JPH09133980A - Silver halide photographic sensitive material and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a green-sensitive silver halide photographic sensitive material having high sensitivity, free from dye stain, excellent in preservability with time and pressure resistance and ensuring satisfactory stability in production by incorporating a specified spectral sensitizing dye into silver halide particles in a photosensitive silver halide emulsion layer. SOLUTION: This sensitive material contains a spectral sensitizing dye represented by the formula in silver halide particles in the photosensitive silver halide emulsion layer. In the formula, Y is O or =NR, each of R, R<1> and R<2> is optionally substd. alkyl, at least one of R<1> and R<2> is a sulfo or carboxy substd. group, each of V<1> -V<5> is H or a substitutable group, V<3> and V<4> may bond with each other to form a condensed ring, V<4> and V<5> may bond with each other to form a condensed ring, at least one of V<1> and V<2> is CF3 and n<1> is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectrally sensitized silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sensitivity, no dye stain, and excellent storage stability, pressure resistance and production stability. The present invention relates to a material and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for rapid processing of silver halide photographic light-sensitive materials. However, in order to speed up the processing, it is necessary to shorten the processing time of each processing step such as development, fixing, washing, and drying, and the load on each processing increases.

For example, when the developing time is simply shortened, the density of the conventional photosensitive material is lowered, that is, the sensitivity is lowered and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality. Further, shortening of each processing time results in insufficient elution of dyes in each processing step of development, fixing and washing, resulting in color contamination due to residual dye (residual color) and deterioration of image quality. Therefore, in order to solve such a problem, for example, the amount of silver is reduced, the developing speed or the fixing speed is increased, the amount of dye is reduced, the amount of dye removed and / or
Alternatively, it is necessary to accelerate decolorization.

On the other hand, in recent years, many techniques using tabular silver halide grains have been disclosed as means for achieving high sensitivity. Since tabular silver halide grains have the same volume and a large surface area as compared with normal grains, the amount of photosensitive dye adsorbed on the grain surface can be increased, and spectral sensitivity and image sharpness can be improved. . However, increasing the amount of the dye is not preferable because it results in an increase in residual color in a rapid process.

Further, the tabular silver halide grains having a large diameter / thickness ratio are remarkably weak against external force due to their shape, and for example, black spots (roller marks) are generated due to the pressure of the conveying roller of an automatic processor. It is known that the pressure resistance in a dry film state is weaker than that of non-tabular grains.

As a technique for improving these problems, for example, EP
-0506584, JP-A-5-88293, and 5-
No. 93975 discloses a technique of using a specific benzimidazolocarbocyanine having good decolorizing performance as a spectral sensitizing dye.

Further, in JP-A-5-61148, a silver halide emulsion having a silver iodide content of 1 mol% or less is combined with oxacarbocyanine and benzimidazolocarbocyanine in a specific ratio, and further, a selenium compound and / or It is disclosed that chemical sensitization with a tellurium compound improves rapid processability and color retention. However, although the residual color property and the rapidity of development are improved, they are still insufficient to meet the recent demand levels for various performances, and particularly when the light-sensitive material is stored for a long time under high humidity and high temperature, It had a drawback that the sensitivity was greatly reduced. Further, there is a problem regarding the pressure resistance of the film.

JP-A-7-114124 discloses specific benzimidazolocarbocyanines as a technique for improving the pressure resistance of tabular silver halide grains, but it completely eliminates the generation of roller marks in rapid processing. It hasn't reached the limit.

By the way, conventionally, it has been general that the spectral sensitizing dyes are dissolved in an organic solvent such as methanol, ethanol, fluorinated alcohol, cellosolve or dimethylformamide and then added to the silver halide emulsion.
However, in recent years, from the viewpoint of worker safety and environmental protection, a method in which, for example, dyes are dispersed and prepared as an aqueous solution system in the presence of a wetting agent or a dispersant without using these organic solvents, and added to an emulsion layer is disclosed. Has been done.

For example, in Japanese Patent Laid-Open No. 52-110012, a sensitizer is ground into an aqueous phase in the presence of a dispersant (surfactant) having a constant surface tension to remove water from the resulting aqueous dispersion. It discloses a method of adding to the emulsion as it is after drying, or after dispersing in water or a gelatin solution and then adding to the emulsion layer.

Further, in JP-A-53-102733, a homogeneous mixture (paste-like mixture) comprising a photographic additive, a dispersant such as sorbitol and a colloid such as gelatin is prepared, and the mixture is made into noodles and dried with warm air to form granules. It is a thing.
This particle size material is added to a photographic aqueous colloid coating composition.

Further, in US Pat. No. 4,006,025, a spectral sensitizing dye is mixed with water to form a slurry, and the temperature is raised to 40 to 50 ° C. in the presence of a surfactant to homogenize or mill. A method is proposed in which a spectral sensitizing dye is uniformly dispersed in water and the resulting dispersion is added to an emulsion.

However, all of these methods are methods of adding a dye and an additive as an aqueous aqueous dispersion without using an organic solvent, but they have the following problems in practical use.

That is, in the case of an adsorptive substance (sensitizing dye, stabilizer, etc.), the time required for adsorption to the silver halide grains varies depending on the particle size and distribution of the dispersion, so that the desired sensitivity is obtained within a certain period of time. Can not be obtained. When the emulsion containing the aqueous dispersion is stagnated for a long period of time, the adsorption time changes, which causes sensitivity fluctuation. Since a large amount of a wetting agent or a dispersant is used to disperse an additive, the emulsion existing in the emulsion may be destroyed or a precipitate may be generated to cause coating failure. For example, the film-forming property of the film after production is deteriorated and there is a problem in product quality.

[0015]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is high sensitivity, no dye stain, excellent storability over time and pressure resistance, improved emulsion stagnation at low temperature and good green stability. An object is to provide a silver halide photographic light-sensitive material. Still another object is to provide a method for processing the silver halide photographic light-sensitive material.

[0016]

The objects of the present invention have been achieved by the following present invention.

(1) A silver halide photographic light-sensitive material characterized in that the silver halide grains in the light-sensitive silver halide emulsion layer contain a spectral sensitizing dye represented by the following general formula (I).

[0018]

Embedded image

In the formula, Y represents an oxygen atom or a = NR group. R, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, and at least one of R ¹ and R ² represents a group that substitutes a sulfo group or a carboxy group. V ¹ , V ² , V ³ , V ⁴
And V ⁵ each represent a hydrogen atom or a substitutable group, and V ³
And V ⁴ and V ⁴ and V ⁵ may be bonded to each other to form a condensed ring. However, at least one of V ¹ and V ² represents a CF ₃ group. n ¹ is an integer of 1 or 2.

X represents an ion necessary for neutralizing the charge in the molecule, and m ¹ represents the number of ions necessary for neutralizing the charge in the molecule.

(2) The silver halide grains in the photosensitive silver halide emulsion layer are represented by the spectral sensitizing dye represented by the following general formula (I) and the following general formula (II) and / or (III). A silver halide photographic light-sensitive material comprising a combination of the spectral sensitizing dyes described above.

[0022]

[Chemical 6]

In the formula, Y represents an oxygen atom or a = NR group. R, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, and at least one of R ¹ and R ² substitutes a sulfo group or a carboxy group. V ¹ , V ² , V ³ , V ⁴ and V ⁵
Each represents a hydrogen atom or a substitutable group, and V ³ and V ⁴ and V ⁴ and V ⁵ may be bonded to each other to form a condensed ring. However, at least one of V ¹ and V ² represents a CF ₃ group.
n ¹ is an integer of 1 or 2.

X represents an ion necessary to neutralize the charge in the molecule, and m ¹ represents the number of ions necessary to neutralize the charge in the molecule.

[0025]

Embedded image

In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a substituted or unsubstituted alkyl group, and at least one of R ¹² and R ¹⁴ represents an alkyl group substituted with a sulfo group.

V ¹¹ , V ¹² , V ¹³ and V ¹⁴ each represent a hydrogen atom or a substitutable group in which the sum of added Hammett σp values is smaller than 2.4. X ¹¹ represents an ion necessary for neutralizing the charge in the molecule, and m ¹¹ represents the number of ions necessary for neutralizing the charge in the molecule.

[0028]

Embedded image

In the formula, R ²¹ and R ²² each represent a substituted or unsubstituted alkyl group, and at least one represents an alkyl group substituted with a sulfo group. Z ²¹ and Z ²² each represent a benzene ring or a naphthalene ring which may have a substituent,
L ²¹ , L ²² and L ²³ each represent a substituted or unsubstituted methine group.

X ²¹ represents an ion necessary for neutralizing the charge in the molecule, and m ²¹ represents the number of ions necessary for neutralizing the charge in the molecule.

(3) The silver chloride content of the silver halide grains contained in the photosensitive silver halide emulsion layer is 60 mol% or more and 100 mol% or less, (1) or ( A silver halide photographic light-sensitive material as described in the item 2).

(4) The total processing time after exposure is 15 seconds or more,
90 seconds or less, The processing method of the silver halide photographic light-sensitive material as described in any one of (1) to (3).

(5) 70% or more of the total projected area of the silver halide grains contained in the photosensitive silver halide emulsion layer is tabular silver halide grains having an average aspect ratio of 2 or more. The silver halide photographic light-sensitive material according to any one of items (1) to (3).

(6) The spectral sensitizing dye represented by the above-mentioned general formula (I) is used as an aqueous solution or an aqueous dispersion without using an organic solvent to form silver halide grains in a photosensitive silver halide emulsion layer. A silver halide photographic light-sensitive material characterized by being added.

The present invention will be described in detail below.

The spectral sensitizing dyes of the above general formula in the present invention all contribute to the sensitization of silver halide grains and do not include an organic dye that functions as a filter.

Examples of the alkyl group substituted in R ¹ and R ² of the general formula (I) and R ^{11 to} R ¹⁴ of the general formula (II) include hydroxyethyl, ethoxycarbonylethyl, ethoxycarbonylmethyl, aralkyl, Benzyl, phenethyl, methoxyethyl, cyanomethyl, 2-
Cyanoethyl, 2,2,2-trifluoroethyl, 2,
2,3,3-tetrafluoropropyl, carboxymethyl, carboxyethyl, sulfobutyl, sulfoethyl, sulfopropyl, sulfopentyl, 6-sulfo-3
-Oxahexyl, 4-sulfo-3-oxapentyl,
10-sulfo-3,6-dioxadecyl, 6-sulfo-
Examples include groups such as 3-thiahexyl, o-sulfobenzyl, p-carboxybenzyl, methanesulfonylaminoethyl, methanesulfonylaminocarbonylmethyl and 3-oxobutyl.

Examples of the unsubstituted alkyl group include lower alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, cyclopentyl and cyclohexyl.

The substituent represented by V ₁ or V ₂ may be any group in which the sum does not exceed 2.4 when the Hammett σp values of the substituents are added, such as a halogen atom (fluorine atom). , Chlorine atom, bromine atom, iodine atom, etc.), aryl group (phenyl, 4-bromophenyl group, etc.), alkyl group (methyl, ethyl, t-butyl group, etc.), alkoxy group (methoxy group), alkylthio group ( Methylthio group),
Trifluoromethyl group, cyano group, carboxy group, alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl group, etc.), acyl group (acetyl group), sulfonyl group (methanesulfonyl, trifluoromethanesulfonyl group, etc.), carbamoyl group (carbamoyl, N , N-dimethylcarbamoyl, N-morpholinocarbonyl group, etc.),
Examples thereof include sulfamoyl group (sulfamoyl, N, N-dimethylsulfamoyl group and the like), acetylamino group, acetyloxy group and the like.

The substituent represented by V ₃ , V ₄ and V ₅ may be any group such as a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), aryl group (phenyl, 4-bromo). Phenyl group, etc.), alkyl group (methyl,
Groups such as ethyl and t-butyl), alkoxy group (methoxy group), alkylthio group (methylthio group), trifluoromethyl group, cyano group, carboxy group, alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl group, etc.), acyl group (Acetyl group), sulfonyl group (methanesulfonyl group), carbamoyl group (carbamoyl, N,
N-dimethylcarbamoyl, N-morpholinocarbonyl group, etc.), sulfamoyl group (sulfamoyl, N, N-
Dimethylsulfamoyl group) and groups such as a hydroxy group.

The condensed ring which can be formed between V ₃ and V ₄ and V ₄ and V ₅ is, for example, a 6-membered saturated or unsaturated carbocyclic group, and a 5- or 6-membered heterocyclic group. And naphtho [2,1-d] azole, naphtho [1,2-d] azole, naphtho [2,3-] together with the azole ring.
d] Form an azole or the like. Examples of the ions represented by X and X ¹¹ are chlorine ion, bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonate ion, ethylsulfate ion, lithium ion, sodium ion, potassium. Ions, magnesium ions, triethylammonium ions and the like can be mentioned.

Hammett σ used in the general formula (II)
The p-value is a substituent constant determined by the electronic effect of the substituent on the hydrolysis of ethyl benzoate by Hammett et al., Journal of Organic Chemistry, Vol. 23, 420-427 (1958), Experimental Chemistry Course. Volume 14 (Maruzen Publishing Co.), Physical Organic Chemistry (McGraw Hill Book)
Company: 1940), Drag Design VII Volume (Aca
demic Press New York: 1976
Year)), structure-activity relationship of drugs (Nankodo: 1979), and the like.

Next, the above-mentioned general formula (I) used in the present invention is used.
Specific examples of the spectral sensitizing dye represented by

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

Next, the above general formula (II) used in the present invention is used.
Specific examples of the spectral sensitizing dye represented by

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

The above general formulas (I) and (II) according to the present invention
The spectral sensitizing dye represented by the formula is, for example, British Patent 955,96.
1, U.S. Pat. Nos. 2,739,149, 43-102.
No. 51, No. 43-10252, No. 44-16589.
No. 5, Japanese Patent Application Laid-Open No. 5-88293, and Harman's cyanine soybean-released compounds (Jhon).
Wiley & Sons, New York, 196
It can be synthesized according to the method described in 4) or the like.

Next, in the dye of the general formula (III) of the present invention, the unsubstituted alkyl group represented by R ²¹ and R ²² is specifically a lower alkyl such as methyl, ethyl, propyl, butyl or pentyl. A group can be mentioned.

Examples of the substituted alkyl group represented by R ²¹ and R ²² include hydroxyalkyl groups such as 2-hydroxyethyl and 2-hydroxypropyl, acetoxyalkyl groups such as 2-acetoxyethyl and 3-acetoxybutyl,
2-carboxyethyl, 3-carboxypropyl, 2-
Carboxyalkyl groups such as (2-carboxyethoxy) ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-
Sulfobutyl, 4-sulfobutyl, 2-hydroxy-3
-Sulfoalkyl groups such as sulfopropyl, alkoxyalkyl groups such as 2-methoxyethyl and 3-methoxypropyl, phenoxyalkyl groups such as 2-phenoxyethyl and 2- (4-carboxyphenyloxy) ethyl, 1-
Carbamoylalkyl groups such as carbamoylmethyl, 2-carbamoylethyl, N-acetylcarbamoylmethyl, N-methanesulfonylcarbamoylmethyl, 2-piperazinocarbamoylethyl, and acylaminoalkyl such as 2-acetylaminoethyl and 3-acetylaminopropyl. Group, sulfamoylalkyl group such as 2-sulfamoylethyl, 2-NN-dimethylsulfamoylethyl, N-acetylsulfamoylmethyl, 2, 2, 3,
Fluorine atom-substituted alkyl group such as 3-tetrafluoropropyl, benzyl, 2-carboxyphenylmethyl, 4-
Examples thereof include aryl-substituted alkyl groups such as carboxyphenylmethyl and 4-sulfophenylmethylphenethyl, and aralkyl groups.

However, as described above, at least one of R ²¹ and R ²² is a sulfoalkyl group or a carboxyalkyl group.

The group substituted on the condensed benzene ring or condensed naphtho ring formed by Z ²¹ and Z ²² is, for example, a lower alkyl group such as methyl, ethyl or propyl, methoxy,
Lower alkoxy group such as ethoxy, aryl group such as phenyl, 4-bromophenyl, 4-ethoxyphenyl and 3-bromophenyl, aryloxy group such as phenoxy and 4-bromophenoxy, trifluoromethyl group, fluorine, chlorine, bromine Etc., halogen atom, carboxy group, hydroxy group, ethoxycarbonyl, alkoxycarbonyl group such as methoxycarbonyl, 2-hydroxybenzoylamino group, 2-furyl, 1-pyrrolyl, 2-
Heterocyclic groups such as thienyl groups are mentioned.

Examples of the group substituted on the methine chain represented by L ²¹ , L ²² and L ²³ are lower alkyl groups such as methyl and ethyl, lower alkoxy groups such as methoxy, ethoxy and propoxy, phenoxy and 2-fluorophenoxy. Aryloxy groups such as, aralkyl groups such as benzyl and phenethyl, heterocyclic groups such as thienyl and furyl, methylthio,
Examples thereof include alkylthio groups such as ethylthio.

Examples of the ion represented by X ²¹ in the general formula [III] include chlorine ion, bromine ion, iodine ion,
Thiocyanate ion, sulfate ion, perchlorate ion, p
-Toluenesulfonate ion, ethylsulfate ion, lithium ion, sodium ion, potassium ion, magnesium ion, triethylammonium ion and the like can be mentioned.

M ² represents 0 or 1, and when forming an intramolecular salt, m ² is 0.

Next, the above general formula (II
Specific examples of the spectral sensitizing dye represented by I) will be given.

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

As the dye represented by the above general formula (III) of the present invention, in addition to the above, for example, II-3, II-4, II-6, II- of the compound examples described in JP-A-4-9040. 7, II-
8, II-10, II-13, II-14, II-16, II-1
7, II-18, II-20, II-21, II-24 to II-4
4 and the like can be similarly used.

The sensitizing dye represented by the above general formula (III) of the present invention is F.I. M. Harmer (Heterocyclic Compounds, Cyanine Giving and Relayed Compounds) IV. V. VI. Chapter 89-199. (J
hon Wiley & Sons, New Yor
K., London 1964) or D.L. M. Sturm
er (Heterocyclic Compounds Special Topics in Heterocyclic Chemistry) Chapter VIII. IV. Pp. 482-515 (Jhon
Wiley & Sons, New York, Lon
can be easily synthesized based on the method described in Don 1977).

All of the above general formulas (I), (II) and (III) show only one state of the resonance structure, and are expressed in the limit state where the + charge enters the symmetrical heterocyclic nitrogen atom. However, it means the same substance.

The combined use technique of three kinds of spectral sensitizing dyes according to the present invention is useful in a light-sensitive material which requires sensitivity to green light. In particular, it is remarkably effective in the application to an X-ray recording photosensitive material using a phosphor that emits green light in order to increase the recording sensitivity to X-rays, and is particularly effective in an X-ray medical photosensitive material.

When applied to an X-ray recording light-sensitive material using a phosphor that emits green light, the dyes represented by the general formulas (I) and (II) and the dye represented by the general formula (III) are combined. It is preferable that the J-band is formed in the same wavelength range as the green light from the phosphor when adsorbed on the silver halide grains and the reflection spectrum thereof is measured. That is, it is preferable to select and combine the spectral sensitizing dyes so that a specific J-band is usually formed in the 520 nm to 560 nm region.

The above general formulas (I) and (II) in the present invention
The addition amount of the spectral sensitizing dyes of (III) and (III) varies depending on the type of the dye and the structure, composition, ripening condition, purpose, use of the silver halide, etc. The monolayer coverage is preferably 40% or more and 90% or less, and more preferably 50% to 80%.

In the present invention, the monolayer coverage is 5
The saturated adsorption amount when the adsorption isotherm is created at 0 ° C. is relatively determined as the amount corresponding to 100% coverage.

The appropriate amount per mol of silver halide varies depending on the total surface area of silver halide grains in the emulsion, but it is 6
Less than 00 mg is preferred. Further, it is preferably 450 mg or less.

As the solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. For example, alcohols, ketones, alkoxy alcohols, etc. have been used. As a specific example, methanol, ethanol, n
-Propyl alcohol, isopropyl alcohol, 2,
There are 2,3,3-tetrafluoropropanol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, 2-methoxyethanol, 2-ethoxyethanol and the like.

However, in the present invention, the effect is enhanced by adding the spectral sensitizing dye as an aqueous solution or an aqueous dispersion without using an organic solvent. In particular, at least one of the spectral sensitizing dyes may be added in the form of a substantially water-insoluble solid fine particle dispersion dispersed in an aqueous system in which substantially no organic solvent and / or surfactant is present. preferable.

When added as an aqueous solution, the dyes of the general formulas (I) and (II) can be adjusted to a concentration suitable for addition by adjusting the pH of the aqueous solution. A technique for dispersing an organic dye in an aqueous medium is disclosed in, for example, JP-A-3-2888.
No. 42. However, this method is for making an organic dye resistant to diffusion in a photographic light-sensitive material, and is merely a dispersion addition method.

On the other hand, in the dispersion addition method of the present invention, the above-mentioned spectral sensitizing dye is made to be adsorbed uniformly and effectively on the surface of silver halide grains, and it is simply dispersed and added. This is different from the above-mentioned technique only in the purpose and effect.

In the present invention, the aqueous system in which the organic solvent and / or the above-mentioned surfactant is substantially absent is water containing impurities at a level not adversely affecting the silver halide photographic emulsion, and more preferably Indicates ion-exchanged water and distilled water.

The spectral sensitizing dye according to the present invention can be added during the chemical ripening step, particularly preferably at the start of the chemical ripening step, and the desalting can be performed from the nucleation step of the silver halide emulsion according to the present invention. A high-sensitivity silver halide emulsion excellent in spectral sensitization efficiency can be obtained by adding it by the end of the process, and the above-mentioned process can be carried out at any time after the completion of the desalting process, through the chemical ripening process, and immediately before the coating process. The spectral sensitizing dye according to the present invention, which is the same as or different from the dye added in the step (from the nucleation step to the end of the desalting step), may be additionally added.

The spectral sensitizing dye of the present invention may be used in combination with other spectral sensitizing dyes. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobora cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
These dyes can be applied to any of the nuclei commonly used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus,
Selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc., nuclei in which aliphatic hydrocarbon rings are fused to these nuclei, that is, indolenine nuclei, benzindolenine nuclei,
Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethine structure, pyrazoline-
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

In addition to these spectral sensitizing dyes, a dye having no spectral sensitizing property or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect is added to the emulsion layer. May be.

The spectral sensitizing dye according to the present invention can be added at the chemical ripening step, particularly preferably at the start of the chemical ripening step. By adding it by the end of the process, a high-sensitivity silver halide emulsion having excellent spectral sensitizing efficiency can be obtained. (From the nucleation step to the end of the desalting step), the same or a different kind of spectral sensitizing dye of the present invention may be additionally added.

The silver halide emulsion of the present invention can be chemically sensitized. Chemical sensitization refers to process conditions such as pH,
The pAg, temperature, time, etc. are not particularly limited, and can be performed under the conditions generally used in the art. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance is used. The reduction sensitization method used, gold or the like, and the noble metal sensitization method using a noble metal can be used alone or in combination, and among them, the selenium sensitization method, the tellurium sensitization method, the reduction sensitization method and the like are preferably used. Particularly, the selenium sensitization method is preferably used.

In the case of selenium sensitization, the selenium sensitizer used comprises a wide variety of selenium compounds. US Patent 1
No. 574944, No. 1602592, No. 162349
9, JP-A-60-150046 and JP-A-4-258.
No. 32, No. 4-109240, No. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), 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-nitrophenylcarbonylselenourea and the like), selenoketones (for example, selenoacetone, selenoacetone) Acetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophos Fates (eg, tri-
p-triselenophosphate, etc., selenides (diethyl selenide, diethyl diselenide, etc.) Phosphine selenides (triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, tris (m-chlorophenyl) ) Phosphine selenide and the like). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and phosphine selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but generally it is 10 ⁻⁸ to 10 mol per mol of silver halide.
^Use about ^-4 moles. The addition method, depending on the nature of the selenium compound used, water or methanol, a method of adding by dissolving in an organic solvent alone or a mixed solvent of an organic solvent such as ethanol, or a method of premixing with a gelatin solution,
It can be added by a method disclosed in JP-A-4-140739, 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.

The temperature of chemical ripening using a selenium sensitizer is 4
A range from 0 to 90C is preferred. More preferably, it is 45 ° C or more and 80 ° C or less. Moreover, pH is 4-9, pAg is 6-
A range of 9.5 is preferred.

Tellurium sensitizers and sensitizing methods are described in US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031, 3,531,289, 3,655,394, British Patents 235,211, 1,121,496, 1,295,462, 1, 396,696, Canadian Patent 800,958,
It is disclosed in JP-A-4-204640 and JP-A-4-330430.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'-. Dimethyl-N'phenyl tellurourea), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg Telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, isotelloocyanates and the like. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

By subjecting the emulsion to an appropriate reducing atmosphere, so-called reduction sensitization can be carried out on the grain surface.
Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of reducing agent added is such as the type of reduction sensitizer, the grain size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, and p.
Although it is preferable to change it depending on environmental conditions such as H and pAg, for example, in the case of thiourea dioxide, a preferable result is obtained by using about 0.01 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

As conditions for reduction sensitization, the temperature is about 40-7.
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1-10.

Silver nitrate is preferred as the water-soluble silver salt. So-called silver ripening, which is one of reduction sensitization techniques, is performed by adding a water-soluble silver salt. The pAg during silver ripening is suitably 1 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but it is disclosed, for example, in JP-A-57-82831. Antioxidants and / or V.I. S. Gahle
r's paper [Zeitshift fur wiss
enschaftriche Photographi
e Bd. 63, 133 (1969)] and JP-A-54.
Good results are often obtained in combination with the thiosulphonic acids described in -1019. The addition of these compounds may be carried out at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

In the present invention, fine grain silver iodide may be added to the silver halide emulsion in the process from chemical ripening to coating. Here, the process from chemical ripening to coating means that fine grain silver iodide is added to the process including chemical ripening and coating. Further, the fine grain silver iodide used in the present invention may be either cubic γ-AgI or hexagonal β-AgI, and may have a crystal structure thereof or a mixture thereof. .

In the present invention, fine grain silver iodide may be added in any step from the chemical ripening step to immediately before coating, but it is preferably added in the chemical ripening step.

The term "chemical ripening step" as used herein means from the time when the physical ripening and desalting operations of the emulsion of the present invention are completed to the time when the chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Points between. Further, the addition of fine grain silver iodide may be carried out in several steps at time intervals, or another chemically ripened emulsion may be added after the addition of fine grain silver iodide. The temperature of the emulsion of the present invention when the fine grain silver iodide is added is preferably in the range of 30 to 80 ° C, more preferably 40 to 6 ° C.
A range of 5 ° C is particularly preferred.

The silver halide grains of the silver halide emulsion used in the present invention include silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Although silver particles can be optionally used, particularly, silver iodochlorobromide, silver chlorobromide, or silver chloride having a silver chloride content of 60 mol% or more can achieve the effect of the present invention well.

The silver halide grains of the present invention may have any shape. For example, cube, octahedron, tetradecahedron,
It may be in the shape of a sphere, a plate, a potato, or the like.

Particularly preferred are tabular grains.

Tabular grains will be described below as typical examples of the silver halide grains of the present invention.

The tabular silver halide grains preferably used in the present invention are crystallographically classified as twin crystals. A twin is a silver halide crystal having one or more twin planes in one grain, but the morphology of twins is classified by Klein and Moiser in the article Photographis Correspondents (Photographisches Korresp).
ondenz) 99, 99, 100, 57.

The tabular silver halide grains preferably used in the present invention mainly have an even number of parallel twin planes, and these twin planes may or may not be parallel to each other. However, those having two twin planes are particularly preferable.

The tabular silver halide grains used in the present invention have an average value (average aspect ratio) of the ratio of grain diameter / thickness (aspect ratio) of 2 or more. The tabular silver halide grains used in the present invention preferably have an average aspect ratio of 2 or more and 12 or less, and more preferably 3 to 8.
It is.

The outer wall of the crystal of the tabular silver halide grains according to the present invention may be substantially composed of {111} planes or {100} planes. Further, it may have both the {111} plane and the {100} plane. In this case, 50% or more of the grain surface is the {111} plane, more preferably 60% to 90% is the {111} plane, and particularly preferably 70 to 95% is the {111} plane. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This surface ratio utilizes the difference in the adsorption dependence between the {111} plane and the {100} plane in the adsorption of the sensitizing dye [T. Tani, J .; Im
aging Sci. 29, 165 (1985)].

The tabular silver halide grains according to the present invention are
It may be polydisperse or monodisperse, but is preferably monodisperse. Specifically, (standard deviation of particle size / average particle size) x 100 = 25% or less when the size of the distribution is defined by the relative standard deviation (variation coefficient) that can be expressed by the width (%) of the particle size distribution Is preferable, 20% or less is more preferable, and 15% is particularly preferable.
It is as follows.

In the present invention, the tabular silver halide grains are preferably hexagonal. A hexagonal tabular grain (hereinafter also referred to as a hexagonal tabular grain) means its main plane ({1
11} surface) is hexagonal, and the maximum adjacency ratio thereof is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grain has a maximum adjacent side ratio of 1.0 to
If it is 2.0, it is also preferable that the corners are rounded. The length of a side when the corner is rounded is represented by the distance between the straight line portion of the side and the intersection with the line obtained by extending the straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular.

In the present invention, each side forming the hexagon of the hexagonal tabular grain preferably has a half or more of a substantially straight line. In the present invention, the ratio of adjacent sides is 1.
It is more preferably 0 to 1.5.

The silver halide grain according to the present invention may have a dislocation line. The dislocation is described, for example, in J. Mol. F. Hamil
ton, Photo. Sci. Eng, 57 (196)
7) and T. Shiozawa, J .; Soc. Pho
t. Sci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
(0 KV or more) can be observed more clearly by using an electron microscope.

The position and number of dislocations in each grain can be determined from the photograph of the grain obtained by such a method. The dislocation position of the silver halide grain according to the present invention is 0.58 from the center of the halide grain toward the outer surface.
It is desirable that it occurs in the region of L to 1.0L, but more preferably it occurs in the region of 0.80L to 0.98L. The direction of the dislocation line is approximately from the center to the outer surface, but it often meanders.

In the present invention, the center of a silver halide grain means that silver halide fine crystals are dispersed in a methacrylic resin in the same manner as the method described in the summary of Inoue et al. Solidified and cut into ultra-thin sections using a microtome, with the maximum cross-sectional area and 90% from that
Focusing on a section sample having the above cross-sectional area, the center of the circle is the smallest circumscribed circle with respect to the cross section. In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn outward from the center of the circle.

With respect to the number of dislocations of the silver halide grain according to the present invention, it is desirable that 50% (number) or more of grains containing one or more dislocations are present, and the ratio of the number of tabular grains having dislocation lines (number) ) Is higher, the more preferable.

In the present invention, the particle size is the diameter when a projected image of particles is converted into a circular image having the same area. The projected area of a grain can be calculated from the sum of the grain areas. All of them can be obtained by observing, with an electron microscope, a silver halide crystal sample distributed on the sample stage to the extent that grains do not overlap.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by the diameter corresponding to the circle of the projected area of the grains, preferably 0.30 µm or more, more preferably 0.30 µm to 5 µm. More preferably 0.40μ
It is m-2 micrometers.

The particle size can be obtained by enlarging and projecting the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the area of the projected image on the print.

The average particle size (φi) is the number of measured particle sizes n
And when the frequency of particles having a particle diameter φi is ni, it can be obtained by the following equation.

Average particle diameter (φi) = Σnidi / n (The number of measured particles is indiscriminately 1.000 or more.) The particle thickness is obtained by observing the sample obliquely with an electron microscope. You can The preferred thickness of the tabular grains preferably used in the present invention is 0.03 to 1.0.
μm, and more preferably 0.05 to 0.5 μm.

The ratio (b / a) of the longest distance (a) between two or more parallel twin planes of the silver halide grain of the present invention and the grain thickness (b) is preferably 5 or more. ,
The ratio is preferably 50% (number) or more.

The tabular silver halide grains preferably used in the present invention may have a uniform composition, but at least 2 grains having substantially different halogen compositions are contained in the silver halide grains.
Grains having a core / shell structure having a three-layer structure may be contained in the light-sensitive silver halide emulsion layer.

The silver halide grains of the present invention may be so-called halogen conversion type grains. The halogen conversion amount is from 0.2 mol% to the silver amount.
2.0 mol% is preferable, and the conversion time may be physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. At this time, the particle size is preferably 0.2 μm or less, more preferably 0.02.
０．１0.1 μm.

The silver halide grains of the present invention are preferably grown by a method of precipitating silver halide on a seed crystal such as the method described in Examples of JP-A-60-138538.

In order to obtain the tabular silver halide emulsion of the present invention, a method for producing a silver halide photographic emulsion, which comprises supplying a water-soluble silver salt solution and a water-soluble halide solution to the presence of a protective colloid, A) Silver iodide content of 0 to 5 mol%
From the beginning of the formation of silver halide precipitate in
A core particle forming step of maintaining pBr of the mother liquor at 2.5 to -0.7 is provided, and (b) following the core particle forming step, a silver halide solvent is added to the mother liquor at 10 ^-5 mol per mol of silver halide. ~
Or providing a seed grain forming step for forming silver halide seed grains containing 2.0 mol and being substantially monodisperse spherical twin crystals;
Alternatively, the temperature of the mother liquor is adjusted to 40 to
A seed grain forming step of forming a silver halide twin seed grain is carried out by raising the temperature to 80 ° C., and (c) a water-soluble silver salt solution and a water-soluble halide solution and / or halogenated fine particles are added to the seed grain. A method of providing a growth step for enlarging the plant is preferably used. Here, the mother liquor is a liquid (including a silver halide emulsion) that is used for the preparation of silver halide emulsions up to the completed photographic emulsion.

The silver halide grains formed in the above grain forming step are twin grains composed of 0 to 5 mol% silver iodide.

A water-soluble silver salt may be added for the purpose of controlling ripening during the seed grain forming step used in the present invention. The seed grain growing process for enlarging the silver halide seed grains is carried out during the silver halide precipitation and during Ostwald ripening.
It is achieved by controlling Ag, pH, temperature, silver halide solvent concentration and silver halide composition, addition rates of silver salt and halide solutions.

In preparing the emulsion according to the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present during the seed grain forming step and the seed grain growth.

In order to obtain tabular silver halide grains according to the present invention, the conditions under which the produced seed grains are enlarged are, for example, JP-A Nos. 51-39027 and 55-14232.
No. 9, No. 58-113928, No. 54-48521 and No. 58-49938, the water-soluble silver salt solution and the water-soluble halide solution are added by the double jet method, and the addition rate is increased. According to the above, a method of gradually changing it within a range in which new nucleation does not occur and Ostwald ripening does not occur may be used. As another condition for enlarging seed particles, a summary of the 1983 Annual Meeting of the Photographic Society of Japan, 88
As can be seen in the section, silver halide fine particles are added and dissolved,
A method of enlarging by recrystallization can also be used.

For growth, an aqueous solution of silver nitrate and an aqueous solution of halide can be added by the double jet method, but iodide can also be supplied to the system as silver iodide.
The rate of addition is such that no new nuclei are generated, and there is no spread of the size distribution due to Ostwald ripening,
That is, it is preferable to add it in the range of 30 to 100% of the rate at which new nuclei are generated.

In the production of the silver halide emulsion of the present invention, the stirring conditions during production are extremely important. As the stirring device, the device shown in JP-A-62-160128, in which the additive liquid nozzle is installed in the liquid near the mother liquor inlet of the stirrer, is particularly preferably used. At this time, the stirring rotation speed is preferably 400 to 1200 rpm.

The silver iodide content and the average silver iodide content of the silver halide grains of the present invention are determined by the EPMA method (Electro
n Probe Micro Analyzer). According to this method, a sample in which emulsion grains are well dispersed so that they do not come into contact with each other is prepared, and elemental analysis of a smaller portion than X-ray analysis by electron beam excitation with electron beam irradiation can be performed. By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensities of silver and iodide emitted from each grain. When the silver iodide content of at least 100 grains is determined by the EPMA method, the average silver iodide content is determined from the average of them.

In the production of the light-sensitive silver halide emulsion of the present invention, the seed emulsion has two or more twin planes in which 50% or more of the total projected area of the seed grains are parallel to each other, and Both the coefficient of variation and the coefficient of variation of the longest distance (at) between the twin planes of the seed grains are preferably 35% or less.

Even if the variation coefficient of only the thickness of the seed grain or only of (at) is 35% or less, the variation coefficient of the twin plane distance (a) of the grain after growth can be suppressed to 35% or less. It is not possible, and it is necessary for both to be established at the same time.

It is generally considered that twin planes are formed at the stage of nucleation, but some twin planes are formed during growth.

Further, the silver halide grain according to the present invention has a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt) and a rhodium salt (in the process of forming and / or growing the grain). At least one metal ion selected from the group consisting of complex salts) and iron salt (including complex salts) can be added to make these metal elements contained inside the particles and / or in the surface layer of the particles, and also suitable reduction can be carried out. The reduction sensitizing nuclei can be imparted to the inside of the grain and / or the surface of the grain by exposing the grain to a selective atmosphere.

Further, the action of the reducing agent added at a desired time of particle formation is to add an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxo acid salt, ozone and I ₂ at a desired time. It is preferable to deactivate the reducing agent and suppress or stop the reducing agent.

The timing of adding the oxidizing agent can be arbitrarily selected from the time of silver halide grain formation to the chemical sensitization step.

In the silver halide emulsion of the silver halide photographic light-sensitive material according to the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be contained therein. When removing the salts,
H. Disclosure (hereinafter abbreviated as RD) No. 17
It can be carried out based on the method described in Item 643, Item II.

The silver halide emulsion layer containing the group of grains in the present invention may contain grains of various shapes as long as the effects of the present invention are not impaired.

The silver halide photosensitive material according to the present invention comprises
Various photographic additives can be used. Known additives include, for example, Research Disclosure (R
D) No. No. 17643 (December 1978);
No. 18716 (November 1979) and the same No. 3081
19 (Dec. 1989). The types of compounds and the locations described in these three RDs are listed below.

[0139]

[Table 1]

The emulsion of the silver halide photographic light-sensitive material according to the present invention contains a developing agent such as aminophenol, ascorbic acid, pyrocatechol, or the like in the emulsion layer or other layers.
Developers such as hydroquinone, phenylenediamine or 3-pyrazolidone may be included.

The support which can be used in the light-sensitive material of the present invention is, for example, the above-mentioned RD-17643-2.
8 and RD-308119, page 1009. A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer to improve the adhesion of the coating layer,
You may give corona discharge, ultraviolet irradiation, etc.

Next, the processing method of the silver halide photographic light-sensitive material of the present invention will be described.

The silver halide photographic light-sensitive material according to the present invention provides a method for processing a silver halide photographic light-sensitive material in which the total processing time is 15 seconds to 90 seconds. The development processing method of the silver halide photographic light-sensitive material of the present invention is to complete the steps from development to drying within 90 seconds by processing with an automatic processor. That is, the time from when the tip of the photosensitive material begins to be dipped in the developing solution to when the tip comes out of the drying zone after the processing step (so-called Dry).
The time (to dry time) is 90 seconds or less, and more preferably 60 seconds or less.

Specifically, the developing time is 5 seconds to 45 seconds, preferably 8 seconds to 30 seconds. Development temperature is 25 ℃ to 50 ℃
Is preferred, and 30 ° C-40 ° C is more preferred.

The fixing temperature and time are about 20 ° C. to 50 ° C. and 6 hours.
The time is preferably from 20 seconds to 20 seconds, and more preferably from 6 seconds to 15 seconds at 30 ° C to 40 ° C. Drying time is usually 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with a heating means by far infrared rays may be installed in the automatic processor.

The automatic developing machine is provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps (Japanese Patent Laid-Open No.
-264953) may be used. Further, a device capable of adjusting a developing solution and a fixing solution may be incorporated.

Preferred developing solutions for developing the silver halide photographic light-sensitive material of the present invention include dihydroxybenzenes such as hydroquinone and paraaminophenol described in JP-A-4-15641 and JP-A-4-16841 as developing agents. Such as p-aminophenol, N
Examples of 3-pyrazolidones such as -methyl-p-aminophenol and 2,4-diammiphenol include 1-
Phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-
Phenyl-3-pyrazolidone and the like are preferably used in combination with them.

The amount of the above-mentioned para-aminophenols and 3-aminopyrazolidones used is preferably 0.004 mol / liter, more preferably 0.04-0.12.
Mol / l.

Further, the total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones contained in the components of all the development processing solutions is preferably 0.1 mol / liter or less.

The preservative may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone, and these are preferably 0.2 to 1 mol / liter. It is preferable to use 0.3 to 0.6 mol / liter. In addition, adding a large amount of ascorbic acid also leads to processing stability.

The alkaline agent includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. Further, borate described in JP-A-61-28708, saccharose, acetoxime, 5-sulfosalicylic acid, phosphate described in JP-A-60-93439,
A buffering agent such as carbonate may be used. The content of these agents is such that the pH of the developer is 9.0 to 13, preferably pH 1
Choose between 0 and 12.5.

As a solubilizing agent, polyethylene glycols and their esters, and as a sensitizing agent,
For example, a development accelerator, a surfactant and the like such as a quaternary ammonium salt can be contained.

As a silver sludge inhibitor, JP-A-56-1 has been used.
No. 06244 silver stain preventive agent, JP-A-3-5
The sulfide and disulfide compounds described in 1844 and the cysteine derivative or triazine compound described in Japanese Patent Application No. 4-92947 are preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazo type, a tetrazole type or a thiadiazole type compound is used.

Examples of the inorganic inhibitor include sodium bromide, potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson's "Photographic Processing Chemistry" published by Focal Press (19
66), pages 226-229, U.S. Pat.
No. 15,2,592,364, JP-A-48-649
No. 33 may be used. As a chelating agent for concealing calcium ions mixed in tap water used as a treatment liquid, an organic chelating agent is disclosed in Japanese Patent Laid-Open No.
A chelating agent having a chelate stabilization constant with iron of 8 or more described in Japanese Patent No. 193853 is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate. The development processing temperature is preferably 25 to 50 ° C., more preferably 30 to 50 ° C.
40 ° C. The developing time is 5 to 90 seconds, more preferably 8 to 60 seconds. Processing time is Dry to D
ry is preferably 20 to 210 seconds, more preferably 30.
~ 90 seconds.

Regarding the replenishment of the treatment liquid, the treatment agent fatigue and oxidative fatigue equivalent amount are replenished. As a replenishment method, JP-A-55-126
Replenishment according to the width and feed rate described in Japanese Patent No. 243, JP-A-60.
Area replenishment described in JP-A-104946, JP-A 1-1491
Area replenishment controlled by the number of continuous treatments described in No. 56 may be used, and the preferable replenishment amount is 500 to 150 cc.
/ M ² .

As the fixer composition used in the method for processing a silver halide photographic light-sensitive material according to the present invention, an ordinary acidic hardener can be used.

[0158]

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

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce 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-1) 12.14 g, (ST-2) 1
0.32 g, and high boiling 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) 12 m.
A magenta coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 1 by using an ultrasonic homogenizer.

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, surfactants (SU-2), (S
U-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 2 below.

[0163]

[Table 2]

[0164]

Embedded image

SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: di (2-ethylhexyl) sulfosuccinate
Sodium salt SU-3: sulfosuccinic acid di (2,2,3,3,4,4)
4,5,5-octafluoropentyl) sodium salt DIDP: di-i-decyl phthalate DBP: dibutyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane (preparation of silver halide emulsion) kept at 40 ° C. 2 % Solution of gelatin, the following (solution A) and (solution B) are simultaneously added while controlling pAg = 7.3 and pH = 3.0, and further (solution C) and solution (D) and (E solution) and (F solution) were added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the control of pAg is disclosed in JP-A-59-45.
No. 437, and the pH was controlled 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 92.1 g Potassium bromide 0. 87 g Water added 538 ml (D liquid) Silver nitrate 269 g Water added 538 ml (E liquid) Sodium chloride 10.6 g Potassium bromide 0.13 g Water added 62 ml (F liquid) Silver nitrate 31 g Water added 62 ml After that, desalting was performed using a 5% aqueous solution of Demol N and a 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.43 μm.
m, coefficient of variation (S / R) = 0.08, silver chloride content 9
A 9.5 mol% monodisperse cubic emulsion (EMP-11) was obtained.

Next, the following compounds were optimally chemically sensitized at 60 ° C. to obtain a green-sensitive silver halide emulsion (Em-G1).
01) was obtained.

In the above Em-G101, GS-1
Except that the sensitizing dyes shown in Table 3 were replaced by the same chemical sensitization, and green-sensitive silver halide emulsions (Em-G102) to (Em-G102).
-G118) was obtained.

Sodium thiosulfate 3.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS- Solid dispersion aqueous solution of 1) 4 × 10 ⁻⁴ mol / mol AgX

[0170]

Embedded image

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole Each of these emulsions was divided into two parts, one of which was a dispersant or another as described above. A coating sample was prepared with the above additives. The other one was once cooled, gelled, stored for 2 days in a low temperature chamber, then redissolved and added with a dispersant and other additives to prepare a coated sample. (Sample Nos. 1-1 to 1-20) Each of the obtained coated samples was tested for storability under the following two conditions.

Condition I: left at 23 ° C., 55% RH for 3 days Condition II: left at 30 ° C., 90% RH for 3 days Each sample was applied to a three primary color separation filter using a sensitometer KS-7 type (manufactured by Konica Corporation). After green light wedge exposure, the following development processing was performed.

As the processing solution, Konica Color QA Paper Type A5 was printed and run in advance until a replenishing solution of twice the tank capacity of the color developing solution was replenished.

The development processing step and the composition of the processing solution are shown below. The amount of replenishment is represented by the amount per 1 m ² of the light-sensitive material.

(Treatment Step) Treatment Step Treatment Temperature Time Replenishment Amount Color Development 39.0 ± 0.3 ° C. 45 seconds 40 ml Bleach-fix 35.0 ± 0.5 ° C. 45 seconds 51 ml Stabilization 30-34 ° C. 90 seconds 250 ml ( Three-tank cascade) Drying 60 to 80 ° C. 60 seconds The composition of the tank liquid and the replenisher of the development processing liquid is shown below.

(Color developer tank solution and replenisher) (Tank solution) (Replenisher) Pure water 800 ml 800 ml Triethanolamine 10 g 14 g N, N-diethylhydroxylamine 3.6 g 5 g Potassium chloride 4.5 g-Diethylenetriaminepentaacetic acid 5.0 g-potassium sulfite 0.4 g-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 12.0 g potassium carbonate 25 g 35 g Water was added to bring the total amount. Adjust to 1 liter and adjust the pH of the tank solution to 10.10 and the replenisher to pH 11.50.

(Bleaching and Fixing Solution Tank Solution and Replenishing Solution) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 53 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 123 ml Ammonium sulfite (40% aqueous solution) 51 ml 1 liter, pH = 5 with potassium carbonate or glacial acetic acid. Adjust to 4.

(Stabilizing Solution Tank Solution and Replenishing Solution) o-Phenylphenol 0.1 g Ubitex (manufactured by Ciba Geigy) 1.0 g Zinc sulfate heptahydrate 0.1 g Ammonium sulfite (40% solution) 5.0 ml 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Water was added to bring the total volume to 1 liter, and pH = 7. Adjust to 8.

[0179]

Embedded image

Performance Evaluation A processed sample was used as a PDA-65 type densitometer (Konica Corporation).
The density of the magenta dye was measured with a product manufactured by K.K.), the characteristic curve was determined, and then the sensitivity was determined by the reciprocal of the exposure amount required to give a density of fog + 0.5.

<Preservation with time> Sample No. stored under the above condition I. The green light sensitivity of I-1 was set to 100 and shown as a relative value.

<Emulsion low-temperature stagnation property> A silver halide emulsion was immediately coated without setting and the obtained sample was preserved under storage condition I.
The sensitivity obtained after the storage was stored as S _O ^I.

On the other hand, a sample coated after the silver halide emulsion was cooled and set for a time (about 12 hours) was stored under the storage condition I.
The sensitivity obtained after the storage was stored as S _S ^I. From the obtained sensitivity, the emulsion low-temperature stagnation property was defined as the sensitivity fluctuation value in the emulsion set by the following formula.

ΔS (S _O ^I / S _S ^I ) The closer the ΔS value is to 1, the better the stability over time during setting. Table 3 shows the obtained results.

[0185]

[Table 3]

* A: (Solid dispersion added) Dye previously at 27 ° C
In addition to the temperature-controlled water, the dispersion aqueous solution obtained by high-speed stirring with a dissolver was adjusted to a concentration of 0.5 w / v% and a predetermined amount was added.

* B: (solution addition) D-methanol and 2,
The dye was adjusted to a concentration of 0.5% in a 1: 1 mixed solvent of 2,3,3-fluoropropanol and a predetermined amount was added. As is clear from the table, (G
The comparative samples using S-2 and II-57) have large sensitivity fluctuations over time, and the magnitude thereof changes due to the difference in the addition method. Similar to the control sample, the sample according to the present invention has suppressed sensitivity fluctuations over time regardless of the method of adding the dye, and has high green light sensitivity.

The control sample had good photographic performance, but was inferior in that strong residual color stain having a maximum absorption at 510 to 515 nm was observed in the white background portion.

On the other hand, the sample of the present invention was excellent in that no clear coloring was observed in the white background and no residual color contamination was observed.

Example 2 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 100 g potassium bromide 2.05 g with water 11.5 l B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml water with 2.6 l C1 ossein gelatin 75 g potassium bromide 950 g potassium iodide 27 g with water 3.0 l D1 silver nitrate 95 g with water 2.7 l E1 silver nitrate 1410 g with water 3.2 l Into the A1 liquid in which the temperature of the reaction vessel was kept at 60 ° C., the B1 liquid and the D liquid
Solution 1 was added by the control double jet method over 30 minutes, and then solutions C1 and E1 were added by the control double jet method over 105 minutes with stirring for 5 minutes.
It was carried out at 00 rpm.

The flow rate was such that new nuclei did not occur with the growth of particles, and so-called Ostwald ripening occurred, so that the particle size distribution did not broaden. When the silver ionic liquid and the halide ionic liquid were added, pAg was adjusted to 8.3 ± 0.05 using potassium bromide liquid, and pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then, in order to remove excess salts, precipitation desalting treatment was carried out using an aqueous solution of Demol N (manufactured by Kao Atlas [Company]) and an aqueous solution of magnesium sulfate.

When the seed emulsion thus obtained was observed with an electron microscope, it was a cubic tetradecahedral monodisperse emulsion having an average grain size of 0.27 μm and a grain size distribution of 17% with a slightly rounded corner.

Preparation of Em-1 A monodisperse core / shell type emulsion was prepared using the above seed emulsion-1 and the following seven kinds of solutions.

A2 Oscein gelatin 10 g Ammonia water (28%) 28 ml Glacial acetic acid 3 ml Seed emulsion-1 0.119 mol equivalent Equivalent to 600 ml B2 ossein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g 110 ml with water Finish with C2 ossein gelatin 2g Potassium bromide 90g Finish with water to 240ml D2 Silver nitrate 9.9g Ammonia water (28%) 7.0ml Finish with water 110ml E2 Silver nitrate 130g Ammonia water (28%) 100ml Finish with water 240ml F2 Potassium bromide 94 g Finish with water to 165 ml G2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Finish with water to 110 ml Solution A2 was kept at 40 ° C. and stirred at 800 rpm with a stirrer. The pH of the A2 solution was adjusted to 9.90 with acetic acid,
Seed emulsion-1 was sampled and dispersed and suspended, and then G2 solution was added at a constant rate over 7 minutes to adjust pAg to 7.3. Further, B
Solution 2 and solution D2 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. PH = 8.83, pAg using potassium bromide solution and acetic acid over 10 minutes
= 9.0, the C2 solution and the E2 solution were simultaneously added over 30 minutes.

At this time, the flow rate ratio at the time of addition and at the end of addition was 1:10, and the flow rate was increased with time.
Also, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio.

When the solution C2 and the solution E2 were added in the amount of ⅔ of the total amount, the solution F2 was additionally injected and added at a constant rate over 8 minutes. At this time, pAg increased from 9.0 to 11.0. Further, acetic acid was added to adjust the pH to 6.0.

After completion of the addition, precipitation desalting was carried out in the same manner as in the above seed emulsion to remove excess salts, and pAg
Emulsion Em-1 having an average silver iodide content of about 2. 5 mol% at pH 5.85 at 8.5 and 40 ° C. was obtained.

Observation of the obtained emulsion with an electron microscope revealed that the average grain size was 0.55 μm and the grain size distribution was 14%.
Was a rounded tetradecahedral monodisperse core / shell type emulsion.

(Preparation of seed emulsion-2) Seed emulsion-2 was prepared as follows.

A3 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B3 2.5N silver nitrate aqueous solution 2825 ml C3 bromide Potassium 824 g Potassium iodide 23.5 g Finish with water to 2825 ml D3 1.75N aqueous potassium bromide solution Silver potential control amount below 35 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828
Using a mixing stirrer described in No. 9, 464.3 ml of each of solution B3 and solution C3 was added to solution A3 by a simultaneous mixing method to obtain 2.0.
Nucleation was performed by adding over a minute.

After stopping the addition of solution B3 and solution C3, it took 60 minutes to raise the temperature of solution A3 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B3 and solution C3 were each mixed by the simultaneous mixing method at 55.4.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B3 and C3 was made + using the solution D3, respectively.
It was controlled to be 8 mV and +16 mV.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of hexagonal tabular grains is 0.06 μm, and the average grain size is 0.06 μm. It was confirmed with an electron microscope that the diameter (converted to a circle diameter) was 0.59 μm.

Preparation of Em-2 A tabular emulsion Em-2 was prepared using the above seed emulsion-2 and the following three kinds of solutions.

A4 ossein gelatin 5.26 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-2 0.094 mol equivalent Equal to 569 ml with water B4 ossein gelatin 15.5 g odor Potassium iodide 114 g Potassium iodide 3.19 g Finish with water to 658 ml C4 Silver nitrate 166 g Finish with water to 889 ml A4 solution vigorously stirred at 60 ° C.
It was added by the double jet method in 7 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7 throughout. B4 liquid and C4
The addition rate of the liquid was linearly increased so as to be 6.4 times at the beginning and at the end.

After completion of the addition, precipitation desalting was carried out in the same manner as Em-1 to remove excess salts, and pAg 8.5, 40
The average silver iodide content at pH 5.85 is about 2.0 at ℃
A mol% emulsion was obtained.

When the obtained emulsion was observed with an electron microscope, 82% of the projected area was a tabular silver halide grain having an average grain size of 0.98 μm, a grain size distribution width of 18% and an average aspect ratio of 4.5. there were.

Preparation of Em-3 A tabular emulsion having a core / shell structure was prepared by using the seed emulsion-2 and the following four kinds of solutions.

A5 ossein gelatin 11.7 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-2 0.10 mol equivalent Equal to 550 ml of water B5 ossein gelatin 5.9 g odor Potassium iodide 4.6 g Potassium iodide 3.0 g Water to make 145 ml C5 Silver nitrate 10.1 g Water to make 145 ml D5 Ocein gelatin 6.1 g Potassium bromide 94 g Water to make 304 ml E5 Silver nitrate 137 g Water to make 304 ml The liquid B5 and the liquid C5 were added to the liquid A5, which was vigorously stirred at 70 ° C., in 58 minutes by the double jet method. Next, D5 liquid and E5 liquid were added to the same liquid by the double jet method for 48 minutes. During this period, the pH was kept at 5.8 and the pAg was kept at 8.7.
After the addition was completed, desalting and precipitation were carried out in the same manner as Emulsion Em-2.
An emulsion having a pAg of 8.5 and a pH of 5.85 and an average silver iodide content of about 2.0 mol% was obtained at 0 ° C.

When the obtained emulsion was observed with an electron microscope, 81% of the projected area had a mean grain size of 0.96 μm, a broad grain size distribution of 18%, and a tabular halogen having an average aspect ratio of 4.5. It was a silver halide grain.

Then, after bringing the obtained emulsion to 60 ° C.,
After adding a predetermined amount of the spectral sensitizing dye shown in Table 4 as a solid fine particle dispersion, a mixed aqueous solution of the following sensitizer formulation was added, and after 60 minutes, a silver iodide fine grain emulsion was added, and the mixture was added for 2 hours in total. Aged. At the end of aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Additives other than the spectral sensitizing dye and their addition amounts are shown below.

Sensitizer Formulation Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Pentafluorophenyl-diphenylphosphine selenide 2.0 mg Silver iodide fine particles 850 mg Stabilizer (TAI) 1 g Spectral sensitizing dye The solid fine particle dispersion of is Japanese Patent Application No. 4-994.
Prepared by a method according to the method described in No. 37. That is, it was obtained by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and stirring with a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

Next, the additives to be described later were added to the emulsion thus spectrally sensitized, and the emulsion coating solution sample No. 1-21 were created. At the same time, a coating solution for the protective layer was prepared.

In order to investigate the stagnation after preparation of the above-mentioned coating liquid samples, a standard coating liquid left at 40 ° C. for 30 minutes and a coating liquid aged at 40 ° C. for 8 hours were prepared.

The obtained coating solution was applied onto a support using two slide hopper type coaters so that the amount of silver per one side of the support was 2.0 g / m ² and the amount with gelatin was 3.1 g / m ^2. Both sides were simultaneously coated and dried to obtain a sample. The support has a thickness of 175 μm and a concentration of 0.15 and is blue-colored. A polyethylene terephthalate film base for X-rays is provided on both sides with 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate, and 40 wt% of butyl methacrylate.
%, The concentration of the copolymer consisting of three kinds of monomers is 10 wt%
The following filter dye (solid dispersion) and gelatin were dispersed in an aqueous copolymer dispersion obtained by diluting the resulting solution to give an undercoating solution, which was used.

[0218]

Embedded image

Additives added to the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10.000) 1.0 g Styrene maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium Chloride 50 mg 1,3-dihydroxybenzene-4-ammonium sulfonate 2.0 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl-5-mercaptotetrazole 15 mg

[0221]

Embedded image

Protective Layer Solution Next, the following was prepared as a protective layer coating solution. The additives are shown in an amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2.0 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (A matting agent having an area average particle diameter of 1.2 μm) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2.0 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0224]

Embedded image

[0225]

[Table 4]

Next, the obtained coating amount sample No. 2-1 to N
o. Each of No. 2-21 was left to stand under the following two conditions, and a storability substitute test was conducted.

Condition A: Reference sample left at 23 ° C., 55% RH for 4 days Condition B: Preservation test sample left at 40 ° C., 80% RH for 4 days The evaluation method was as follows. It was sandwiched between sensitive papers KO-250 (manufactured by Konica Corporation), exposed to X-rays through an aluminum wedge for 80 seconds at a tube voltage of 80 kVp and a tube current of 100 mA for 0.05 seconds. Then, using an automatic processor SRX-502 (manufactured by Konica Corp.), processing was performed with a developing solution and a fixing solution having the following formulations.

Developer Formulation Part-A (for 12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-Phenyl-5-mercapto Tetrazole 0.2 g Hydroquinone 340 g Water is added to make 5000 ml.

Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1.0 l. .

Fixer Formula Part-A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18g Part-B Aluminum sulphate 800g To prepare a developing solution, simultaneously add Part A and Part B to about 5 liters of water, add water while stirring and dissolve to make 12 liters, and adjust the pH to 10.40 with glacial acetic acid. It was adjusted. This is used as a developing solution. 20m of the starter for 1 liter of this developer
1 / l is added to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part A and P to about 5 liters of water.
artB was added at the same time, and water was added while stirring and dissolving.
and the pH was adjusted to 4.4 using sulfuric acid and NaOH. This is used as a fixing replenisher.

The processing temperature and processing time are as follows: development 38 ° C. 15 seconds, fixing 35 ° C., 15 seconds, water washing 20 ° C., 10 seconds.
Seconds, drying at 50 ° C., and the total treatment time was 45 seconds in dry to dry.

<Evaluation of stagnation and storability> Sensitivity is fogging +
It was determined by the reciprocal of the exposure amount that gives a density of 1.0.

The stagnation property was determined by setting the sensitivity of the sample stored under the above storage conditions A to S _i ^A, and then allowing the coating solution to stand for 30 minutes at 40 ° C. for 8 hours. With respect to the coated sample, the sensitivity of the sample stored under the storage condition A was taken as S _C ^A , and the value of ΔS ^p (S _i ^A / S _C ^A ) was used as a measure of the sensitivity fluctuation due to stagnation after the preparation of the coating solution. . Further, the sensitivity of the sample stored under the storage condition B is S _C ^{B, which} is obtained by applying the sample which has been aged at 40 ° C. for 8 hours,
Wherein the sensitivity of the samples stored in the storage conditions A as S _C ^A, △ was ^{_{S S (S C A / S}} C B) measure value storage of the sensitivity variation of. It was also a measure of the respective fog from ^{_{△ F S (F C A /}} F C B) the determined storage of fog variation at that time. The closer the values of ΔS and ΔF are to 1, the better the manufacturing stability (stagnation) and the storage stability over time.

Pressure Resistance (Roller Mark) The pressure resistance was evaluated as follows. 40 of the above
An unexposed sample stored under storage condition A after being aged at 8 ° C. for 8 hours was uniformly exposed to a blackening density of 1.0 in a size of 10 × 12 inches, and then developed in the same manner as above. Treated. However, the developing rack used at this time and the developing-to-fixing transition rack were intentionally fatigued. That is, the rollers of each rack were fatigued so that unevenness of about 500 microns was formed on the entire surface. Due to the pressure caused by the unevenness, many speckled density unevenness was generated in the processed sample in the sample with poor pressure resistance. This level was visually evaluated according to the following ranks.

5: No spots are generated 4: Slight spots are generated but this is not a problem for practical use 3: Small amount of spots are generated but not normally on a rack Level 2: Spots are generated Ordinarily, it sometimes occurs even in racks. 1: Many spots occur. It is always generated even in a normal rack. <Evaluation of residual color> A sample obtained by treating the unexposed sample stored at the storage condition A after being stored for 30 minutes at 40 ° C. in the above-mentioned processing step The residual color property of was visually evaluated on a scale of 5 levels. The one with no residual color is given the highest rank of "5",
Below, according to the degree of occurrence of residual color, "4", "3",
The rank was sequentially lowered to "2" and "1" for evaluation. "2"
And "1" are levels that are not practically preferable. Table 5 shows the above results.

[0237]

[Table 5]

As is apparent from the table, the sample of the present invention showed little fluctuation in sensitivity due to the stagnation of the coating solution, and had good storage stability of the raw film over time. Furthermore, the sample of the present invention had excellent pressure resistance and had little residual color stain due to the dye.

[0239]

As demonstrated in the examples, according to the present invention, a low-temperature stagnation property of the emulsion and a stagnation property of the coating solution are stable, and a green-sensitive silver halide photographic emulsion having no sensitivity fluctuation deterioration is obtained. It was useful in manufacturing. Further, according to the present invention, it is possible to obtain a green-sensitive silver halide photographic light-sensitive material which has good storability of raw film over time, little residual color contamination, and excellent pressure resistance, and a processing method thereof.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 5/26 G03C 5/26

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material comprising a silver halide grain in a light-sensitive silver halide emulsion layer containing a spectral sensitizing dye represented by the following general formula (I). Embedded image In the formula, Y represents an oxygen atom or a = NR group. R, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group,
At least one of R ¹ and R ² represents a group substituting a sulfo group or a carboxy group. V ¹ , V ² , V ³ , V ⁴ and V ⁵ each represent a hydrogen atom or a substitutable group, and V ³ , V ⁴ and V
⁴ and V ⁵ may be bonded to each other to form a condensed ring. However, at least one of V ¹ and V ² represents a CF ₃ group. n ¹ is 1
Or an integer of 2. X represents an ion required to neutralize the intramolecular charge, and m ¹ represents the number of ions required to neutralize the intramolecular charge. 2. A silver halide grain in a photosensitive silver halide emulsion layer is represented by a spectral sensitizing dye represented by the following general formula (I) and a general formula (II) and / or (III) below. A silver halide photographic light-sensitive material comprising a combination of the following spectral sensitizing dyes. Embedded image In the formula, Y represents an oxygen atom or a = NR group. R, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group,
At least one of R ¹ and R ² substitutes a sulfo group or a carboxy group. V ¹ , V ² , V ³ , V ⁴ and V ⁵ each represent a hydrogen atom or a substitutable group, and are bonded to each other between V ³ and V ⁴ and between V ⁴ and V ⁵ to form a condensed ring. Good. However, V ¹ ,
At least one of V ² represents a CF ₃ group. n ¹ is 1 or 2
Is an integer. X represents an ion required to neutralize the intramolecular charge, and m ¹ represents the number of ions required to neutralize the intramolecular charge. Embedded image In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each represent a substituted or unsubstituted alkyl group, and at least one of R ¹² and R ¹⁴ represents an alkyl group substituted with a sulfo group. V ¹¹ , V ¹² , V ¹³ ,
Each V ¹⁴ represents a hydrogen atom or a substitutable group in which the sum of added Hammett σp values is smaller than 2.4. X ¹¹ represents an ion necessary for neutralizing the charge in the molecule, and m ¹¹ represents the number of ions necessary for neutralizing the charge in the molecule. Embedded image In the formula, R ²¹ and R ²² each represent a substituted or unsubstituted alkyl group, and at least one represents an alkyl group substituted with a sulfo group. Z ²¹ and Z ²² each represent a benzene ring or a naphthalene ring which may have a substituent, and L ²¹ , L ²² and L ²³
Each represents a substituted or unsubstituted methine group. X ²¹ represents an ion necessary for neutralizing the charge in the molecule, and m ² represents the number of ions necessary for neutralizing the charge in the molecule. 3. The silver chloride content of the silver halide grains contained in the photosensitive silver halide emulsion layer is 60 mol% or more,
3. The silver halide photographic light-sensitive material according to claim 1, which is 100 mol% or less. 4. The total processing time after exposure is 15 seconds or more and 90.
The method for processing a silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein the processing time is within seconds. 5. The tabular silver halide grains having an average aspect ratio of 2 or more account for 70% or more of the total projected area of the silver halide grains contained in the light-sensitive silver halide emulsion layer. Item 4. The silver halide photographic light-sensitive material according to any one of Items 1 to 3. 6. The spectral sensitizing dye represented by the general formula (I) is added to the silver halide grains of the photosensitive silver halide emulsion layer as an aqueous solution or an aqueous dispersion without substantially using an organic solvent. A silver halide photographic light-sensitive material characterized in that