JPH07120860A - Silver halide photographic emulsion, silver halide photographic sensitive material and image forming method for the silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color print of high image quality which can be rapidly processed, is hardly affected by the atmosphere up to the time of printing and the atmosphere of a developer and has stable images by specifying the maximal frequency of a dielectric loss curve. CONSTITUTION:At least 95mol% of a silver halide compsn. consists of a silver chloride and the maximal frequency fmax of the dielectric loss curve by a dielectric loss method is >=5 times fmax of the comparing emulsion satisfying all conditions; (1) the average grain size is substantially the same as the average grain size of the silver halide photographic emulsion, (2) the silver halide photographic emulsion and the silver halide compsn. are substantially the same, (3) the silver halide compsn. is substantially uniform, (4) substantially regular hexahedron. More preferably, the compds. expressed by the formula, etc., are incorporated in the silver halide compsn. In the formula, V1, V2 denote hydrogen atoms, cyano groups, etc.; W1, W2 denote hydrogen atoms, alkyl groups, etc.; X1, X2 denote hydrogen atoms, carboxyl groups, etc.; L1 to L3 denote unsubstd. or substd. methine groups; m denotes 0, 1, or 2; n denotes 1, 2, or 3; M<m+> denotes cation of n-valence.

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 emulsion, a silver halide photographic light-sensitive material and a photographic image forming method, and in particular, rapid processing is possible and a plurality of color prints can be printed from the same negative. The present invention relates to a silver halide photographic light-sensitive material capable of stably obtaining a high-quality color print when prepared, and a silver halide photographic emulsion suitable for obtaining such a silver halide photographic light-sensitive material. It is about.

[0002]

2. Description of the Related Art A high chloride silver halide photographic emulsion consisting of a high concentration of silver chloride has come to be used for color paper. The currently used method of printing an image recorded on a color negative on a color paper is very excellent in that it can form an image easily at high speed, but a high chloride silver halide photographic emulsion is used. The color paper used has the drawback that the finish varies when trying to obtain the same prints from the same color negative. This phenomenon is mitigated by lengthening the time interval when exposing the same pattern, but the effect is not sufficient, and it is not possible to realize it because it causes a significant decrease in productivity. Moreover, even if the silver halide photographic light-sensitive material exposed with the same pattern was wound up and subjected to development processing in the reverse order of the exposure, it was confirmed that the variation in density varies depending on the position in the roll. , It became clear that this variation depends not only on the problem at the time of exposure but also on the factor at the time of development. Such a defect impairs the advantages of the above-described silver halide photographic light-sensitive material, and improvement has been desired.

JP-A-3-237451 discloses that the surface layer of a silver halide grain is a silver halide grain having a silver iodide content higher than that of an internal phase adjacent to the surface layer, thereby providing a halogen having high sensitivity and excellent storage stability. It is disclosed that a silver halide photographic light-sensitive material can be obtained. In the upper right column of page 4 of the publication, when determining whether or not a layer having a high silver iodide content is formed in the surface layer, confirmation is made by measuring the interstitial silver ion conductivity of the silver halide emulsion grains. It is stated that it is possible. further,
In the lower right column of page 2 of the publication, two major factors that control the photosensitization process are interstitial silver ions and photoelectrons, and the conductivity of interstitial silver ions increases as the silver iodide content increases. It is described that the latent image forming efficiency is expected to be improved by increasing the silver iodide content. However, this publication does not mention anything about the above problems caused by a silver halide photographic light-sensitive material using a high chloride silver halide emulsion, let alone mention nothing about problems occurring during development. None, and there was no suggestion of a solution.

The inventors of the present invention have disclosed, in Japanese Patent Laid-Open No. 5-204071, a silver halide photographic emulsion having a silver bromide content of 30 mol% or more and 98 to 99.9 mol% of silver chloride, and a silver halide photographic emulsion represented by the above general formula [I]. ] A silver halide photographic light-sensitive material containing a combination of at least one of the compounds [III] to [III] has improved density fluctuation when producing a plurality of prints of the same pattern, and is a color excellent in whiteness and sharpness. It has been disclosed that a print can be obtained. However, the above-mentioned publication does not mention that the density fluctuation remarkably increases when an image is obtained in a developing time of 25 seconds or less, and does not suggest any means for solving the problem.

The inventors of the present invention have disclosed, in Japanese Patent Application No. 4-216107, that an unchemically sensitized emulsion having 90 mol% or more of silver chloride and satisfying specific requirements is chemically sensitized with a specific sulfur compound and a gold compound. It has been disclosed that the change in gradation caused by continuous processing of a roll-shaped silver halide photographic light-sensitive material using this emulsion is improved. But,
In the above-mentioned specification, nothing is mentioned about the phenomenon that the density fluctuation is remarkably increased when an image is obtained with a developing time of 25 seconds or less, and no suggestion is made as to a solution.

The inventors of the present invention have disclosed that, in JP-A-5-165164, a silver bromide-containing phase of 30 mol% or more and reduction sensitization, 95 to 99.9 mol% of silver chloride are contained. A silver halide photographic light-sensitive material containing a high chloride silver halide photographic emulsion was developed with a color developer containing an aromatic primary amine developing agent and containing substantially no benzyl alcohol. It has been disclosed that the problem that the contrast of the highlight portion is remarkably lowered is improved by the color image forming method characterized in that the total time of color development, bleach-fixing and washing is within 2 minutes. . However, in the above publication, nothing is mentioned about the problem of the fluctuation of the density which occurs when continuously exposed and developed, and there is nothing about that the problem becomes more remarkable in the developing time of 25 seconds or less. Not mentioned. Nor is there any suggestion of a solution to this problem.

Photosensitive materials processed by using a high chloride silver halide photographic light-sensitive material in JP-A-3-204636, JP-A-4-335348, JP-A-5-204105, JP-A-5-204111 and the like. When processing a large amount of silver halide photographic light-sensitive material while replenishing the processing solution according to the amount of material, the disadvantage that the performance changes immediately after the start of development and after processing a large amount of light-sensitive material is improved. Disclosure. However, as mentioned above, these are problematic in the fluctuations in performance that occur when a relatively large amount of silver halide photographic light-sensitive material is continuously developed, and are caused by the difference in the positions on the rolls which are very close to each other. It is a phenomenon that is completely different from the fluctuation of performance, and does not suggest how to solve these problems.

[0008]

SUMMARY OF THE INVENTION The present inventors have found that when the color paper using the above-mentioned high chloride silver halide photographic emulsion is printed at high speed, the cause of the variation in the finish is
Since this color paper is most likely to be affected by the atmosphere that was most familiar at the time of printing, the front color paper is strongly affected by the atmosphere of the printing part, and the back color paper is strongly affected by the atmosphere inside the color paper magazine. We found that the finish varies due to the difference in these atmospheres, and the reason why the finish varies when developing rapidly is that this color paper is affected by the atmosphere of the developing solution during development. For the sake of simplicity, the front color paper is processed in a normal developer atmosphere, while the back color paper is processed in a developer atmosphere in which the dissolved components in the previous color paper are not sufficiently diffused. Therefore, it was discovered that the density varies depending on the atmosphere of these developing solutions.

The object of the present invention is that rapid processing is possible, and it is not easily affected by the atmosphere until printing and the atmosphere of the developing solution, and the images are stable when a plurality of color prints are made from the same negative. To provide a silver halide photographic emulsion for obtaining a high-quality color print, a silver halide photographic light-sensitive material using the same, and an image forming method thereof.

[0010]

While the inventors of the present invention have been earnestly researching a photographic light-sensitive material using a silver halide photographic emulsion containing a high concentration of silver chloride, the object of the present invention is to find a silver halide composition. In a silver halide photographic emulsion containing at least 95 mol% of silver chloride, the maximum frequency f _max of the dielectric loss curve by the dielectric loss method is 5 times or more of the f _max of the comparative emulsion satisfying all the following conditions. Silver halide photographic emulsion i) having the same average grain size as the silver halide photographic emulsion ii) having substantially the same silver halide composition as the silver halide photographic emulsion iii) having a silver halide composition Iv) Substantially uniform iv) The present invention has been completed by finding out what is achieved by a substantially regular hexahedron.

The composition of the silver halide photographic emulsion according to the present invention is characterized in that it is a silver halide emulsion containing silver chloride in an amount of 95 mol% or more. It may have any halogen composition such as silver chlorobromide and silver chloroiodobromide, but silver chlorobromide containing substantially no silver iodide is preferable. Silver chlorobromide containing silver chloride of preferably 97 mol% or more, and more preferably 98 to 99.9 mol% is preferable.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The average grain size of the silver halide grains according to the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm,
More preferably, it is in the range of 0.2 to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on Light Microscopy, 94-122).
Page, 1955) or "Theory of Photographic Processes, 3rd Edition"
(Mies and James, co-authored, Chapter 2, Macmillan, 1966).

The term "particle size" as used herein means a photograph taken with an electron microscope, and the diameter of spherical silver halide grains, or the projected image of cubic or non-spherical grains. Shows the diameter when converted to a circular image of the same area.
The average particle size is the arithmetic average of the particle size of 100 or more randomly selected particles.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The coefficient of variation is preferably 0.22 or less, more preferably 0.15.
The following are monodisperse silver halide grains. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution, and R is the average grain size.) Various devices known in the art can be used as the apparatus and method for preparing a silver halide emulsion. Any method can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor described in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The characteristics of the silver halide photographic emulsion according to the present invention are that the maximum frequency f of the dielectric loss curve by the dielectric loss method is f.
_{The max} is at least 5 times the f _max of an emulsion composed of regular hexahedral grains having substantially the same composition and uniform composition. More preferably, it is 6 times or more.

The dielectric loss method is a method widely used as a method for measuring the electrical conductivity of silver halide photographic emulsion grains. It is edited by the Chemical Society of Japan, Vol. 5, "Basic Technology 4 Electricity", New Experimental Chemistry Course. , P.160, Maruzen (1976) and ibid., P.271,
Shunji Takada, Journal of the Photographic Society of Japan, 44 , 81 (1981), etc., describe the measuring principle and measuring method in detail.

Whether or not the silver halide photographic emulsion is the silver halide photographic emulsion according to the present invention is prepared by preparing a sample of a comparative emulsion satisfying the following requirements by the same method and measuring it by the same method. It can be determined by obtaining the dielectric loss curve and comparing the maximum frequencies. The requirements to be satisfied by the comparative emulsion are: i) the grain size is the same as the silver halide photographic emulsion; ii) the silver halide composition is substantially the same as the silver halide photographic emulsion; iii) the silver halide composition is Substantially uniform iv) Substantially regular hexahedron.

The above-mentioned pAg controlled double jet method can be used for the preparation of the comparative emulsion, and the composition can be made uniform by using the same mixed halide salt in the solution through the steps of preparing the silver halide emulsion grains. The sex is almost satisfactory. By making the solution of the halide salt used for controlling pAg the method described in JP-A-59-45437, a comparative emulsion having a higher degree of uniformity can be obtained. It is also possible to prepare fine grain silver halide emulsion in advance and add this to the reaction mother liquor to prepare silver halide emulsion grains.

The homogeneity of the composition of the comparative emulsion is described in, for example, Masamitsu Inoue and Tadahiro Nagasawa, “Halogen distribution in silver halide grains by analytical electron microscope, observation of multi-structure grains”, Annual Meeting of the Photographic Society of Japan, 1987. As described in p.46 (1987) of the conference proceedings, an ultrathin section of silver halide grain was prepared,
It is possible to measure the composition by measuring this with an analytical electron microscope at the liquid nitrogen temperature, and it is possible to evaluate the deviation of the distribution within the particles. The standard deviation of the composition values thus obtained may be within 3 mol%. The standard deviation can be calculated by the following formula.

(Sum of deviation square) = Σ ((measured value) _i− (average of measured values)) ² (standard deviation) = ((sum of deviation squared) / (number of measured values)) ^{1/2 For} comparison The condition of being a regular hexahedron of emulsion grains can be easily confirmed by an electron micrograph, and it can be expressed by the radius of curvature of the apex of a square when one face of the regular hexahedron is observed from directly above. Is. Radius of curvature
The purpose can be achieved within 1/10.

In order to obtain the dielectric loss curve, it is necessary to remove water from the sample to be measured, and especially in the case of a high chloride silver halide photographic emulsion, the success or failure thereof greatly affects the reliability of the measured value. Therefore caution is required. For this purpose, a vacuum deaeration method or a dehumidification method using a desiccant such as phosphorus pentoxide can be used.

The silver halide emulsion according to the present invention comprises a sensitizing method using a gold compound, a sensitizing method using a chalcogen sensitizer,
Sensitization methods such as reduction sensitization method can be used alone or in combination.

As the sulfur sensitizer applied to the silver halide emulsion according to the present invention, thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-
Examples thereof include toluene thiosulfonate, rhodanine, triethyl thiourea, and inorganic sulfur. The addition amount of the sulfur sensitizer used in the chemical ripening of the silver halide emulsion according to the present invention is preferably changed depending on the silver halide emulsion to be applied, but it is 5 × 10 5 per mol of silver halide.
^{-10 to} 5 × 10 ^-5 mol range, preferably 5 × 10 ^{-8 to} 3 × 1
0 ^-5 mols is preferred.

As the gold sensitizer used when chemically sensitizing the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of gold compound used is
Although it does not vary depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., it is usually preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The sensitizer used for selenium sensitization of the silver halide photographic emulsion according to the present invention can contain a wide variety of selenium compounds. For example, U.S. Pat.
No. 1602592, No. 1623499, JP-A-60-150046,
The compounds described in JP-A-4-25832, 4-109240, 4-147250 and the like can be mentioned.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N, N-).
Dimethylselenourea, N, N, N'-triethylselenourea,
N, N, N'-trimethyl-N'-heptafluoroselenourea, N,
N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N '-(4-nitrophenyl) carbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetone) Acetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophos Examples thereof include phenates (eg, tri-p-triselenophosphate, etc.) and selenides (diethylselenide, diethyldiselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenoketones.

Specific examples of the technique of using these selenium sensitizers are disclosed in the following patent specifications. US Patent 1574
No. 944, No. 1602592, No. 1623499, No. 3297446
No., No. 3297447, No. 3320069, No. 3408196,
No. 3408197, No. 3442653, No. 3420670, No. 3
591385, French Patent No. 2693038, No. 2093209,
Japanese Patent Publications No. 52-34491, No. 52-34492, No. 53-295, and No. 57-2
2090, JP-A-59-180536, 59-185330, 59-181
337, 59-187338, 59-192241, 60-150046
No. 60-151637, No. 61-246738, JP 3-4221,
3-24537, 3-111838, 3-116132, 3-14864
No. 8, No. 3-237450, No. 4-16838, No. 4-25832, No. 4-3
2831, 4-96059, 4-109240, 140738, 4
-140739, 4-147250, 4-149437, 4-184331
Nos. 4-190225, 4-191729, 4-19535, and British Patent 255846, 861984. It is also disclosed in the chemical literature such as HE Spencer et al., Journal of Photographic Science, Vol. 31, pp. 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. Further, the addition method, depending on the properties of the selenium compound used, water or methanol, a method of adding by dissolving in an organic solvent such as ethanol alone or in a mixed solvent, is also disclosed in JP-A-4-140739. A method, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer in the present invention is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. Also, the pH is 4-9, p
Ag is preferably in the range of 6 to 9.5.

Specific examples of preferred compounds as the selenium sensitizer are shown below.

[0037]

[Chemical 4]

Regarding the tellurium sensitizer and the sensitizing method according to the present invention, US Pat. Nos. 1623499, 3320069 and 377203 are applicable.
1, 3531289, 3655394, British Patent No. 235211
No. 1121496, No. 1295462, No. 1396696, Canadian Patent No. 800958, and Japanese Patent Laid-Open No. 4-204640. Examples of useful tellurium sensitizers include telluroureas,
Telluramides and the like can be mentioned. The technique for using the tellurium sensitizer may be the same as the technique for using the selenium sensitizer described above.

Specific examples of preferred compounds as the tellurium sensitizer are shown below.

[0040]

[Chemical 5]

A known method can be used for reduction sensitizing the silver halide emulsion according to the present invention. For example,
It is also possible to use a method of adding various reducing agents,
A method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

As the reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention, stannous salts such as stannous chloride, boranes such as tri-t-butylamine borane, sodium sulfite, potassium sulfite, etc. Sulfites, reductones such as ascorbic acid, and thiourea dioxide can be used. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or added at the time of forming silver halide grains to reduce and increase them simultaneously with grain formation. You may feel.

The amount of these reducing agents added needs to be adjusted according to the pH of the silver halide emulsion, the silver ion concentration, etc., but is generally 10 per mol of the silver halide emulsion.
^-7 to 10 ^-2 mol is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of the compound used for such purpose include
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Antifoggant known in
Stabilizers can be used. As an example of a compound that can be used for such a purpose, JP-A-2-146036 discloses.
The compounds represented by the general formula (II) described in the lower column of the page can be mentioned, and specific compounds thereof include (IIa-1) to (IIa-8) described on page 8 of the publication. , (II
Examples thereof include compounds b-1) to (IIb-7), and compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds, depending on their purpose,
It is added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step, and the step of preparing a coating solution. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide, and 1 × 10 ^-5 mol to 5 mol.
× 10 ^-3 mol is more preferable. In the coating liquid preparation process,
When it is added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 mol to 1 × 10 ^-2 mol. Is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

The compounds of the general formulas [I] to [III] used in the silver halide photographic light-sensitive material of the present invention are known dyes used for the purpose of preventing irradiation and halation.

[0048]

[Chemical 6]

[In the formula, V ₁ and V ₂ are a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, -COOR ₁ and -C, respectively.
OR ₁ , -CONR ₁ R ₂ , -OR ₁ , -NR ₁ R ₂ , -NR ₁ COR ₂ , -NR ₁ SO ₂ R
₂ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group, wherein W ₁ and W ₂ are a hydrogen atom, —NR ₃ R ₄ , —NR ₃ COR ₄ , and —NR _{3 respectively.} SO ₂ R ₄ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group is represented, and X ₁ and X ₂ are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, -COOR.
₅ , -COR ₅ , -CONR ₅ R ₆ , -NR ₅ R ₆ , -NR ₅ COR ₆ , -NR ₅ SO ₂
R ₆ , SO ₂ R ₅ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and L ₁ , L ₂ , L ₃
Each represents an unsubstituted or substituted methine group, m is 0, 1
Or 2, n represents 1, 2 or 3, and M ^{n +} represents an n-valent cation.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each
It represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ may be linked to form a 5- or 6-membered ring.

However, at least one of V ₁ , V ₂ , W ₁ , W ₂ , X ₁ and X ₂ represents a group containing a carboxyl group or a sulfo group. ]

[0052]

[Chemical 7]

[Wherein, R ₇ represents an alkyl group, an aryl group or a heterocyclic group, and R ₈ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, —COR ₂₀ or —SO ₂ R, respectively. ₂₀
R ₉ is a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, —COOR ₂₀ , —CONR ₂₁ R ₂₂ , or —OR.
₂₀ , -NR ₂₁ R ₂₂ , -NR ₂₁ COR ₂₂ , -NR ₂₁ SO ₂ R ₂₂ , -NR ₂₁ CON
R ₂₁ R ₂₂ represents an alkyl group or an aryl group, L ₄ , L ₅ , L
₆ represents an unsubstituted or substituted methine group, 1 is 0,
Represents 1 or 2. Y ₁ and Y ₂ represent an oxygen atom or NR ₂₃ .

R ₂₀ represents an alkyl group or an aryl group,
R ₂₁ and R ₂₂ each represent a hydrogen atom, an alkyl group or an aryl group. R ₂₃ represents a group of nonmetallic atoms necessary for forming a 5-membered ring by linking with R ₇ .

However, at least one of R ₇ , R ₈ and R ₉ represents a group containing at least one carboxyl group or sulfo group. ]

[0056]

[Chemical 8]

[In the formula, R ₁₃ and R ₁₄ are —CN and —CO, respectively.
R ₁₇ , —COOR ₁₇ , or —CONR ₁₈ R ₁₉ is represented, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and L ₇ , L ₈ and L ₉ represents an unsubstituted or substituted methine group, and k represents 0, 1 or 2. R ₁₇ represents an alkyl group or an aryl group. R ₁₈ , R
Each ₁₉ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and one of R ₁₈ and R ₁₉ is a hydrogen atom.

However, at least one of R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ represents a water-soluble group or a substituent containing a water-soluble group. The present invention will be specifically described below.

First, the compound represented by the general formula [I] will be described.

In the formula, V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R
Examples of the alkyl group represented by _{1 to} R ₆ include methyl,
Examples include ethyl, propyl, isopropyl, butyl, t-butyl, etc., and these alkyl groups are further hydroxyl groups,
Sulfo group, carboxyl group, halogen atom (eg fluorine, chlorine, bromine etc.), alkoxy group (eg methoxy, ethoxy etc.), aryloxy group (eg phenoxy, 4-sulfophenoxy, 2,4-disulfophenoxy etc.) ), Aryl groups (eg, phenyl, 4-sulfophenyl, 2,5-disulfophenyl, etc.), cyano groups, alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, etc.) aryloxycarbonyl groups (eg,
Phenoxycarbonyl) or the like.

V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R _{1 to} R ₆
Examples of the aryl group represented by are phenyl, 2-methoxyphenyl, 4-nitrophenyl, 3-chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-methanesulfonylphenyl, 4-sulfophenyl and 3-sulfophenyl. Phenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2-chloro-5-
Sulfophenyl, 2-methoxy-5-sulfophenyl, 2-hydroxy-4-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 2,6-diethyl-4-sulfophenyl, 2,5-disulfophenyl , 3,5-disulfophenyl, 2,4-disulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5
-Sulfophenyl, 4-carboxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 3,6-disulfo-α-naphthyl, 8-hydroxy-3,6 -Disulfo-α-naphthyl, 5-hydroxy-7-sulfo-β-naphthyl, 6,8-disulfo-β-naphthyl and the like can be mentioned.

V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R _{1 to} R ₆
The heterocyclic group represented by, for example, pyridyl group (2-pyridyl, 3-pyridyl, 4-pyridyl, 5-sulfo-2-pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2- Pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, 3-nitro-2-
Pyridyl), oxazolyl group (5-sulfo-2-benzoxazolyl, 2-benzoxazol, 2-oxazolyl, etc.), thiazolyl group (5-sulfo-2-benzothiazolyl, 2
-Benzothiazolyl, 2-thiazolyl, etc.), imidazolyl group (1-methyl-2-imidazolyl, 1-methyl-5-sulfo-2-
Benzimidazolyl etc.), furyl group (3-furyl etc.), pyrrolyl group (3-pyrrolyl etc.), thienyl group (2-thienyl etc.), pyrazinyl group (2-pyrazinyl etc.), pyrimidinyl group (2-pyrimidinyl, 4-chloro) -2-pyrimidinyl etc.), pyridazinyl group (2-pyridazinyl etc.), purinyl group (8-purinyl etc.), isoxazolinyl group (3-isooxazolinyl etc.), selenazolyl group (5-sulfo-2-selenazolyl) Etc.), sulforanyl (3-sulfolanyl etc.), piperidinyl group (1-methyl-3-piperidinyl etc.), pyrazolyl (3-pyrazolyl etc.), tetrazolyl group (1-tetrazolyl etc.) and the like. The methine groups represented by L ₁ , L ₂ and L ₃ include those having a substituent (eg, methyl group, ethyl group, phenyl group, chlorine atom, etc.). Examples of the n-valent cation represented by M ^{n +} include Na ⁺ , K ⁺ , Ca ²⁺ , NH ₄ ⁺ , HN (C ₂ H ₅ ) ₃ ⁺ , and C ₅ H ₆ N ^+.
Etc. Typical specific examples of the dye of the present invention represented by the above general formula [I] are shown below, but the dye of the present invention is not limited thereto.

[0063]

[Chemical 9]

[0064]

[Chemical 10]

[0065]

[Chemical 11]

[0066]

[Chemical 12]

[0067]

[Chemical 13]

[0068]

[Chemical 14]

[0069]

[Chemical 15]

[0070]

[Chemical 16]

These dyes are described in British Patent 1,278,621,
It can be synthesized using the method described in Nos. 1,512,863 and 1,579,899.

Next, the compound represented by the general formula [II] will be described.

In the formula, R ₇ , R ₈ , R ₉ , R ₂₀ , R ₂₁ , and R ₂₂
Examples of the alkyl group represented by are the same groups as the alkyl groups described for V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ and R _{1 to} R ₆ in the general formula [I]. To be R ₇ , R ₈ ,
Examples of the aryl group represented by R ₉ , R ₂₀ , R ₂₁ , and R ₂₂ include V ₁ , V ₂ , W ₁ , W ₂ , and W ₂ in the above general formula [I].
The same groups as the aryl groups described for X ₁ , X ₂ , and R _{1 to} R ₆ can be mentioned. Examples of the heterocyclic group represented by R ₇ and R ₈ include V ₁ , V ₂ , W ₁ , W ₂ , X ₁ in the above general formula [I],
The same groups as the heterocyclic groups described for X ₂ and R _{1 to} R ₆ can be mentioned. The methine group represented by L ₄ , L ₅ and L ₆ is a substituent (eg, methyl group, ethyl group, phenyl group, chlorine atom)
Including those having.

Typical specific examples of the dye of the present invention represented by the general formula [II] are shown below, but the dye of the present invention is not limited thereto.

[0075]

[Chemical 17]

[0076]

[Chemical 18]

[0077]

[Chemical 19]

[0078]

[Chemical 20]

[0079]

[Chemical 21]

[0080]

[Chemical formula 22]

These dyes can be synthesized by reacting a dioxopyrazolopyridine compound with an appropriate monomethine source, trimethine source, or pentamethine source compound. Specifically, JP-B-39-22069, No. 43-3504,
52-38056, 54-38129, 55-10059, JP-A-49
-99620, 59-16834 or US Pat. No. 4,181,225 and the like.

Next, the compound represented by the general formula [III] will be described.

In the formula, the alkyl groups represented by R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ include V ₁ , V ₂ , W ₁ , W ₂ and X _{1 in the} above general formula [I]. , X ₂ , R _{1 to} R ₆ include the same groups as the alkyl groups described above. R ₁₅ , R ₁₆ , R ₁₇ ,
Examples of the aryl group represented by R ₁₈ and R ₁₉ include V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , and R _{1 to} R ₁ in the general formula [I].
_{The same} group as the aryl group described in ₆ can be mentioned.
Examples of the alkenyl group represented by R ₁₈ and R ₁₉ include vinyl,
Allyl etc. are mentioned. The heterocyclic group represented by R ₁₅ , R ₁₆ , R ₁₈ and R ₁₉ includes V ₁ in the general formula [I],
V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R _{1 to} R ₆ include the same groups as the heterocyclic groups described above. Examples of the cycloalkyl group represented by R ₁₅ and R ₁₆ include cyclopentyl and cyclohexyl.

Typical specific examples of the dye of the present invention represented by the general formula [III] are shown below, but the dye of the present invention is not limited thereto.

[0085]

[Chemical formula 23]

[0086]

[Chemical formula 24]

[0087]

[Chemical 25]

[0088]

[Chemical formula 26]

[0089]

[Chemical 27]

These dyes are described in JP-A-58-143342 and JP-A-6-143342.
2-165656 etc. can be used for the synthesis.

These compounds can be used in an appropriate amount depending on the relationship with the required sharpness and sensitivity. For example, regarding the red-sensitive emulsion layer, which is currently the most inferior in sharpness, it is preferable to use an amount such that the spectral reflection density at a wavelength of 680 nm is 0.70 or more.

When the silver halide photographic light-sensitive material of the present invention has an infrared-sensitive silver halide emulsion layer, it preferably contains an infrared absorbing dye. As the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left column have preferable spectral characteristics, and silver halide It is preferable because there is no influence on the photographic characteristics of the photographic emulsion and there is no stain due to residual color. As specific examples of preferable compounds, Exemplified Compounds (1) to (3) in the lower left column of page 3 to the lower left column of page 5
(45) can be mentioned.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention.
BS-1 to BS-8 described on page 28 of JP 1840 can be preferably used alone or in combination. Examples of the green-sensitizing sensitizing dye include GS-1 to GS-1 described on page 28 of the same publication.
5 is preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When image exposure is performed by infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye needs to be used.
The dyes of IRS-1 to 11 described in 4-285950, pages 6 to 8 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the publication in combination with these dyes.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water and adding it as a solution, or as a solid dispersion. You may add.

The solid dispersion of the sensitizing dye can be obtained by mechanically dispersing in a water system at 1 μm by using a high speed stirring type disperser.
In addition to the method of pulverizing and dispersing into the following fine particles, JP-A-58-1
As described in No. 05141, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in a water system under the conditions of pH 6 to 8 and 60 to 80 ° C., the surface tension described in Japanese Patent Publication No. 60-6496 is 38 dyn.
It is possible to use a method of dispersing in the presence of a surfactant that suppresses e / cm or less.

As a dispersing device that can be used for preparing a dispersion liquid, for example, Japanese Patent Laid-Open No. 4-125631 can be used.
In addition to the high-speed stirring type disperser shown in the figure, a ball mill, a sand mill, an ultrasonic disperser, etc. may be mentioned.

When using these dispersing devices, as described in Japanese Patent Laid-Open No. 4-125632, a method such as performing pretreatment such as dry pulverization in advance and then performing wet dispersion may be adopted.

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
JP-A-4-114154, the general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC on pages 18 to 21 of the specification.
Those described as -1 to CC-9 can be mentioned.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, the general formulas (MI) and (M-II) described on page 12 of JP-A-4-114154 can be used. A coupler represented by Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are preferable because they are excellent in the reproduction of colors from blue to purple and red and are also excellent in the depiction of details.

As a yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a coupler represented by the general formula (Y-I) described on page 8 of JP-A-4-114154 can be used. Can be mentioned.
Specific compounds are described in YC-1 to YC on pages 9 to 11 of the same specification.
Those listed as -9 can be mentioned.
Among them, YC-8 and YC- described on page 11 of the same specification
No. 9 is preferable because it can reproduce a preferable yellow color.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described on page 33 of JP-A-4-114154 and the compound (A'- on page 35 of the specification).
Compounds such as 1) can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The support used in the silver halide photographic light-sensitive material of the present invention may be made of any material, including white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, and white pigment-containing polypropylene. ,
A polyethylene terephthalate support or the like can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina,
Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support is preferably 10% by weight or more, more preferably 13% by weight or more, as the content in the waterproof resin layer. Is preferable, and more preferably 15% by weight or more. The dispersity of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

The silver halide photographic light-sensitive material of the present invention may be directly or undercoated (adhesiveness of the surface of the support, after the surface of the support is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

Further, in the silver halide photographic light-sensitive material according to the present invention, various hardeners are used for the purpose of preventing damage or dissolution of the film during processing. As these hardeners, many compounds such as epoxy compounds, aziridine compounds, acryloyl compounds, vinylsulfonyl compounds, chlorotriazine compounds are known, and the silver halide photographic light-sensitive material according to the present invention. Any known hardener can be preferably used for the above.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It is especially useful for printing after image formation, but once the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and the image is printed on the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or may be printed by changing the intensity of laser light based on digital information and scanning.

When exposure is carried out using a laser beam, the exposure time per pixel is not particularly limited, but is 100 nanoseconds to 1 nanosecond.
Often exposed in 00 microseconds. In the case of exposure for an extremely short time, the phenomenon that the slope of the characteristic curve greatly changes at a certain density point often occurs. When the density fluctuation occurs due to the above-mentioned problem, the image quality is remarkably deteriorated, such as a pseudo contour being generated in the image depending on the density range. The silver halide photographic light-sensitive material according to the present invention can be remarkably improved in stability even with respect to such characteristics under exposure of 100 microseconds or less, and can be preferably used.

The exposure time per pixel is the outer edge of the light flux when the light intensity becomes 1/2 of the maximum value in the spatial change of the light flux intensity, is parallel to the scanning line, and is the light intensity. When the distance between two points where the line passing through the maximum point and the outer edge of the light flux intersects is the light flux diameter, the (light flux diameter) / (scanning speed) is defined as the exposure time per pixel.

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-4.
071, JP-A-59-11062, JP-A-63-197947, JP-A
2-74942, Japanese Patent Laid-Open No. 2-236538, Japanese Patent Publication No. 56-14963, Japanese Patent Publication No. 56-40822, European Wide Area Patent 77410, Department of Electronic Communication, Technical Report 80, No. 244, and Movie Television Technical Journal 1984.
/ 6 (382), pages 34-36, etc.

A semiconductor laser is also preferably used as a light source used for exposing the silver halide photographic light-sensitive material of the present invention. In particular, in the case of a silver halide photographic light-sensitive material using an infrared sensitizing dye, any semiconductor laser may be used as long as it has sufficient intensity at a wavelength of 720 nm or more.・ Phosphorus, aluminum gallium arsenide, indium gallium
Examples include arsenic / phosphorus, aluminum / gallium / arsenic / antimony. Among them, 750, 780, 810, 8
A semiconductor laser of 30, 880 nm is advantageously used in terms of light intensity and handling of silver halide photosensitive materials.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4-Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) Aniline CD-6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl)
Methanesulfonamide CD-8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl- N-Ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline The color developer contains the above-mentioned color developing agent. In addition, known developer component compounds can be added. Usually pH
A buffering alkali agent, a chloride ion, a development inhibitor such as benzotriazole, a preservative, and a chelating agent are used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. The development processing device used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is sandwiched between rollers arranged in a processing tank, and a photosensitive material may be used for the belt. It may be an endless belt method of fixing and transporting, but a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and the photosensitive material is transported, and the processing solution is atomized. Spray method,
A web method by contact with a carrier impregnated with a treatment liquid,
A method using a viscous treatment liquid can also be used.

[0122]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

Magenta coupler (M-1) 12.14 g, additive (ST-3) 12.14 g, (ST-4) 10.32 g, and high boiling point organic solvent (DIDP) 7.9 g, (DBP) 7.9 g ethyl acetate. 60 ml was added and dissolved, and this solution was added with 20% surfactant (SU
1) 220 ml of 10% gelatin aqueous solution containing 12 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a magenta coupler dispersion.

This dispersion was mixed with a silver halide emulsion (containing 8.5 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second layer coating liquid was also prepared in the same manner as the first layer coating liquid. Further, (H-1) was added to the second layer as a hardener. As the coating aid, a surfactant (SU-2),
(SU-3) was added to adjust the surface tension.

Using the coating solution prepared as described above,
A silver halide photographic light-sensitive material was prepared. The layer structure is shown in Table 1 below.

[0127]

[Table 1]

[0128]

[Chemical 28]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2,2,3,3,4,4) sulfosuccinate , 5,5-Octafluoropentyl) sodium salt DIDP: di-i-decylphthalate DBP: dibutylphthalate H-1: tetrakis (vinylsulfonylmethyl) methane (preparation of red-sensitive emulsion) 2% kept at 40 ℃ By pAg control double jet method in 1 liter of gelatin aqueous solution,
The following (A solution) and (B solution) were simultaneously added while controlling pAg = 7.3 and pH = 3.0, and further (C solution) and (D solution) below.
Was simultaneously added while controlling the pH to 8.0 and the pH to 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10.0 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added 600 ml (solution D) Add 300 g of silver nitrate to 600 ml of water, and after the addition of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution on average. A silver halide emulsion (EMP-11) consisting of cubic grains having a grain size of 0.50 μm and a silver chloride content of 99.5 mol% was obtained.

Gelatin of this silver halide emulsion was decomposed to separate silver halide grains, and then the thickness of this was about 0.08 μm.
The composition of silver halide was determined by using a transmission electron microscope (electron beam diameter of about 0.04 μm) with an acceleration voltage of 200 kV. When the position irradiated with the electron beam was changed and the measurement was performed at 10 measurement points, the standard deviation was 2 mol%.

Evaluation of how the corners of the cube were rounded from the electron micrographs of these grains revealed that the radius of curvature was 1/10 or less of the length of one side, satisfying the conditions for the comparative emulsion of the present invention. It was

This silver halide emulsion was coated on an unsubbed cellulose triacetate base so that the coating amount was 1 g / m ² , and the coated sample was vacuum degassed and sufficiently dried, and then gelatinized. The film was peeled off and the dielectric loss curve was determined.

Next, in the preparation of (EMP-11), the addition rate was adjusted, and at the time of adding 90% of the total silver amount during the mixing of (C liquid) and (D liquid), 2 g was added. Imidazole is added as an aqueous solution, and while adding (C liquid) and (D liquid) for 3% of the total silver amount, the light of an incandescent lamp is irradiated at an illuminance of 1 lux, and at the same time the light irradiation is stopped. A silver halide emulsion with an average grain size of 0.50 μm and a silver chloride content of 99.5 mol% (EMP) was added in the same manner except that imidazole and an equimolar sulfuric acid solution were added, and (C solution) and (D solution) were continuously added. -12) was prepared. Using this (EMP-12), a dielectric loss curve was obtained in the same manner as (EMP-11).

When read from the dielectric loss curve, (EM
(P-11) shows the maximum value at the position of 720 Hz, (EMP-12) shows 3
It was found to have a maximum at the position of 760 Hz.

Sensitizing dyes (RS-1) and (RS-2) were dissolved in methanol, and each emulsion was chemically sensitized at 55 ° C. with the following compounds (Em-R101) and (Em-R102). Was prepared.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye (RS-1) 1 × 10 ^-4 mol / mol AgX sensitizing dye (RS-2) 1 × 10 ^-4 mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5- Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole

[0138]

[Chemical 29]

The sample using (Em-R101) was designated as No. 101, and
The sample using m-R102) was designated as No.102. The sample after coating is cut into a roll of 89 mm width and cut into NPS-602QA
With the printer processor, continuous exposure was carried out through the uniformly exposed negative for setup (conditions were adjusted in advance so that the density was 0.75), and then development was performed. In this way, 30 prints were prepared from the same negative, the densities of the first and 30th prints were measured, and the difference between them was determined. The results are shown in Table 2.

[0140]

[Table 2]

In the comparative sample, the density fluctuation was found to be 0.09, whereas in the silver halide photographic light-sensitive material of the present invention, the density fluctuation was 0.04, showing that the density fluctuation was small. .

The development processing conditions are as shown below.

(Processing step) Processing temperature Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80 ml Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120 ml Stabilization 30 to 34 ℃ 60 seconds 150 ml Dry 60 to 80 ℃ 30 seconds Development processing The compositions of the liquid tank liquid and the replenishing liquid are shown below.

(Color developer tank solution and replenisher) (Tank solution) (Replenisher) Pure water 800 ml 800 ml Triethylenediamine 2 g 3 g Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0g 10.0g N, N-diethylhydroxylamine 6.8g 6.0g Triethanolamine 10g 10g Diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make a total volume of 1 liter, tank solution pH = 10.
Adjust to 10 and replenisher to pH = 10.60.

(Bleach-fixing solution tank solution and replenishing solution) Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4- Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

(Stabilizing Solution Tank Solution and Replenishing Solution) o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0g Optical brightener (Tinopearl SFP) 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8g Bismuth chloride (45% aqueous solution) 0.65g Magnesium sulfate heptahydrate 0.2g PVP 1.0g Ammonia water (hydroxide Ammonium 25% aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

(Example 2) In the preparation of the silver halide photographic light-sensitive material of Example 1, Sample Nos. 101 and 102, Comparative Dye A, Exemplified Compounds (I-10) and (II-1) were used in the second layer. (III-20) was added to prepare sample Nos. 201 to 208. At this time, the amount of dye is 6
The addition amount was adjusted so that the spectral reflection density at 80 nm was 0.70. Next, in the preparation of Samples 201 to 208, Sample 211 was similarly prepared except that the coating amount of the first layer was set to 90% of the coating amount of Table 1.
~ 218 was prepared.

[0148]

[Chemical 30]

These samples were evaluated in the same manner as in Example 1, and the results are shown in Table 3.

[0150]

[Table 3]

The density variation tends to increase a little by adding a dye, but when the silver halide emulsion according to the present invention is used, the effects of the present invention can be obtained without deterioration even in such a sample. I was able to get it. The use of the dye according to the present invention is useful for improving sharpness, and the dye according to the present invention is useful for obtaining a high-quality color print without impairing the performance of reproducing to a certain density.

Further, although the density fluctuation tends to increase a little by decreasing the amount of coated silver, the silver halide photographic light-sensitive material of the present invention shows a small density fluctuation even under such a condition. I was able to maintain it.

Next, in the preparation of Sample No. 202, various dyes were changed and the same evaluation was carried out to confirm that the effects of the present invention were obtained.

[0154]

[Table 4]

(Example 3) In the same manner as in the preparation of (Em-R102) in Example 1, except that 2.1 mg / mol AgX of Exemplified Compound (SE-1) was added instead of sodium thiosulfate and chloroauric acid.
(Em-R301) was prepared. Similarly, the exemplified compound (TE
-1) was prepared with 4.1 mg / mol AgX (Em-R302) and thiourea dioxide was used with 0.5 mg / mol AgX to prepare (Em-R303).

Next, in the preparation of samples No. 102 and No. 204,
From (Em-R102) to (Em-R301) to (Em-R30)
It changed to 3) and prepared sample No.301-303, 311-313.

These samples were evaluated by the same method as in Example 1. The results are shown in Table 5.

[0158]

[Table 5]

It was confirmed that each of the silver halide photographic light-sensitive materials according to the present invention had an effect of reducing density fluctuation. Above all, it was confirmed that the effect was large in the emulsions subjected to selenium sensitization, tellurium sensitization and reduction sensitization.

(Example 4) Sample Nos. 101 and 102 of Example 1
Also, the same evaluations as in Example 1 were performed using Sample Nos. 201 to 208 of Example 2 in the same manner except that the development processing was changed as described below.

(Processing step) Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 25 seconds 81ml Bleach fixing 35.0 ± 0.5 ℃ 25 seconds 54ml Stabilization 30-34 ℃ 25 seconds 150ml Dry 60-80 ℃ 30 seconds Development processing The compositions of the liquid tank liquid and the replenishing liquid are shown below.

(Color developer tank solution and replenisher) (Tank solution) (Replenisher) Pure water 800 ml 800 ml Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g N-ethyl-N -(Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5g 10.5g N, N-diethylhydroxylamine 3.5g 6.0g N, N-bis (2-sulfoethyl) hydroxyamine 3.5g 6.0g Triethanolamine 10g 10g Diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter, and tank liquid Is pH = 10.
Adjust to 10 and replenisher to pH = 10.60.

(Bleaching Fixing Solution Tank Solution and Replenisher) (Tank Solution) (Replenisher) Diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 50 g Diethylenetriamine pentaacetate 3 g 3 g Ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino -5-Mercapto-1,3,4-thiadiazole 2.0g 1.0g Ammonium sulfite (40% aqueous solution) 50ml 25ml Add water to bring the total volume to 1 liter, and add potassium carbonate or glacial acetic acid to the pH of the tank solution to 7.0. The solution is adjusted to pH = 6.5.

(Stabilizing Solution Tank Solution and Replenishing Solution) o-Phenylphenol 1.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0g Optical brightener (Tinopearl SFP) 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8g PVP 1.0g Ammonia water (25% ammonium hydroxide solution) 2.5g Ethylenediaminetetraacetic acid 1.0g Water To 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

The evaluation results are shown in Table 6 below.

[0166]

[Table 6]

It was found that when the color development time is set to 25 seconds, the density fluctuation becomes large, but the silver halide photographic light-sensitive material of the present invention can suppress the density fluctuation to be small. It is a preferable mode that the development processing is carried out for a shorter period of time because it further enhances the superiority of the photographic light-sensitive material using the high chloride silver halide emulsion containing a high concentration of silver chloride. Had a major drawback that it appeared remarkably. By using the silver halide photographic light-sensitive material according to the present invention, this drawback was ameliorated and more rapid processing was achieved.

Example 5 A blue light-sensitive emulsion and a green light-sensitive emulsion were prepared by the following method, and the silver halide photographic emulsion added to the first layer was replaced with these, and added to the second layer. Sample N of Example 2 except that various dyes were changed.
A silver halide photographic light-sensitive material was prepared and evaluated in the same manner as o.201. At this time, the amount of the dye added was adjusted so that the spectral absorption at a wavelength of 470 nm for the sample using the blue-sensitive silver halide emulsion and 0.7 at the wavelength of 550 nm for the green-sensitive silver halide emulsion.

(Preparation of Blue Sensitive Silver Halide Emulsion) In the preparation of (EMP-11) and (EMP-12) of Example 1, (A solution) and (B)
A silver halide emulsion was prepared in the same manner as in (EMP-11) and (EMP-12) except that the addition time of (Solution) and the addition time of (Solution C) and (Solution D) were changed. As a result, the average particle size is 0.85μ
m, emulsion with silver chloride content of 99.5 mol% (EMP-51), (EMP-52)
Got

Next, the above emulsions (EMP-51) and (EMP-52) were optimally chemically sensitized at 60 ° C. using the following compounds,
Blue-sensitive silver halide emulsions (Em-B501) and (Em-B502) were obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (STAB-3) 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / Molar AgX sensitizing dye (BS-2) 1 × 10 ⁻⁴ mol / mol AgX (Preparation of green-sensitive silver halide emulsion) Example 1 (EMP-1
1) In preparation of (EMP-12), (EMP-11), (EMP-) except that the addition time of (A solution) and (B solution) and the addition time of (C solution) and (D solution) are changed. A silver halide emulsion was prepared in the same manner as in 12). As a result, an emulsion with an average grain size of 0.43 μm (EMP-
53) and (EMP-54) were obtained.

Then, the above emulsions (EMP-53) and (EMP-54) were optimally chemically sensitized at 60 ° C. using the following compounds,
Green-sensitive silver halide emulsions (Em-G501) and (Em-G502) were obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 4 × 10 ^-4 mol / mol AgX

[0174]

[Chemical 31]

STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the same manner as in Example 1, from the electron micrographs of (EMP-51) and (EMP-53), how to round the corners of a cube. The radius of curvature was 1/10 or less of the length of one side, and the variation in the halogen composition of this silver halide emulsion was examined. All emulsions had an average silver chloride content of 99.5 mol% and a standard deviation of 2 %, Which means that the conditions for the comparative emulsion of the present invention are satisfied.

The dielectric loss of this silver halide emulsion was measured and f _max was determined. As a result, (EMP-52) was 6.2 times that of (EMP-51), and (EMP-54) was (EMP-53). Was 5.7 times.

The evaluation results are shown in Table 7 below.

[0178]

[Table 7]

It was confirmed that all of them are light-sensitive materials using the silver halide emulsion according to the present invention, and the effect of the present invention that the density fluctuation is small can be obtained. Especially f
_It can be seen that the silver halide photographic light-sensitive material according to the present invention using (EMP-52) having a large _max shows an excellent effect.

Example 6 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material, Sample 601. The coating liquid was prepared as follows. First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, dye image stabilizer (ST-2) 3.
34 g, anti-staining agent (HQ-1) 0.33 g, compound A5.
60 g of ethyl acetate to 0 g and 5.0 g of high boiling organic solvent (DBP)
ml to dissolve and add 20% surfactant (SU-
1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 7 ml using an ultrasonic homogenizer. This dispersion was mixed with the blue-sensitive silver halide emulsion (Em-B501) of Example 5 to prepare a coating solution for the first layer.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 8 and 9.

Further, as a hardener (H-1), (H-
2) was added. As a coating aid, a surfactant (SU
-2) and (SU-3) were added to adjust the surface tension.
Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

[0183]

[Table 8]

[0184]

[Table 9]

[0185]

[Chemical 32]

[0186]

[Chemical 33]

[0187]

[Chemical 34]

[0188]

[Chemical 35]

[0189]

[Chemical 36]

[0190]

[Chemical 37]

DNP: dinonyl phthalate DOP: di (2-ethylhexyl) phthalate PVP: polyvinylpyrrolidone H-2: 2,4-dichloro-6-hydroxy-s-triazine
Sodium compound A: p- (t-octyl) phenol In preparing silver halide photographic light-sensitive material, Sample No. 601, a blue-sensitive silver halide emulsion (Em-B501) was added to (Em-B502),
Sample No. 602 was prepared in the same manner except that the green-sensitive silver halide emulsion (Em-G501) was replaced with (Em-G502) and the red-sensitive silver halide emulsion (Em-R501) was replaced with (Em-R502). did.

Samples 601 and 602 were exposed through the same frame of developed Konica Color XG-400 to form a color print. In Sample 601, the print density was slightly magenta from the first sheet to the back, and the print was slightly magenta, but the finish was almost the same from the 20th sheet.
On the other hand, similarly in Sample 602, a decrease in the density was recognized from the first sheet to the 20th sheet, but the decrease in the density was small, and the imbalance was not a problem.

Further, prints were prepared by laser exposure using samples 601 and 602. Image data is 4 × 5
Image of inch size color slide (portrait)
A digital value of 25 × 25 μm per pixel was digitized by a scanner.

The exposure apparatus uses helium.
We prepared a cadmium laser (about 442 nm), a helium-neon laser (about 544 nm) as a green light source, and a helium-neon laser (about 633 nm) as a red light source, and assembled the optical system. The light emitted from the three lasers is modulated according to the image data and then focused into one beam, which is 20mm
Silver halide photographic light-sensitive material conveyed at a speed of
Scanning exposure was performed at a right angle to the carrying direction at a main scanning speed of 160 m / sec. The beam diameter at this time was about 80 μm, and the exposure time per pixel was 500 nanoseconds.

Image exposure was continuously performed with the same image data, and continuous processing was subsequently performed. As a result, sample No. 601 showed an unnatural density change in the face area after the 10th sheet, although it was very slight. Although the occurrence of (pseudo contour) was observed, Sample No. 602 was able to obtain an excellent image without such defects.

As described above, it was possible to confirm the feature of the silver halide photographic light-sensitive material according to the present invention, which was excellent in the stability of finish when images were continuously formed, even when the conditions for actual use were approached.

[0197]

The present invention has the effect of being less susceptible to the effect of the atmosphere even during high-speed printing, and less susceptible to the effect of the atmosphere of the developing solution even during rapid processing, and obtaining a stable high-quality image. .

Claims (3)

[Claims] 1. At least 95 mol% of the silver halide composition.
A silver halide photographic emulsion consisting of silver chloride, wherein the maximum frequency f _max of the dielectric loss curve by the dielectric loss method is 5 times or more of f _max of the comparative emulsion satisfying all the following conditions. Photographic emulsion. i) the silver halide photographic emulsion has the same average grain size ii) the silver halide photographic emulsion has substantially the same silver halide composition iii) the silver halide composition has substantially uniform iv ) Virtually a regular hexahedron 2. A silver halide photographic light-sensitive material containing the silver halide photographic emulsion according to claim 1, wherein at least one of compounds represented by the following general formulas [I] to [III] is used.
A silver halide photographic light-sensitive material containing two compounds. [Chemical 1] In the formula, V ₁ and V ₂ are each a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, -COOR ₁ , -COR ₁ , -CONR.
₁ R ₂ , -OR ₁ , -NR ₁ R ₂ , -NR ₁ COR ₂ , -NR ₁ SO ₂ R ₂ , alkyl group, aralkyl group, cycloalkyl group, aryl group,
Represents a heterocyclic group or an amino group, W ₁ and W ₂ are each a hydrogen atom, —NR ₃ R ₄ , —NR ₃ COR ₄ , —NR ₃ SO ₂ R ₄ , an alkyl group,
Represents an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group, X ₁ and X ₂ are each a hydrogen atom,
Cyano group, carboxyl group, sulfo group, -COOR ₅ , -COR
₅ , -CONR ₅ R ₆ , -NR ₅ R ₆ , -NR ₅ COR ₆ , -NR ₅ SO ₂ R ₆ , -SO
₂ R ₅ , an alkyl group, an aralkyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group, L ₁ , L ₂ and L ₃ each represent an unsubstituted or substituted methine group, m represents 0, 1 or 2, n represents 1, 2 or 3, and M ^{n +} represents an n-valent cation. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ may be linked to form a 5- or 6-membered ring. . However, V ₁ ,
At least one of V ₂ , W ₁ , W ₂ , X ₁ , and X ₂ represents a group containing a carboxyl group or a sulfo group. [Chemical 2] In the formula, each R ₇ represents an alkyl group, an aryl group or a heterocyclic group, and each R ₈ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, —COR ₂₀ or —SO ₂ R ₂₀ . ,
R ₉ is a hydrogen atom, a cyano group, a hydroxyl group,
Carboxyl group, -COOR ₂₀ , -CONR ₂₁ R ₂₂ , -OR ₂₀ , -N
R ₂₁ R ₂₂ , -NR ₂₁ COR ₂₂ , -NR ₂₁ SO ₂ R ₂₂ , -NR ₂₁ CONR
₂₁ R ₂₂ represents an alkyl group or an aryl group, L ₄ , L ₅ , L ₆
Each represents an unsubstituted or substituted methine group, and l is 0, 1
Or represents 2. Y ₁ and Y ₂ represent an oxygen atom or = NR ₂₃ . R ₂₀ represents an alkyl group or an aryl group, and R ₂₁ ,
Each R ₂₂ represents a hydrogen atom, an alkyl group or an aryl group. R ₂₃ represents a group of nonmetallic atoms necessary for forming a 5-membered ring by linking with R ₇ . However, at least one of R ₇ , R ₈ and R ₉ represents a group containing a carboxyl group or a sulfo group. [Chemical 3] In the formula, R ₁₃ and R ₁₄ are a cyano group, —COR ₁₇ , and —COOR, respectively.
₁₇ or -CONR ₁₈ R ₁₉ , R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and L ₇ , L ₈ and L ₉ are each unsubstituted. Alternatively, it represents a substituted methine group, and k represents 0, 1, or 2. R
₁₇ represents an alkyl group or an aryl group. R ₁₈ and R ₁₉ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and one of R ₁₈ and R ₁₉ is a hydrogen atom. However, at least one of R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ represents a water-soluble group or a substituent containing a water-soluble group. 3. A photographic image is formed by treating the silver halide photographic light-sensitive material according to claim 2 with a color developing solution containing an aromatic primary amine color developing agent and containing substantially no benzyl alcohol. In the method, the color development processing time is 25 seconds or less.