substituent, and R ² represents a substituent. The substituents of R ¹ and R ² include aryl group, alkyl group, cyano group, acyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, formylamino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonyl group. Amino group, sulfonamide group, ureido group,
Sulfamoylamino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, heteryloxy group, alkylthio group, arylthio group, heterylthio group, heterocyclic group, halogen atom, hydroxy group, nitro group, sulfamoyl group, sulfonyl Examples thereof include groups, acyloxy groups, carbamoyloxy groups, imide groups, sulfinyl groups, phosphoryl groups, carboxyl groups, phosphono groups, and unsubstituted amino groups. Among these, the groups which can further have a substituent may be substituted with the above-mentioned substituent.

Specific examples of the substituents of R ¹ and R ² include an aryl group (preferably having 6 to 30 carbon atoms, for example, phenyl, m-acetylaminophenyl, p-methoxyphenyl) and an alkyl group (preferably having 1 carbon atom). ~ 30, for example methyl, trifluoromethyl, ethyl, isopropyl,
Heptafluoropropyl, t-butyl, n-octyl,
n-dodecyl), a cyano group, an acyl group (preferably having a carbon number of 1 to 30, such as acetyl, pivaloyl, benzoyl, furoyl, 2-pyridylcarbonyl), a carbamoyl group (preferably having a carbon number of 1 to 30, such as methylcarbamoyl, ethyl). Carbamoyl, dimethylcarbamoyl,
n-octylcarbamoyl), an alkoxycarbonyl group (preferably having a carbon number of 1 to 30, such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), an aryloxycarbonyl group (preferably having a carbon number of 7 to 30, such as phenoxycarbonyl, p-methoxy). Phenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl), formylamino group, acylamino group (preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (eg, acetylamino, propionylamino, cyanoacetylamino), preferably Is an arylcarbonylamino group having 7 to 30 carbon atoms (for example, benzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably Heterylcarbonylamino group having a prime number of 4 to 30 (eg, 2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)}, alkoxycarbonylamino group (preferably having a carbon number of 2 to 30, such as methoxycarbonylamino, ethoxycarbonylamino) , Methoxyethoxycarbonylamino), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino), sulfonamide. A group (preferably having 1 to 30 carbon atoms, for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), an ureido group (preferably having 1 to 30 carbon atoms, for example, Ruureido, dimethyl ureido, p- cyanophenylureido), a sulfamoylamino group (preferably 1 to carbon atoms
30, for example methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino),
Alkylamino group (preferably having 1 to 30 carbon atoms, for example, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino), arylamino group (preferably having 6 to 30 carbon atoms, such as anilino), alkoxy group (preferably Represents 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy), an aryloxy group (preferably 6 to 30 carbon atoms, such as phenoxy, m-chlorophenoxy, p-. Methoxyphenoxy, o-methoxyphenoxy), a heteryloxy group (preferably having a carbon number of 3 to
30, such as tetrahydropyranyloxy, 3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), an alkylthio group (preferably having 1 to 30 carbon atoms such as methylthio, ethylthio, n-butylthio, t-butylthio), Arylthio group (preferably having 6 to 3 carbon atoms)
0, for example, phenylthio, a heterylthio group (preferably having 3 to 30 carbon atoms, for example, 2-pyridylthio, 2-
(1,3-benzoxazolyl) thio, 1-hexadecyl-1,2,3,4-tetrazolyl-5-thio, 1-
(3-N-octadecylcarbamoyl) phenyl-1,
2,3,4-tetrazolyl-5-thio), a heterocyclic group (preferably having 3 to 30 carbon atoms, for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro- 1-tetrazolyl, 1
-Pyrrolyl, 2-furanyl, 2-pyridyl, 3-pyridyl), a halogen atom (e.g. fluorine, chlorine, bromine), a hydroxy group, a nitro group, a sulfamoyl group (preferably having a carbon number of 0 to 30, such as methylsulfamoyl, Dimethylsulfamoyl), a sulfonyl group (preferably having a carbon number of 1 to 30, such as methanesulfonyl, benzenesulfonyl, toluenesulfonyl), an acyloxy group (preferably having a carbon number of 1 to 30, such as formyloxy, acetyloxy, benzoyloxy), Carbamoyloxy group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyloxy, diethylcarbamoyloxy), imide group (preferably having 4 to 30 carbon atoms, for example, succinimide, phthalimido), sulfinyl group (preferably having 1 carbon atom) ~ 3
0, for example, diethylaminosulfinyl), a phosphoryl group (preferably having 0 to 30 carbon atoms, for example, dimethoxyphosphoryl), a carboxyl group, a phosphono group, and an unsubstituted amino group.

[0009] Preferably, at least one of R ^1, R ² is the value of the substituent constant sigma _p of Hammett is 0.35 or more electron-withdrawing group, more preferably at least one of R ^1, R ² One of them is an electron-withdrawing group having a value of σ _p of 0.60 or more, and particularly preferably, at least one of R ¹ and R ² is a cyano group.

Here, the Hammett's substituent constant used in the present specification will be briefly described. Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Substituent constants obtained by Hammett's law include σ _p values and σ _m , and these values can be found in many general textbooks. For example, JA Dean,
"Lange's, Handbook of Chemistry" 12th Edition, 197
9th year (McGraw-Hill) and special issue of "Chemical field", 122
No. 96-103, 1979 (Nankodo).
In the present invention, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited only to a substituent having a known value found in the above-mentioned book. It goes without saying that, even if the value is unknown in the literature, it also includes a substituent that may be included in the range when measured based on Hammett's rule.

The electron-withdrawing group having a σ _p value of 0.35 or more includes a cyano group (σ _p value of 0.66) and a nitro group (0.7 _p value).
8), carboxyl group (0.45), perfluoroalkyl group (for example, trifluoromethyl (0.54), perfluorobutyl), acyl group (for example, acetyl (0.50), benzoyl (0.43)) ), A formyl group (0.42), a sulfonyl group (eg, trifluoromethanesulfonyl (0.92), methanesulfonyl (0.
72), benzenesulfonyl (0.70)), a sulfinyl group (for example, methanesulfinyl (0.49)),
A carbamoyl group (for example, carbamoyl (0.36),
Methylcarbamoyl (0.36), phenylcarbamoyl, 2-chloro-phenylcarbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl (0.4
5), ethoxycarbonyl, diphenylmethylcarbonyl), a heterocyclic residue (for example, pyrazolyl (0.37),
1-tetrazolyl (0.50)), an alkylsulfonyloxy group (for example, methanesulfonyloxy (0.3
6)), a phosphoryl group (for example, dimethoxyphosphoryl (0.60), diphenylphosphoryl), a sulfamoyl group (0.57), a pentachlorophenyl group, a pentafluorophenyl group or a sulfonyl group-substituted aromatic group (for example, 2,4 -Dimethanesulfonylphenyl) and the like are preferable. Preferable examples of the electron withdrawing group having a σ _p value of 0.60 or more include a cyano group, a nitro group and a sulfonyl group.

X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with a color developing agent, for example, an oxidation product of an aromatic primary amine developing agent (hereinafter referred to as a coupling-off group).

Specific examples of the coupling-off group include:
Halogen atom (eg fluorine, chlorine, bromine), alkoxy group (eg ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy group (eg 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), an acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), a sulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (for example, dichloroacetylamino, heptafluorobutyrylamino), Sulfonamide group (eg, methanesulfonamide, p-toluenesulfonamide), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarboxyl) Boniruokishi), an aryloxycarbonyl group (e.g., phenoxycarbonyloxy), an alkylthio group (e.g., carboxymethylthio), an arylthio group (e.g., 2-butoxy -5-te
rt-octylphenylthio), a heterocyclic thio group (eg tetrazolylthio), a carbamoylamino group (eg N
-Methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (For example, succinimide, hydantoinyl), aromatic azo group (for example, phenylazo), sulfinyl group (for example, 2-butoxy-5-tert-octylphenylsulfinyl), sulfonyl group (for example, 2-butoxy-5-tert-octylphenylsulfonyl).
Etc., and these groups may be further substituted with a group which is allowed as a substituent for R ¹ .

There is also a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator.

Z ¹ represents a group of non-metal atoms necessary for forming a nitrogen-containing 6-membered heterocycle and has at least one dissociative group. Four 2's for constituting the nitrogen-containing 6-membered heterocycle
As the valent linking group, -NH-, -N (R)-, -N
=, -CH (R)-, -CH =, -C (R) =, -CO
-, - S -, - SO -, - SO 2 - , and the like.
(R represents a substituent, and examples thereof include the groups mentioned for R ¹ and R ^2. ) Examples of the dissociative group are —NH— and —CH (R) —.
And the like, and those having a pKa value in water of 3 to 12 are preferable.

The cyan coupler represented by the general formula (I) can be preferably represented by the general formula (II) to the general formula (XIX).

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

(Wherein R ¹ , R ² and X are represented by the general formula (I)
Is synonymous with that in. R ³ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a substituent, and R ⁴ represents a substituent. EWG represents an electron-withdrawing group having a Hammett's substituent constant σ _p of 0.35 or more. )

Examples of the groups R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as those described for R ¹ and R ² .

The coupler represented by the general formula (I) has R
The group of ^{1 to} R ⁸ may have a coupler residue represented by the general formula (I) to form a dimer or higher polymer, and the group of R ^{1 to} R ⁸ may be a polymer chain. And may form a homopolymer or a copolymer. The homopolymer or copolymer bound to the polymer chain is typically an addition polymer having a coupler residue represented by the general formula (I), a homopolymer or copolymer of an ethylenically unsaturated compound. In this case, one or more kinds of color-forming repeating units having a coupler residue represented by the general formula (I) may be contained in the polymer, and an acrylic acid ester, a methacrylic acid ester, a maleic acid ester as a copolymer component. It may be a copolymer containing one or more non-color-forming ethylenic monomers such as those described above.

Next, typical compounds of the coupler used in the present invention will be shown, but the present invention is not limited thereto. The substituents used in the compound examples are described below in numerical order.

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

Typical compounds of the coupler of the present invention are shown in the table below, but the present invention is not limited thereto.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

Next, synthesis examples of typical couplers of the present invention will be shown.

(Synthesis Example 1) Synthesis of coupler (III) -1

[0040]

[Chemical 13]

2-amino-3-cyano-4-phenylpyrrole (Compound a) (18.3 g) and diethyl ethoxyethylidene malonate (25.30) which are easily obtained by condensing 2-aminoacetophenone hydrochloride and malononitrile in the presence of an alkali. 3 g was dispersed in 300 ml of ethanol, 22.0 ml of 28% methanol solution of sodium methylate was added thereto, and the mixture was heated under reflux for 5 hours. After cooling
After adding ethyl acetate and washing with water, the organic solvent was concentrated, and the precipitated crystals were collected by filtration to obtain 11.6 g of compound b. Next, 50 ml of Fine Oxocor 1600,
Titanium isopropoxide (Ti (O-i-Pr)
₄ ) Add 2.0 g, and add 6 at an oil bath temperature of 130-140 ° C.
Heated for hours. After cooling, the residue was purified by silica gel chromatography (hexane / ethyl acetate = 1/1) to obtain 14.7 g of coupler (III) -1 as a pale yellow oily substance.

(Synthesis Example 2) Synthesis of coupler (III) -3

[0043]

[Chemical 14]

2-Amino-3-cyano-4-phenylpyrrole (compound a) (18.3 g) and diethyl ethoxymethylenemalonate (24.0 g) were dispersed in ethanol (400 ml), and sodium methylate 28% methanol solution 22. 0 ml was added and the mixture was heated under reflux for 1 hour. After cooling
The precipitated crystals were collected by filtration to obtain 28.0 g of compound c. Then, fine oxochol 16001
50 ml and Ti (Oi-Pr) ₄ 4.0g were added and it heated at oil bath temperature 130-140 degreeC for 2 hours. After cooling
Purified by silica gel chromatography, coupler (I
II) -3 36.2 g was obtained.

(Synthesis Example 3) Synthesis of coupler (II) -1

[0046]

[Chemical 15]

2-Amino-3-cyano-4-phenylpyrrole (Compound a) (18.3 g) and ethyl p-octadecyloxybenzoylacetate (46.0 g) were dispersed in 300 ml of acetic acid and heated under reflux for 8 hours. After cooling, 1 liter of ethyl acetate and 1 liter of water were added, and the precipitated crystals were collected by filtration,
29.0 g of coupler (II) -1 was obtained. In the light-sensitive material of the present invention, the amount of the cyan coupler used is usually 0.001 to 100 mol, preferably 0.01 to 10 mol, and more preferably 0.1 to 1 mol, based on 1 mol of silver halide.

The internal latent image type emulsion of the present invention must be chemically sensitized to a depth of less than 0.02 μm from the grain surface. When the position 0.02 μm or more from the surface is chemically sensitized, the black and white / color negative / color reversal light-sensitive material is not sufficiently developed even if it is developed with a practical developer, resulting in substantial loss of sensitivity. In addition, the effect of the addition of the tellurium compound of the present invention is not remarkable. The above-mentioned practical developing solution means a developing solution from which a silver halide solvent is intentionally removed so as to develop only a surface latent image, or a large amount of silver halide intended to develop an internal latent image. Instead of a developing solution containing a solvent, it contains a silver halide solvent capable of exhibiting optimum sensitivity by causing a reduction reaction while appropriately dissolving silver halide. However, if the solvent is contained in a large amount, the silver halide is excessively dissolved during the processing, and the graininess is deteriorated by infectious development, which is not preferable. Specifically, it is preferable that the developer contains 100 mg / liter or less and 20 mg / liter or more of potassium iodide or 100 g / liter or less and 20 mg / liter or more of sodium sulfite or potassium sulfite as a silver halide solvent. In addition, potassium thiocyanate or the like can be used as a silver halide solvent in the developing solution.

The more preferable position of the chemically sensitized portion is 0.002 μm or more and less than 0.015 μm, and more preferably 0.004 μm or more and less than 0.01 μm. Further, more preferably, it is necessary to pay attention not only to the site to be chemically sensitized, but also to the latent image distribution in the grain including the ratio of the surface sensitivity to the internal sensitivity. In this case, the latent image distribution in the particle generated by exposure has at least one local maximum value inside the particle, the position where this one local maximum value exists is less than 0.01 μm from the particle surface, and the particle surface also has the above-mentioned value. Most preferably, it is chemically sensitized so that it is 1/5 or more and less than 1 time the maximum value.

Here, the latent image distribution is the depth of the latent image from the particle surface (x μm) on the horizontal axis and the number of latent images (y) on the vertical axis, where x is

[Equation 1] S: average grain size of silver halide emulsion (μm) Ag ₁ : amount of silver remaining after unexposed emulsion-coated sample was subjected to the following treatment Ag ₀ : amount of silver coated before treatment, and y was 1 / 100
It is the reciprocal of the exposure amount that gives a density of fog + 0.2 when the following processing is performed after white exposure for 2 seconds. The processing conditions for obtaining the latent image distribution are as follows: N-methyl-p-aminophenol sulfate 2.5 g L-sodium ascorbate 10 g sodium metaborate 35 g potassium bromide 1 g Water added 1 liter (pH 9.6). Sodium thiosulfate is added to the treatment liquid in an amount of 0 to 10 g / liter and treated at 25 ° C. for 5 minutes. By changing the amount of sodium thiosulfate from 0 to 10 g / liter, the depth from the surface of the latent image in the silver halide grains developed during processing is changed, and the number of latent images in the depth direction is changed. You can know the change of.

The method for preparing the internal latent image type emulsion is described in US Pat. No. 29405, No. 45-13259 and the like can be used. In any method, a chemical sensitization method or a chemical sensitization method is used to obtain an emulsion having a latent image distribution of the present invention. The amount of silver halide precipitated after chemical sensitization and the conditions for precipitation must be adjusted. That is, U.S. Pat. No. 3,966,476 also implements a method of precipitating silver halide beyond the emulsion grains after chemical sensitization by the control double jet method. However, when chemically sensitized silver halide is precipitated by the method as practiced in this patent, the photosensitive nuclei cannot be embedded inside the grain. Therefore, in order to obtain the latent image distribution of the present invention, the amount of silver halide precipitated after the chemical sensitization is larger than that carried out in U.S. Pat. No. 3,966,476 and the precipitation conditions ( For example, it is necessary to control the solubility of silver halide in the precipitation and the rate of adding the soluble silver salt and the soluble halogen salt) so that the thickness is less than 0.02 μm.

Further, in US Pat. No. 3,979,213, an internal latent image type emulsion is prepared by a method of precipitating silver halide again on the emulsion grains whose surfaces are chemically sensitized by the control double jet method. .. If the amount of silver halide practiced in this patent were to be precipitated on the grains, the ratio of surface sensitivity to total sensitivity would be less than one tenth. Therefore, the amount of silver halide precipitated after chemical sensitization should be less than that practiced in U.S. Pat. No. 3,979,213 for the most favorable latent image distribution.

Of the internal latent image type emulsions of the present invention, the most preferable one is a photographic emulsion having a step of forming a shell on a silver halide core grain as described in Japanese Patent Application No. 1-1150728. In the method, it can be obtained by a method for producing a silver halide photographic emulsion, which comprises chemically sensitizing the core grains and then forming a shell in the presence of a tetrazaindene compound. In this method, the tetrazaindene-based compound is used in a dispersion system in which seed grains and / or silver halide grains growing with seed grains as nuclei are dispersed, that is, in the emulsion in an amount of 10 per 1 mol of silver halide contained in the emulsion. It is preferably present in the range of ^-2 to 10 ^-5 mol, more preferably 10 ^-2 to 10 ^-5.
-4 mol range. The addition amount of the tetrazaindene-based compound has a great influence on the latent image distribution from the surface of the silver halide grain to the inside thereof, but the optimum amount thereof is the halogen composition of the emulsion grains and the precipitation of silver halide in the core, that is, the core. Is appropriately increased or decreased within the above-mentioned addition amount range depending on pAg, pH, temperature and the like when further growing.

For example, a large amount of Ag used for shell formation,
When the number of latent images on the shell surface is small, it is preferable to add a larger amount of the tetrazaindene compound in the above addition amount range, but on the other hand, the amount of Ag used for shell formation is small and the number of latent images on the shell surface is large. When it tends to occur, it is preferable to add a smaller amount. The tetrazaindene-based compound may be added directly to a water-soluble protective colloid solution containing seed particles, and the tetrazaindene-based compound may be dissolved in a water-soluble silver halide aqueous solution to form seed particles as a nucleus. It is also possible to gradually add it as it grows. The tetrazaindene-based compound may be present at the time of further grain growth from the core grain, and may be added before the chemical sensitization of the core. In particular, the tetrazaindene compound is adsorbed on the silver halide grains and has a function of specifying the site to be chemically sensitized, and therefore it is preferable that the compound is present even during the chemical sensitization of the core.

In the present method, the amount of silver used in the step of forming a shell on the chemically sensitized core and the amount of silver (M) in the shell portion preferably satisfy the following general formula. That is,

[Equation 2] M ₀ : Silver amount of seed particles R: Final particle size (μ) The silver potential (SCE) in the step of forming the shell on the core particles in this method is +80 mV or less, −30 mV.
The above is preferable. When it is higher than +80 mV, the chemical sensitizer which is not used during the chemical sensitization during the shell formation process easily reacts with the shell portion, so that the surface sensitivity is made higher than the internal sensitivity. Also,
When the shell formation on the core particles is performed at less than -30 mV,
The chemically sensitized core particle surface undergoes an oxidation reaction due to excess halogen, resulting in a decrease in sensitivity. A more preferable silver potential in the step of growing the core particles is −10 mV or higher, +60.
It is mV or less.

In the present invention, the temperature in the step of forming the shell on the core particles is preferably + 70 ° C. or lower, + 35 ° C. or higher. When the temperature is higher than + 70 ° C., the residual chemical sensitizer easily reacts with the shell portion as described above, so that the surface sensitivity cannot be lower than the internal sensitivity. Further, when the core grains are grown below + 35 ° C., new nuclei are likely to be generated during the crystal growth process, and new silver halide is not sufficiently precipitated on the chemically sensitized site of the core grains. That is, new nuclei are likely to be generated in the shell forming step, which is not preferable. A more preferable temperature in the shell forming step is 45 ° C. or higher and 60 ° C. or lower. In the present invention, the addition rate of the water-soluble silver salt solution in the grain growth step from the core grain is preferably within the range of 30 to 100% of the crystal growth critical rate. What is the critical speed of crystallization?
It is defined as the upper limit at which new nuclei are not substantially generated in the process of grain growth. In addition, the term "substantially not generated" means that the weight of newly generated crystal nuclei is preferably 1 of the total silver halide weight.
It means 0% or less.

In the present invention, the chemical sensitization of the core particles is performed by James (TH James), The Theory of Photographic Process, 4th edition, published by MacMillan, 1977 (TH James, The Theory). of the P
hotographic Process, 4thed, Macmillan, 1977) 67
~ Research Disclosure 1 can be carried out using activated gelatin as described on pages 76-76.
Volume 20, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 1345.
2, U.S. Pat. Nos. 2,642,361 and 3,297,
No. 446, No. 3,772, 031, No. 3,857, 7
No. 11, No. 3,901,714, No. 4,266,01
8 and 3,904,415, as well as several combinations of sulfur, selenium, tellurium, gold, platinum, iridium as described in GB 1,315,755. In the most preferred embodiment, the silver potential (SCE) is ± 0 mV or more and +120 mV or less, more preferably +30 mV or more and +120 mV or less, and further preferably +60 mV or more and +120 mV or less. Increasing the silver potential, ie, pulling pAg, not only obtains good sensitivity by effectively promoting the chemical sensitization reaction, but also reduces the residual chemical sensitizer remaining even during the formation of the shell. , Which is preferable because the surface sensitivity is lower than the internal sensitivity.

In the present invention, the layer containing the internal latent image type emulsion is not particularly limited, but a red-sensitive emulsion layer is preferable, and the same layer as the cyan coupler represented by the general formula (I) is preferably contained. The latent image ratio formed on the surface of the internal latent image type emulsion is preferably 0.1 to 0.
8, more preferably 0.2 to 0.7. Further, the silver halide color photographic light-sensitive material of the present invention is preferably subjected to a developing treatment with a developing solution containing a silver halide solvent to form an image. The silver halide color photographic light-sensitive material of the present invention is preferably a silver halide color reversal light-sensitive material.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. 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 at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light,
In the multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer 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. Non-photosensitive layers 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. In the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-
The couplers and DIR compounds as described in the specifications of 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751, JP-A-62-200350,
As described in JP-A Nos. 62-206541 and 62-206543, 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.
As a specific example, from the side farthest from the support, a 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 / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-639.
As described in Japanese Patent No. 36, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer. In addition, they may be 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. Also, in the case of four layers or more, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat. Nos. 4,663,271 and 4,705,744,
No. 4,707,436, JP-A-62-160448.
No. 63-89850, and BL, G described in the specification.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

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%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less, but the projected area diameter is about 10 μm.
It may be a large-sized grain up to and including a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (R
D) No. 17643 (December 1978), 22-23
Page, "I. Emulsion preparation and type
s) ", and No. 18716 (November 1979),
Pp. 648, No. 307105 (November 1989),
Pp. 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et P.
hisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
Monodisperse emulsions described in 655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform or may have different halogen compositions inside and outside,
It may have a layered structure, or silver halides having different compositions may be joined by epitaxial junction, or may be joined with a compound other than silver halide such as silver rhodanide or lead oxide. . Also, a mixture of particles having various crystal forms may be used. The internal latent image type emulsion used in the present invention may be the core / shell type internal latent image type emulsion described in JP-A-63-264740. 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 of this emulsion varies depending on the development process and the like, but is 3-40.
nm is preferable, and 5 to 20 nm is particularly preferable.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additives used in such a process are Research Disclosure No. 17643, No. 18716, and No. 30.
No. 7105, the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion are mixed in the same layer. Can be used. Surface-fogged silver halide grains described in US Pat. No. 4,082,553, US Pat. No. 4,62.
No. 6,498 and JP-A No. 59-214852, in which the inside of the grains are fogged, colloidal silver is used as a photosensitive silver halide emulsion layer and / or a substantially non-photosensitive hydrophilic colloid layer. Can be preferably used. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498, JP-A-59-2.
No. 14852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain 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 0.75 μm, particularly 0.05 to 0.6 μm.
Is preferred. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are ± 40 of the average grain size). %) Is preferable.

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 developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain diameter (average value of circle-equivalent diameters of projected areas) of 0.01 to 0.5 μm, and 0.02 to
0.2 μm is more preferable. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. 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, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. The coating amount of silver of the light-sensitive material of the present invention is 6.
It is preferably 0 g / m ² or less, and most preferably 4.5 g / m ² or less.

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 23 648 page right column 866 page 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23 to page 648 right column 866 to 868 Supersensitization Agent ~ page 649 right column 4 whitening agent page 24 647 page right column 868 page 5 antifoggant, page 24 ~ 25 page 649 right column 868 ~ 870 stabilizer 6 light absorber, page 25 ~ 26 page 649 right column Page 873 Filter dye, page 650 Left column UV absorber 7 Anti-staining agent Page 25 Right column Page 650 Left column Page 872 Right column 8 Dye image stabilizer Page 25 Page 650 Left column Page 872 9 Hardener 26 Page 651 Page left column 874 to 875 page 10 Binder page 26 page 651 page left column 873 to 874 page 11 Plasticizer, lubricant 27 page 650 page right column 876 12 Coating aid, page 26 to 27 page 650 right column 875 to 876 page Surface active agent 13 Static protection page 27 page 650 right column 876 to 877 stop agent 14 matting agent page 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, the international publication WO88 / 04
No. 794, Dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to incorporate the dyes described in No. Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 176 above.
43, VII-C to G, and No. 307105, VII-
It is described in the patents described in C to G. Yellow couplers include, for example, U.S. Pat. No. 3,933,501.
No. 4,022,620, 4,326,02
No. 4, No. 4,401,752, No. 4,248,9
No. 61, Japanese Patent Publication No. 58-10739, British Patent Nos. 1 and 4
25,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023,
No. 4,511,649, European Patent No. 249,473.
Those described in No. A, etc. are preferable.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable. Examples of the polymer couplers of the present invention include US Pat.
No. 6,619, No. 4,351,897, European Patent No. 73,636, US Pat. No. 3,061,432,
No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-
33552, Research Disclosure No. 24
230 (June 1984), JP-A-60-43659.
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Pat. No. 4,500,630, No. 4,540,654.
No. 4,556,630, International Publication WO88 / 0
Those described in No. 4795 and the like are particularly preferable. Examples of cyan couplers that can be used in the present invention include phenol-based and naphthol-based couplers. US Pat. Nos. 4,052,212 and 4,146,396
No. 4,228,233, 4,296,20
No. 0, No. 2,369,929, No. 2,801,1
No. 71, No. 2,772, 162, No. 2,895.
No. 826, No. 3,772,002, No. 3,75
No. 8,308, No. 4,334,011, No. 4,3
27,173, West German Patent Publication No. 3,329,729
No., European Patent Nos. 121,365A and 249,45
3A, US Pat. Nos. 3,446,622 and 4,3.
No. 33,999, No. 4,775,616, No. 4,
451,559, 4,427,767, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658. Those described are preferred. Furthermore, JP-A-64-553
No. 64, No. 554, No. 64-555, No. 64-5
The pyrazoloazole-based couplers described in No. 56 and the imidazole-based couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,820.
No. 4,048,211 and No. 4,367,282
No. 4,409,320, No. 4,576,91
No. 0, British Patent 2,102,137, European Patent 34
No. 1,188A and the like.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) No. 3 , 234,533 are preferred. Researched Disclosure No. 1 is a colored coupler for correcting unwanted absorption of color forming dyes.
7643, Item VII-G, No. 307105, Item VII-G
, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
9413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers releasing a development inhibitor are disclosed in RD17643, VII-F and JP-A No. 307105, VII-F, JP-A-57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
63-37350, U.S. Pat. No. 4,248,9.
Those described in No. 62 and No. 4,782, 012 are preferable. RD No. 11449, 24241, JP-A-6
The bleaching accelerator releasing coupler described in JP-A No. 1-2201247 is effective for shortening the time of the processing step having a bleaching ability. In addition, the effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, and JP-A-59-157638.
Those described in JP-A-59-170840 are preferable. Further, JP-A-60-107029 and JP-A-60-25234.
Compounds which release a fog, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A No. 0-44940 and JP-A-1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. 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 (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate etc.), amides (N, N-diethyldodecane amide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-)
Amylphenol), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2) -Butoxy-5-t
ert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. 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, and a typical example is ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,54.
1, 230 and the like.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
No. 272248 and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2 described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Suitable supports that can be used in the present invention are described, for example, in RD. No. 1
7643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 897. 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, and 1
8 μm or less is more preferable, and 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. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photogr. Sci., Eng.
), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. The film 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 150
~ 400% is preferred. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to the side opposite to the side having the emulsion layer.
It is preferable to provide a 20 μm hydrophilic colloid layer (referred to as a back layer). This back layer includes the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, No. 18;
No. 307, 651, left column to right column, and No. 307105, pages 880-881. 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, and a typical example thereof is 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-ethyl-N-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2
-Hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N-
(3-hydroxypropyl) aniline, 4-amino-3
-Propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-
N- (4-hydroxybutyl) aniline, 4-amino-
3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N- Ethyl-N- (3-hydroxy-2
-Methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4
-Amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N-
(5-Hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N -Bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4
-Hydroxybutyl) aniline, and their sulfates,
Hydrochloride or p-toluene sulfonate may be used. Among these, especially 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxy Butyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles,
It is common to include a development inhibitor such as benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo. -N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N,
Representative examples include N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used 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 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and 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 0.1. It is 001-0.05. As a method of 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, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature and high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

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 processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment may be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt are preferable from the viewpoint of rapid treatment 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 the bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

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 are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45. -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644, and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. 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 is a compound having an acid dissociation constant (pka) of 2 to 5, specifically, acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred. As a fixing agent used in a fixing solution or a bleach-fixing solution, thiosulfate,
Thiocyanates, thioether compounds, thioureas,
Although a large amount of iodide salt and the like can be mentioned, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixer or the bleach-fixer has a pKa of 6.0 to adjust the pH.
It is preferable to add a compound of 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / liter.

The total time for the desilvering process is preferably as short as possible within the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the occurrence of stains after the treatment is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, Japanese Patent Laid-Open No. 62-62160
No. 183460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using a rotating means of JP-A No. 62-183461, and a wiper provided in the solution. Examples include a method of moving the light-sensitive material while bringing the blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby further improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. The improvement of stirring is due to the bleaching agent in the emulsion film,
It is considered that the supply of the fixing agent is accelerated, and as a result, the desilvering rate is increased. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action 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 60-1912.
It is preferable to have the photosensitive material transporting means described in JP-A No. 58 and 60-191259. JP-A-60-
As described in Japanese Patent No. 191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as couplers), the application, and the temperature of the rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. 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 Pictur.
e and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue). According to the multistage countercurrent method described in the above document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
Nos. 8542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society. The pH of washing water in the processing of the light-sensitive material of the present invention is
It is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected.
Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58
All known methods described in Nos. 14834 and 60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and 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. be able to. 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 that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14850 and N.
Schiff base type compound described in No. 15159, No. 1
Aldol compounds described in 3924, US Pat. No. 3,7
Metal salt complexes described in JP-A-53-135.
The urethane compound described in No. 628 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-144547.
No. 58-115438 and the like.
Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0078]

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

Example 1 (1) Preparation of emulsion a. Emulsion A 15% AgNO ₃ aqueous solution 800 cc and KBr while keeping pH 6.8 and silver potential (SCE) +60 mV in a 1,560 cc 3.4% gelatin aqueous solution kept at 75 ° C.
KI is 0.85 mol / liter and 0.03, respectively.
An aqueous solution containing 1 mol / liter was added by a double jet for 60 minutes to prepare monodisperse cubic core particles having a ridge length of 0.35 μm. Next, 1.8 mg of Compound A-5 was used as a sulfur sensitizer in the core particles, and sodium chloroaurate was used as a gold sensitizer, and Compounds A-2 and A-.
1.1 mg, 4.0 mg, 0.3 mg of 3 were added, respectively,
Chemical sensitization was carried out for 60 minutes at pH 6.8 and silver potential +80 mV. Here, 0.14 g each of the compounds A-1 and A-4,
After adding 0.3g, lower the temperature to 50 ℃ and re-add 15%
An aqueous solution containing 200 cc of AgNO ₃ aqueous solution, 0.85 mol / liter of KBr and 0.031 mol / liter of KI was added over 5 minutes at pH 6.8 and silver potential of +10 mV to precipitate the shell, and the average edge of the final particles. Length is 0.38 μm, average silver iodide content is 3.5 mol%
Cube monodisperse particles of were obtained. The soluble silver salt was removed by a conventional flocculation precipitation method to obtain an internal latent image type emulsion (emulsion A) having a final pH of 6.2 and a pAg of 8.4. Coefficient of variation of the grain size (ridge length) distribution of this emulsion (value obtained by dividing the standard deviation of the distribution by the average value and multiplying by 100)
Was 8%, and the variation coefficient of the silver iodide content distribution was 5%.
Alternatively, the particles obtained here have a (100) plane of 92%,
The (111) plane had a crystal habit of 8%. In addition, Table 1 shows the ratio of the latent image formed on the surface of the particles, which is determined by the method described in the text.

[0080]

[Chemical 16]

[0081]

[Table 7]

B. Emulsions B to E AgNO used for core formation and shell formation in Emulsion A
Internal latent image type emulsions (emulsions B to E) having different depths from the grain surface to the chemically sensitized position as shown in Table 7 were prepared by changing the ratio of the ₃ aqueous solutions. c. Emulsion F The conditions for forming a shell in Emulsion A are as follows:
An internal latent image type emulsion (Emulsion F) in which the ratio of the latent image formed on the surface was higher than that of the emulsion A was obtained by setting the temperature to 60 ° C. and the silver potential to 60 mV. d. Emulsion G The conditions for forming a shell in Emulsion A were set to a temperature of 40.
The internal latent image type emulsion (Emulsion G) in which the ratio of the latent image formed on the surface was smaller than that of the emulsion A was obtained by increasing the addition rate of the aqueous AgNO ₃ solution to 5 ° C. at a silver potential of −30 mV. e. Emulsion H Sulfur sensitizer added after core grain formation in Emulsion A,
The gold sensitizer and the compounds A-1, A-2, A-3, and A-4 were not added before the formation of the shell, but were added after the formation of the shell and the removal of the soluble silver salt to chemically sensitize the shell surface. A surface latent image type emulsion (emulsion H) was obtained by carrying out. At this time,
Optimum sensitivity was achieved by adding 1.2 times the sensitizer to Emulsion A. (2) Preparation of coating sample A multilayer color light-sensitive material comprising layers of the following compositions was prepared on a 127 µm-thick cellulose triacetate film support which was undercoated, and was designated as Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic Solvent Oil-1 0.1 g Microcrystalline solid dispersion of Dye E-1 0.1 g Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil -3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Fine grained silver iodobromide emulsion with surface and inside fogged (average grain size 0.06 μm, variation coefficient 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion 1 Silver amount 0.1 g Emulsion B (Emulsion B of Example 1) Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15g Coupler C-2 0.05g Coupler C-3 0.05g Coupler C-9 0.05g Compound Cpd-C 10mg High boiling point organic solvent Oil-2 0.1g Additive P-1 0.1g

Fifth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Emulsion B (Emulsion B of Example 1) Silver amount 0.2 g Emulsion 2 Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion 3 Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g Seventh layer: intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd -I 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g UV absorber U-5 0.01 g Dye D-1 0.02 compound Cpd-C 5 mg compound Cpd-J 5 mg compound Cpd-K 5mg High boiling point Dot organic solvent Oil-1 0.02g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1. 0g Additive P-1 0.2g Color mixing inhibitor Cpd-A 0.1g 9th layer: low sensitivity green sensitive emulsion layer Emulsion 4 Silver amount 0.1g Emulsion 5 Silver amount 0.2g Emulsion 6 Silver amount 0.2g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g Compound Cpd-C 10 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02g Compound Cpd-G 0.02g High-boiling point organic solvent Oil-1 0.1g High-boiling point organic solvent Oil-2 0.1g 10th layer: Medium-speed green sensitive emulsion layer Emulsion 6 Silver amount 0. Three g Emulsion 7 Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd- E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling point organic solvent Oil-2 0.01 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion 8 Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil -1 0.02 g High boiling point organic solvent Oil-2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g Layer 14: Intermediate layer Gelatin 0.6 g Layer 15: Low sensitivity blue sensitive emulsion layer Emulsion 9 Silver amount 0.2 g Emulsion 10 Silver amount 0.3 g Emulsion 11 Silver amount 0.1 g Gelatin 0.8 g Coupler C-50 .2 g Coupler C-6 0.1 g Coupler C-10 0.4 g 16th layer: Medium-speed blue-sensitive emulsion layer Emulsion 11 Silver amount 0.1 g Emulsion 12 Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0. 3 g Coupler C-6 0.1 g Coupler C-10 0.1 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion 13 Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler -6 0.6 g Coupler C-10 0.1 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: second protective layer Colloidal silver Ag amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methylmethacrylate and acrylic acid 4: 6 Copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents. The silver iodobromide emulsions 1 to 13 used are as follows.

[0090]

[Table 8]

[0091]

[Table 9]

[0092]

[Table 10]

[0093]

[Chemical 17]

[0094]

[Chemical 18]

[0095]

[Chemical 19]

[0096]

[Chemical 20]

[0097]

[Chemical 21]

[0098]

[Chemical formula 22]

[0099]

[Chemical formula 23]

[0100]

[Chemical formula 24]

[0101]

[Chemical 25]

[0102]

[Chemical formula 26]

[0103]

[Chemical 27]

[0104]

[Chemical 28]

[0105]

[Chemical 29]

[0106]

[Chemical 30]

Next, the emulsion B and the cyan coupler of Sample 101 were replaced as shown in Table 11 to prepare Sample 10
2-116 were produced. The obtained sample was exposed through a wedge at 1000 lux for 1/50 second. Then, in the first step as shown below, a negative image development was carried out, and a positive image forming treatment was carried out in which color development was carried out using the remaining silver halide. Table 8 shows the relative sensitivities obtained from the exposure amount necessary to obtain a cyan color density of 1.0 higher than the minimum density of the image thus obtained. Further, the transmission density of each of the treated samples was measured, a characteristic curve thereof was obtained, and the following performance evaluation was performed. The results are shown in Table 11.

(1) Coloring property The logarithm of the exposure amount giving the density of the minimum density (Dmin) +1.0 is found from each characteristic curve, and this is taken as the sensitivity point (S). (ΔS) was calculated. Further, from the sensitivity point S to the high exposure dose side, log = 0.3
The density of the point giving the exposure amount of
The concentration ratio (D%) was calculated with reference to the concentration value of. The results are shown in Table 11. As for ΔS, the larger the plus value is, the higher the feeling is. The value of D is larger than 100, the higher the coloring density is. (2) Color image fastness The image was stored for 10 days under conditions of 80 ° C. and 70% RH as wet heat fastness. As for light fastness, a xenon fading tester (illuminance: 80,000 lux) was used for exposure for 10 days. After the end of the test, the density of these samples was measured again, and the density after the test at the exposure amount giving the density before test disclosure of 2.0 was calculated as the residual ratio (%) of the read color image.
Shown in 1. A numerical value closer to 100 indicates that the color image fastness is excellent. The following can be seen from the results in Table 11.
In contrast to the sample 102, the sample 110 using the cyan coupler of the present invention improves the color-developing color image fastness, but the sensitivity is lowered. On the other hand, when the emulsion of the present invention is used, it is sensitized (0.07) to sample 102 as in sample 101.
However, the color development and color image fastness cannot be improved. Here, Sample 11 using the coupler of the present invention
In contrast to Sample No. 104 using the emulsion B of the present invention,
Sensitization higher than 07 is observed, and sensitivity, color developability, and color image fastness can all be improved.

[0109]

[Table 11]

Treatment process time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 2 minutes 38 ° C. 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C. 4 liters 1100 ml / m ² color development 6 min 38 ° C. 12 liters 2200 ml / m ² adjustment 2 minutes 38 ° C. 4 liters 1100 ml / m ² Bleaching 6 min 38 ° C. 12 liters 220 ml / m ² Fixing 4 min 38 ° C. 8 liters 1100 ml / m ² second Washing with water 4 minutes 38 ° C 8 liters 7500 ml / m ² stability 1 minute 25 ° C 2 liters 1100 ml / m ²

The composition of each processing liquid was as follows. (First developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylene phosphonic acid-5 sodium salt 1.5 g 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 ml 1000 ml pH 9.60 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide. (Reversal liquid) (Tank liquid) (Replenishing liquid) Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 3.0 g Same as tank liquid Stannous chloride dihydrate 1.0 g p-aminophenol 0 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide. (Color developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylene phosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl- 4-aminoaniline / 3/2 sulfuric acid monohydrate 11g 11g 3,6-dithiaoctane-1,8-diol 1.0g 1.0g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH is hydrochloric acid or water. Adjusted with potassium oxide. (Adjusting liquid) (Tank liquid) (Replenishing liquid) Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g 8.0 g Sodium sulfite 12 g 12 g 1-Thioglycerol 0.4 g 0.4 g Formaldehyde sodium bisulfite adduct 30 g 35 g Water was added to 1000 ml 1000 ml pH 6.30 6.10 The pH was adjusted with hydrochloric acid or sodium hydroxide.

(Bleaching solution) (Tank solution) (Replenishing solution) Ethylenediaminetetraacetic acid / disodium salt / dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g 240 g Bromide Potassium 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 H was adjusted with hydrochloric acid or sodium hydroxide. (Fixing solution) (Tank solution) (Replenishing solution) Ammonium thiosulfate 80 g The same sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to the tank solution 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. (Stabilizing liquid) (Tank liquid) (Replenishing liquid) Benzisothiazolin-3-one 0.02 g 0.03 g Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 g 0.3 g Water added 1000 ml 1000 ml pH 7.0 7.0

[0113]

The silver halide photographic light-sensitive material of the present invention is excellent in color developability, color image fastness and color reproducibility, and exhibits excellent sensitivity.

Claims (1)

[Claims] 1. A photographic light-sensitive material having one or more silver halide emulsion layers on a support, the photographic light-sensitive material containing at least one cyan coupler compound represented by the following general formula (I): At least one of the silver halide emulsion layers contains negative internal latent image type silver halide grains chemically sensitized to a depth of less than 0.02 μm from the grain surface. Color photographic light-sensitive material. [Chemical 1] (In the formula, R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidation product of a color developing agent, and Z ¹ represents Represents a group of non-metal atoms necessary for forming a nitrogen-containing 6-membered heterocycle, provided that the heterocycle has at least one dissociative group.)