JPS63316039A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain superior reciprocity law failure characteristic causing no change in sensitivity and gradation against a change of illumination by producing a silver halide photographic sensitive material by incorporating an Ir compd. into a silver halide emulsion, and allowing inorganic S to be present before a stopping stage of a chemical sensitization is completed. CONSTITUTION:A silver halide photographic sensitive material having at least one silver halide emulsion layer on a base contg. an Ir compd. in the silver halide emulsion contained in the silver halide emulsion layer is produced while allowing inorganic S to be present before a stopping stage of chemical sensitization of the silver halide emulsion is completed. The addition of the Ir compd. to be used is carried out pref. during formation of silver halide particles or during chemical sensitization. By this constitution, a silver halide photographic sensitive material having superior reciprocity law failure characteristic is provided, wherein said photographic sensitive material causes only slight variation of sensitivity and almost no variation of gradation due to its reciprocity law failure characteristic.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved reciprocity law failure characteristics. be.

[Background of the invention]

In general, reciprocity law failure refers to not following the reciprocity law, as explained in the ``Dictionary of Photographic Terms'' (Complete edition of the Photographic Terminology Committee of the Photographic Society of Japan, published by Shashin Kogyo Publishing). In other words, in a photochemical reaction, the reaction behavior is the product of light illuminance and irradiation time,
In other words, a reciprocity law that is proportional to the amount of irradiation light is often established, but failure to follow this law is called reciprocity law failure. In the process of photographic exposure, the reciprocity law does not hold even if the illuminance is too strong or too weak.
A phenomenon called low-light reciprocity failure often occurs.

On the other hand, it is desired for silver halide photographic materials to improve their exposure characteristics in response to changes in various photographing and printing conditions, and in particular, the reciprocity law failure characteristics of photosensitive materials, which are closely related to the slope characteristics during printing. is one of the important characteristics.

Here, the slope characteristic is "Photography Terminology Dictionary" (mentioned above) 1
As explained in Section 39 as slope control, the exposure and color of the print obtained when the same subject is photographed using color negative film and printed using an integral neutral printer. The balance changes, so when the horizontal axis is the exposure change value of a color negative that has been changed from the appropriate exposure, and the vertical axis is the reflection density of each color in the print, the deviation from the horizontal plane is called the slope. Generally, all three colors will be different. Changes in print density and color balance with respect to the negative density are called slope characteristics. The slope characteristics are largely caused by the shape of the negative characteristic curve, the deviation of the average transmitted light of the negative, the characteristics of the printer, and the reciprocity law failure characteristics of the photosensitive material that provides the print.

Printers are equipped with automatic adjustments to control the slope characteristics, but depending on the type of negative film and the degree of overexposure, this may not be sufficient, so the slope characteristics may also be adjusted in terms of the photosensitive material that provides the print. A technology that is easy to control, that is, an improvement in reciprocity law failure characteristics, is desired. Conventionally, it has been reported in Japanese Patent Publication No. 43-4935 that sensitivity fluctuations due to reciprocity failure can be reduced by adding an iridium compound to a silver halide photographic emulsion.
No. 45-32738; JP-A No. 52-88340; JP-A No. 54-96024.

However, if the amount of iridium compound added is increased in order to reduce sensitivity fluctuations due to reciprocity failure, the sensitivity fluctuations will indeed become smaller, but on the contrary, the gradation fluctuations will tend to increase, and the two are not necessarily mutually exclusive. The reality is that the amount added could not be increased to a satisfactory level. Furthermore, in the case of multilayer color photographic materials, there are generally regular emulsion layers,
The ortho emulsion layer and panchromatic emulsion layer are coated, but since each layer contains different silver halide emulsions, exacerbators, sensitizing dyes, inhibitor couplers, coating aids, etc., the color balance of the three layers is the most required. It was extremely difficult to improve the reciprocity law failure characteristics while maintaining this. In particular, it is difficult to reduce gradation fluctuations in the three layers and match the directions of movement.

Therefore, if the exposure amount is constant, even if the illuminance changes, there will be little variation in sensitivity and gradation, and in particular, there will be little variation in gradation, that is, silver halide photographic materials with improved reciprocity law failure characteristics. It is hoped that it will appear.

[Object of the Invention] Therefore, the object of the present invention is to provide a silver halide photographic material having improved reciprocity law failure characteristics in which the sensitivity and gradation do not change even if the illuminance changes as long as the exposure amount is constant. That's true.

[Structure of the invention]

The object is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion contained in the silver halide emulsion layer contains an iridium compound, and the silver halide emulsion layer contains an iridium compound. This was achieved by a silver halide photographic material characterized in that it was produced in the presence of inorganic sulfur until the end of the chemical sensitization process of the emulsion.

The present invention will be explained in more detail below.

The iridium compound used in the present invention is not particularly limited in its type, but water-soluble iridium compounds are particularly preferred, and halogenated iridium compounds are more preferred in terms of compound stability, safety, economic efficiency, etc. (I
[[) compounds [e.g. iridium chloride (■), iridium bromide (Ill), etc.], iridium halide (■) compounds [e.g. iridium chloride (■), iridium bromide (Ill), etc.]
IV), etc.), iridium complex salts having a halogen atom, amines, oxalato, etc. as a ligand, for example,
Hexachloroiridium (I[[) complex salt, hexachloroiridium (F/)ti salt, hexamineiridium (I
Examples include [[) complex salt, hexamine iridium (IV) complex salt, and the like. In the present invention, trivalent and tetravalent compounds can be used in any combination. These iridium compounds are used by dissolving them in water or a suitable solvent, but in order to stabilize the solution of iridium compounds, the commonly used method is to stabilize the iridium compound solution, i.e., using a hydrogen halide aqueous solution (e.g. hydrochloric acid, hydrobromic acid, fluoric acid). ) or alkali halides (e.g. KCI, NaCl, KBr, NaBr
etc.) can be used.

The iridium compound used in the present invention can be added at any step in the production process of a silver halide emulsion, but specifically, the iridium compound is added before the formation of silver halide grains in the production process, before the formation of silver halide grains, When silver oxide grains are formed,
Any period selected from during silver halide grain formation, from the end of silver halide grain formation to before the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and until the end of chemical sensitization. , preferably during silver halide grain formation or chemical sensitization.

The iridium compound used in the present invention may be added at one time or at multiple times.

In this case, a mixed solution of Ir(DI) and Ir(IV) is
It may be divided into more than one time and added in different processes, or I
The solution of r(III) and the solution of Ir(IV) may be added separately in different processes, and the amounts of addition are as follows: Ir(Ill) compound and Tr(r
l/) The total number of moles of the compound is io-”~10-S
A molar range is preferable; if the amount is less than this amount, the effect will be small, and if the amount is more than this amount, desensitizing effect or fog may occur, which is generally not preferred.

The silver halide emulsion according to the present invention uses inorganic sulfur in the chemical aggravation process in combination with the iridium compound, thereby suppressing gradation fluctuations while maintaining the improvement in sensitivity fluctuations caused by reciprocity failure due to the addition of the iridium compound. It is something that can be done.

The term "inorganic sulfur" used in the present invention means so-called simple sulfur that does not form a compound with other elements. Therefore, in the art, sulfur-containing compounds known as photographic additives, such as sulfides, sulfuric acid (or its salts), sulfurous acid (or its salts), thiosulfuric acid (or its salts), sulfonic acids (or its salts), ), thioether compounds, thiourea compounds, mercapto compounds,
Sulfur-containing heterocyclic compounds and the like are not included in the "inorganic sulfur" in the present invention.

It is known that the simple substance sulfur used as "inorganic sulfur" in the present invention has several allotropes, and any of these allotropes may be used.

Among the above allotropes, the one that is stable at room temperature is α-sulfur, which belongs to the orthorhombic system.
- Preference is given to using sulfur.

When adding the "inorganic sulfur" according to the present invention, it may be added as a solid, but it is preferably added as a solution. Inorganic sulfur is insoluble in water, but is known to be soluble in carbon disulfide, sulfur chloride, benzene, diethyl ether, ethanol, etc., and it is preferable to dissolve it in these solvents before adding it. Among these inorganic sulfur solvents, ethanol is particularly preferably used from the viewpoint of ease of handling and photographic effects.

When chemical sensitization is carried out in the presence of inorganic sulfur, the appropriate amount of inorganic sulfur to be added varies depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect.
lXl0-'mg to 10m per mole of silver halide
g range, preferably I x 10-3 mg to 5 m
g range.

Regarding the timing of adding inorganic sulfur, it can be added at any step up to the end of the chemical sensitization stopping step. Specifically, chemical sensitization is performed before the formation of silver halide grains, during the formation of silver halide grains, from the end of silver halide grain formation to before the desalting process, and from after the desalting process to before the start of chemical sensitization. It may be carried out at any time selected from the beginning of sensitization, during chemical sensitization, and until the end of chemical sensitization. It is preferably added at any time selected from the time of silver halide grain formation, during chemical sensitization, and before the end of chemical sensitization.

In order to obtain a particularly remarkable effect of suppressing tone variation without causing sensitivity variation due to reciprocity law failure, it is more preferable to add it during silver halide grain formation or chemical aggravation.

In the present invention, inorganic sulfur may be added all at once, or may be added in multiple portions.

The present invention may be used in combination with other sensitizers, specifically,
Chemical sensitizers such as chalcogen sensitizers can be used. Chalcogen sensitizers include sulfur sensitizers, selenium sensitizers,
It is a general term for tellurium sensitizers, but for photography, sulfur sensitizers and selenium sensitizers are preferred. As the sulfur sensitizer, known ones can be used. Examples include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, P-toluenethiosulfonate, and rhodanine. Others, U.S. Patent L574,9
44, No. 2.410689, No. 2.278,947
No. 2,728,668, No. 3.501.313, No. 3,656,955, OLS 1
, No. 422.869, JP-A No. 56-24937, No. 5
Sulfur sensitizers described in JP 5-45016 and the like can also be used.

The amount of sulfur enhancer added varies over a considerable range depending on various conditions such as pH2 temperature and silver halide grain size, but as a guide, halide 1! The amount is preferably about 10-7 to 10-1 mol per mol.

Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas,
Selenides such as selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenophosphates, diethylselenide, and diethylselenide can be used, and specific examples thereof are described in U.S. Patent No. 1.5.
No. 74,944, No. 1,602,592, No. 1.62
It is described in the specification of No. 3,499, etc. Furthermore, reduction and exacerbation can also be used together. The reducing agent is not particularly limited, but includes known stannous chloride, urea dioxide, hydrazine, polyamine, and the like. Also, noble metal compounds such as platinum compounds, palladium compounds, etc. can be used.

In the present invention, the conditions for chemical sensitization to be carried out vary depending on the silver halide grains used and the expected photographic properties, but as a rough guide, the temperature should be between 35°C and 7°C.
0°C, pH 5.0 to 7.5, pAg 6.
It is 0 to 8.5.

The chemical sensitization time is usually determined by examining the photographic characteristics for each time step in advance under the chemical sensitization conditions, and selecting the most favorable photographic characteristics (for example, low capri, high sensitivity, high contrast, etc.). It is set to the time, but
Manufacturing stability and work efficiency in the process are often considered, and a rough guideline is several tens of minutes to several hours.

The chemical sensitization described above can be stopped by methods known in the art. Methods for terminating chemical sensitization include lowering the temperature, lowering the pH, and using a chemical sensitization stopper, but considering the stability of the emulsion, etc. A method using is preferred. Examples of chemical sensitization stoppers include halide salts (e.g., potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (e.g., 7-hydroxy-5-methyl-1,3, 4,7a-detrazaindene, etc.) are known. These compounds may be used alone or in combination.

In the case where the inorganic sulfur according to the present invention is added before the end of the chemical sensitization termination step, the "chemical sensitization termination step" refers to the step of adding the above chemical sensitization termination agent. The timing of adding sulfur may be substantially during the chemical sensitization termination process, and specifically, at the same time as the addition of the chemical sensitization termination agent or within 10 minutes before or after, preferably at the same time or within 5 minutes before or after the addition of the chemical sensitization termination agent. Including when added within minutes.

(Left below) In the silver halide emulsion of the present invention, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc. are used in ordinary silver halide emulsions. Any one can be used.

As a photosensitive material for printing, in order to impart high contrast gradation, the silver iodide content is preferably 1 mol % or less, or it is preferable to contain no silver iodide at all, and in order to impart rapid processability, it is preferable to contain salt. Silver bromide and silver chloride are preferred.

Most preferred are high silver chloride containing silver chlorobromide and silver chloride.

The silver halide grains according to the present invention may be mixed with silver halide grains other than the present invention, but in that case, all the silver halide in the silver halide emulsion layer containing the silver halide grains according to the present invention The ratio of the projected area occupied by the silver halide grains of the present invention to the projected area occupied by the grains is preferably 5.
It is 0% or more, more preferably 75% or more.

The silver halide grains of the present invention can be used, for example, in JP-A-59-16
No. 2540, No. 59-48755, No. 60-
It can be formed using the methods described in JP-A No. 222844, JP-A No. 60-222845, JP-A No. 60-136735, and the like.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1, [iILm], more preferably 0. The range is from 25 to 1.2 pm. Incidentally, the above particle size can be measured by various methods commonly used in the technical spectrometer. A typical method is Loveland's "Particle Size Analysis Method J.
A, S, T, M, Symposium on Light Microscopy 1955.

pp. 94-122 or “Theory of the Photographic Process” by Mies and James, 3rd edition, published by Macmillan (19
It is described in Chapter 2 of 1966). The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is determined by the following equation.

Here, rl represents the particle size of each particle, and ni represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. .

The silver halide grains according to the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the pAg-chondrold-double jet method described in No. 48521 and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Patent No. 4,183,756, U.S. Patent No. 4,225°666,
Japanese Patent Publication No. 55-28.58!1, Special Publication No. 55-4273
Specifications such as No. 7, The Journal on Photographic Science (J, Photogr, 5ci)
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 21.39 (1973) and used. Furthermore, particles having twin planes or irregularly shaped particles may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes, but it is better to use grains of a single shape. preferable.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains according to the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

The silver halide emulsion of the present invention contains antifoggants, stabilizers,
It is possible to add a compound called

These compounds are 4-hydroxy-6-methyl-1,
Although many heterocyclic compounds and mercapto compounds are known, including 3,3a,7-titraazaindene, 3-methylbenzothiazole, and 1-phenyl-5-mercaptotetrazole, in the present invention, the following general formula [ A compound represented by [S] is particularly preferably used.

General formula [S] (wherein, Q represents a 5- or 6-membered heterocycle or an atomic group necessary to form a 5- or 6-membered heterocycle fused with benzene rings, and M is a hydrogen atom or represents a cation.) The mercapto compound represented by the general formula [S] will be described below.

In the general formula [S], Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a fused 5- or 6-membered heterocycle with a benzene ring; Examples of the ring include an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, etc. can be mentioned.

Examples of the cation represented by M include alkali metals (
Examples include sodium, potassium, etc.), ammonium groups, and the like.

The mercapto compound represented by the general formula [S] can be further synthesized by the following general formulas [RA, [SB], [Se3 and [SD]
The mercapto compounds shown respectively are preferred.

General formula [SA] In the formula, RA represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group, and Z represents -N)I- Represents 1-0-5 or -S-, M
are M and clonic in the general formula [S].

General formula [SBcor] In the formula, Rn represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group, or a sulfonamide group. represent. n represents an integer from 0 to 2. M has the same meaning as M in general formula [S].

In the general formulas [RA and [SB], examples of the alkyl group represented by RA and R3 include methyl group, ethyl group, butyl group, etc., and examples of the alkoxy group include methoxy group, ethoxy group, etc. Examples of salts of carboxyl groups or sulfo groups include sodium salts and ammonium salts.

In the general formula [SA], examples of the aryl group represented by RA include a phenyl group and a naphthyl group, and examples of the halogen atom include a chlorine atom and a bromine atom.

Examples of the acylamino group represented by Re in the general formula [SB] include a methylcarbonylamino group and a benzoylamino group, examples of the carbamoyl group include an ethylcarbamoyl group and a phenylcarbamoyl group, and examples of the sulfonamide group include, for example, Examples include methylsulfonamide group and phenylsulfonamide group.

The above-mentioned alkyl groups, alkoxy groups, aryl groups, amine groups, acylamino groups, carbamoyl groups, sulfonamide groups, etc. further include those having substituents.

General formula [SC Co. R.A. In the formula, Z represents -N-, an oxygen atom or a sulfur atom.

RA represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, a -5RA l group, and R
AI is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -(:0RA4, or -5O
2RAS, RA2 and RA3 represent a hydrogen atom, an alkyl group, or an aryl group, and RA4 and L
s represents an alkyl group or an aryl group. M has the same meaning as M in general formula [S].

General formula [RA in SC, RAI, RA2.
Examples of the alkyl group represented by RA3°RA4 and RAS include a methyl group, benzyl group, ethyl group, and propyl group, and examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the alkenyl group represented by RA and RAI include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group. Examples of the heterocyclic group represented by RA include furyl group and pyridinyl group.

The above RA, RAI, RA2. RA3. RA4
The alkyl group and aryl group represented by RAS, the alkenyl group and cycloalkyl group represented by RA and RAI, and the heterocyclic group represented by RA further include those having a substituent.

General formula [S D] In the formula, RA and M each represent a group having the same meaning as RA and M in the general formula [SC], and RBI and R112 each represent a group having the same meaning as RAI and RA□ in the general formula [SC1]. represents a group.

Specific examples of the compound represented by the general formula [S] are shown below, but the present invention is not limited thereto.

Below margin 5A-I 5
A-2SA-35A-4 S8-55A-6 Below margin S8-758-8 R-1 SB-55B-8 R^ Tsuta V The compound represented by the above general formula [3] is, for example,
No. 0-28496, JP-A-50-89034, Journal on Chemical Society 4 (J, Che+n,
Soc, )49°1748 (1927), 423
7 (1952), Journal on Organic Chemistry (J, Org, Chem,) 39, 24
69 (1965), U.S. Patent No. 2,824,001;
Journal on Chemical Society, 1723
(1951), Japanese Patent Application Publication No. 56-111846, British Patent No. 1.275°701, U.S. Patent No. 3,266.89
No. 7, No. 2,403,927, etc., and can be synthesized according to the methods described in these documents.

In order to incorporate the compound represented by the general formula [31 (hereinafter referred to as compound [S]) according to the present invention into a silver halide emulsion layer containing silver halide grains according to the present invention, water or water and optionally It may be added after being dissolved in an organic solvent (for example, methanol, ethanol, etc.) that is miscible with the organic solvent. Compound [S] may be used alone, or in combination with 2 or more compounds represented by the general formula [S], or other stabilizers or fog suppressants other than the compound represented by the general formula [S]. May be combined with

Compound [S] is generally added at the end of chemical sensitization of silver halide, but it can be added at the beginning or in the middle of chemical sensitization after the formation of silver halide grains. is also possible. The most preferable method for enhancing the effect of the present invention is to add it in portions at the beginning and end of chemical sensitization.

There is no particular restriction on the amount added, but it is usually I x 10-' mol to 1 x 10-1 mol per mol of silver halide.
mol, preferably I x 10-' mol to 1x10
- It is added in a range of 2 moles.

The emulsion according to the present invention can be spectrally sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dye may be used alone, but 2 fffi
The above may be combined. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. You can let me.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, a pyridine nucleus, an oxazoline nucleus, a thiazoline nucleus, a virol nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus,
These include naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus. These nuclei are
May be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat. No. 2,519.001, No. 2
, No. 912,329, No. 3,856,959, No. 3,
No. 672.897, No. 3,694゜217, No. 4.0
No. 25,349, No. 4,048,572, British Patent 1
, No. 242,588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 1, No. 2,072,908, No. 2,739,149
No. 2,945.7fi3, British Patent No. 505,97
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 9 and the like. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2,442,710, No. 2,454,629, No. 2,776゜280, etc. . Furthermore, U.S. Patent Nos. 2,213,995 and 2,493,748,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in Patent No. 2.519.001 and West German Patent No. 929.080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions. can.

These @-sensitive dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publications No. 43-4932, No. 34-49.33, No. 43-4936, No. 44-32753, No. 45-2.
No. 5831, No. 45-26474, No. 46-1162
No. 7, No. 46-18107, No. 47-8741, No. 47-11114, No. 47-25379, No. 47-
No. 37443, No. 48-28293, No. 48-384
No. 06, No. 48-38407, No. 48-38408, No. 48-41203, No. 48-41204, No. 4
No. 9-6207, No. 50-40682, No. 53-12
No. 375, No. 54-34535, No. 55-1569, JP-A No. 50-33220, No. 50-33828,
No. 50-38526, No. 51-107127, No. 5
No. 1-115820, No. 51-135528, No. 51
-151527, 52-23931, 52-5
No. 1932, No. 52-104911i, No. 52-10
No. 4917, No. 52-109925, No. 52-110
No. 618, No. 54-80118, No. 5B-25728
No. 57-1483, No. 58-10753, No. 5
No. 8-91445, No. 5B-153926, No. 59-
No. 114533, No. 59-116645, No. 59-1
No. 16647, U.S. Patent No. 2. [No. 8,545, same 2,
No. 977.229, No. 3,397,060, No. 3,5
No. 06.443, No. 3,578,447, No. 3,67
No. 2,898, No. 3,679,428, No. 3,769
No. 301, No. 3,814,609, No. 3.837.
It is described in No. 862.

The amount of the sensitizing dye added is not particularly limited, but it is preferably used in the range of approximately 1X10-' to IX10-' mole per mole of silver halide, more preferably 5X10-' mole.
10-' to 5 x 10-' moles.

As a method for adding the sensitizing dye, a method well known in the art can be used.

For example, these sensitizing dyes can be dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or mixtures of such solvents), in some cases diluted with water, and In some cases they can be dissolved in water and added in the form of these solutions. It is also advantageous to use ultrasonic vibrations for this dissolution. Furthermore, the sensitizing dye used in the present invention can be prepared by dissolving the dye in a volatile organic solvent and dispersing the solution in a hydrophilic colloid, as described in U.S. Pat. No. 3,469,987. Method of adding
As described in Japanese Patent No. 185, etc., a method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added. Further, the sensitizing dye used in the present invention can be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method. Other methods of addition include U.S. Patent No. 2,
The methods described in Japanese Patent Nos. 912,345, 3.34'2,605, 2,996,287, and 3.425,835 can also be used.

The sensitizing dyes to be contained in the silver halide emulsion of the present invention can be dissolved in the same or different solvents, and these solutions can be mixed or added separately before being added to the silver halide emulsion. If they are added separately, the order, time and interval can be arbitrarily determined depending on the purpose. The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion manufacturing process, but it is preferably added during or after chemical ripening, and more preferably during chemical ripening.

The silver halide photographic emulsion according to the present invention is used as a light-sensitive material for black-and-white printing, but it can also be used as a light-sensitive material for color printing. The effects of the present invention are more effectively exhibited in the latter case.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The order may be changed as appropriate depending on the important performance and purpose of use.

When the silver halide photographic light-sensitive material used in the present invention is a multicolor light-sensitive material, the specific layer structure includes a yellow dye image-forming layer, an intermediate layer, a magenta dye image-forming layer, an intermediate layer, and a magenta dye image-forming layer on the support. Particularly preferred is an arrangement of an image forming layer, an intermediate layer, a cyan dye image forming layer, an intermediate layer, and a protective layer.

The dye image-forming coupler used in the present invention is not particularly limited, and various couplers can be used, but the compounds described in the following patents are representative examples.

Yellow dye image-forming couplers include 4- or 2-equivalent couplers of the acylacetamide type and benzoylmethane type, which are described, for example, in U.S. Pat. No. 2,778.
, No. 658, No. 2,875,057, No. 2,90
No. 8,573, No. 52,908,513, No. 3, 2
27゜155, same No. 3,227,550, same No. 3,
No. 253,924, No. 3,285,506, No. 3
, 277.155, 341.331, 3,369,895, 3,384,657, 3,408,194, 3,415,652 ,
Same No. 3,447,928, Same No. 3,551.155, Same No. 3,582゜322, Same No. 3,725,072
German Patent No. 1,547°868, German Patent No. 2,05
No. 7,941, No. 2,162,899, No. 2,1
No. 63,812, No. 2,213,461, No. 2゜219.917, No. 2,261,361. No. 2,263,875, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 48-29432, Japanese Patent Publication No. 48-66834, Japanese Patent Publication No. 48-66834
No. 9-10736, No. 49-122335, No. 50-
No. 28834, No. 50-132926, No. 55-14
It is described in the specifications of No. 4240 and No. 56-87G41.

The magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers of the 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indacylon type, and cyanoacetyl type. Patent No. 2,600,788,
No. 3,061,432, No. 3,062,653, No. 3,127,269, No. 3,311゜476
No. 3,152,896, No. 3,419,39
No. 1, No. 3,519,429, No. 3,558,3
No. 18, No. 3684.514, No. 3,705,
No. 896, No. 3,888,680, No. 3,907
, No. 571, No. 3,928,044, No. 3.93
No. 0,861, No. 3,930,816, No. 3,9
33゜500, Japanese Patent Publication No. 4'1-29639, 49
-111631, 49-129538, 51-
No. 112341, No. 52-58922, No. 55-62
No. 454, No. 55-118034, No. 5 [1-386
No. 43, No. 5B-135841, Special Publication No. 46-604
No. 79, No. 52-34937, No. 55-29421, No. 55-35696, British Patent No. 1.247,49
No. 3, Belgian Patent No. 792,525, West German Patent No. 2,156,111 specifications, Japanese Patent Publication No. 4B-60
No. 479, JP-A-59-125732, JP-A No. 59-22
No. 8252, No. 59-162548, No. 59-171
No. 956, No. 60-33552, No. 60-43659
No. 1, West German Patent No. 1.070,030, and US Pat. No. 3,725,067.

Cyan dye image-forming couplers include phenolic,
Naphthol type 4-equivalent or 2-equivalent type cyan dye image-forming couplers are typical, and U.S. Patent No. 2,306,4
No. 1Q, No. 2.356.475, No. 2,382,
No. 598, No. 2,367.531, No. 2,369
No. 929, No. 2,423,730, No. 2,47
No. 4,293, No. 2,476.008, No. 2,4
No. 98,466, No. 2゜545.687, No. 2,
No. 728,660, No. 2,772,162, No. 2
, 895,826, 2,976.146, 3.002,836, 3,419,390, 3,446°622, 3,476.563 ,
No. 3,737,316, No. 3,758,308, No. 3,839,044, British Patent No. 478,99
No. 1, No. 945.542, No. 1.084.480
No. 1,377.233, No. 1,388,02
4 and 1,543,040, as well as JP-A Nos. 47-37425, 50-10135, 50-25228, 50-112038, and 50
-117422, 50-130441, 51-
No. 8551, No. 5l-371i47, No. 51-528
No. 28, No. 51-108841, No. 53-10983
No. 0, No. 54-48237, No. 54-66129,
No. 54-131931, No. 55-32071, No. 5
No. 9-146050, No. 59-31!153 and No. 6
It is described in various publications such as No. 0-117249.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either equivalence is acceptable.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin conductors, graft polymers of gelatin and other polymers, proteins, Hydrophilic colloids such as sugar conductors, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.

The silver halide photographic light-sensitive material of the present invention further contains color clouding preventive agents, image stabilizers, ultraviolet absorbers, plasticizers, latex, surfactants, matting agents, lubricants, antistatic agents, hardeners, etc. Additives may optionally be used.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to a development process known in the art.

Specifically regarding color development processing, the color developing agent used in the color developer in the present invention includes aminophenol derivatives and p-phenylenediamine derivatives which are widely used in various color photographic processes.

In addition to the above-mentioned primary aromatic amine color developing agent, known developer component compounds can be added to the color developing solution applied to the processing of the silver halide photographic light-sensitive material of the present invention.

The pH value of the color developer is usually above 7, most commonly about 10-13.

Color development temperature is usually 15°C or higher, generally 20°C.
It is in the range of °C to 50 °C. For rapid development, it is preferable to carry out the process at 30°C or higher. In addition, conventional processing takes 3 minutes or more.
Although the color development time is generally 4 minutes, the color development time for rapid IA filling is preferably within 120 seconds, more preferably within 90 seconds.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments are not limited thereto.

(Left below) Example 1 In the presence of inert gelatin, 5°C, pAg7.2,
Silver nitrate aqueous solution, potassium bromide and sodium chloride (Br/CZ −=”/5°) under pH 3.0 conditions.
A silver chlorobromide emulsion having a silver chloride content of 50 mol % was prepared by adding and mixing an aqueous solution consisting of the following. At that time, when silver chlorobromide was formed, a silver halide emulsion to which 5 x 10-h mol of (I r (IV) Cl b ) was added per 1 mol of silver chlorobromide and an emulsion to which no silver halide was added were mixed. It was adjusted. As a result of silver observation under an electron microscope, this silver halide emulsion contained monodisperse tetradecahedral grains with an average grain size (in terms of spheres) of 0.38 μm. Next, this silver halide emulsion was precipitated and washed with water in a conventional manner, and then I) Ap was adjusted to 7.5, and additional inert gelatin was added and redispersed.

After dividing the obtained emulsion, the sensitized side (sodium thiosulfate) and inorganic sulfur (commercial product, purity 99.99) shown in Table 1 were added.
Optimum chemical sensitization was carried out at 60°C using 99%). 4-hydroxy-6-methyl-(1,3,3a
,? )-Tetraazaindene (abbreviated as TAI) and Exemplary Mercapto Compound 5B-2 in lXl0-”mol/A g
X moles were added to prepare a ripening emulsion.

In the chemical sensitization, sodium thiosulfate was added to start the sensitization, inorganic sulfur was added during the chemical sensitization, and TAI or 5B-2 was added when the chemical sensitization was stopped.

(Margin below) Table 1 υNa Next, the obtained coating sample 1-14 was subjected to sensitometry and reciprocity law failure characteristic tests. The test method is to adjust the illuminance so that the exposure amount is constant for 0.2 seconds (standard exposure) and 16 seconds (low-light exposure), perform a light contract exposure, and then follow the processing method shown below. After processing and drying, sensitometry was measured using a Sakura color densitometer PDA-65 model (Konishi Roku Photo Industry KK!!).
．． Relative sensitivity (S) and floor at 2 second exposure and 16 second exposure! Calculate IJ (γ), and then calculate the sensitivity change rate S"(S16'/So,2'X100)% and the gradation change rate r"(r16'/ro,2'X100)%.
were determined, and the results are shown in Table 2. 3
m and r− respectively represent reciprocity law failure characteristics, and S
o indicates the rate of change in sensitivity of low light exposure (16 seconds) with respect to standard exposure (0,2 seconds), T9 is standard exposure (0,2 seconds)
Indicates the rate of change in gradation of low light exposure (16 seconds) for
In either case, the closer the value is to 100%, the less fluctuation there is.

In addition, the phenomenon processing conditions were all performed in the same manner as follows.

[Processing process]

Temperature Time Development 20±0.3℃ Stop for 4 minutes
Fixed for 1 minute
Washing with water for 2 minutes Drying for 2 minutes 60-80℃ 2 minutes (developer) Metol 2g Anhydrous sodium sulfite 90g Hydroquinone 8g Soda carbonate (l hydrate)
52.5g potassium bromide
Add 5 g of water 11 (stop solution) Sodium acetate 1% solution (fixed young solution) Conifix (manufactured by Konishiroku Photo Industry Co., Ltd.) Table 2 From Table 2, Kz (Tr (IV) C11b
) Even if inorganic sulfur is added to an unadded emulsion during chemical sensitization, the sensitivity fluctuation (S") and gradation fluctuation (.gamma.0) are large and the reciprocity law failure characteristics are not improved.

On the other hand, emulsion 8 containing Kt (I r (IV) CA6), which does not contain inorganic sulfur, has S'', γ0
Emulsion 9 according to the present invention has large fluctuations and small improvement effect.
It is clear that in the case of 14 to 14, the fluctuation becomes significantly smaller and the reciprocity law failure characteristics are greatly improved. Furthermore, it was found that emulsion 13.14 using the exemplified mercapto compound further enhanced the effects of the present invention.

Example-2 Kz (I r (IV) C1h used in Example-1
) instead of Ks (I r (Ill) C16)
Similar tests were conducted on silver halide emulsions produced in exactly the same manner except that
Similarly, excellent effects were obtained with the method of the present invention.

Example 3 A silver chlorobromide emulsion having a silver chloride content of 99.5 mol % was prepared in the same manner as in Example 1. This emulsion contained monodisperse cubic grains with an average grain size of 0.35 μm. Regarding this emulsion, as shown in Table 3, Ks (I
r (In) C1h) was included in the emulsion in varying amounts. It was then precipitated, washed with water, added additional gelatin, and redispersed.

After dividing the resulting emulsion, sodium thiosulfate (4.0X
IO-' mol/AgX mol), silver chloride (3,0X10
-' mol/A g x mol), inorganic sulfur (shown in Table 3), exemplary mercapto compound 5B-5 (3,0XIO
-' mol/A g x mol) and the following red-sensitive sensitizing dye (IXIO-' mol/A g x mol (IXIO-
"mol/A g x mole) was added.

Before starting chemical sensitization, S, B-5, inorganic sulfur, and chloroauric acid were added in this order, and then sodium thiosulfate was added to start chemical sensitization, and during chemical sensitization, red sensitization was carried out. Added dye. Furthermore, 5B-2 was added when sensitization was stopped.

The obtained chemically enhanced emulsion was coated in the composition shown below to prepare a multilayer sample.

A silver halide color photographic material was prepared by sequentially coating the following eight layers on a corona discharge treated paper support whose both sides were treated with polyethylene resin.

In addition, the amount of addition shown below is 1 m2 unless otherwise specified.
The hit amount is shown.

Ml: layer containing 1.0 g of gelatin.

Layer 2: 1.2 g of gelatin, 0.38 g (same in terms of silver) for the front layer photosensitive silver chlorobromide emulsion (silver chloride composition 99.
7 mol %: cubic crystal; average particle size 0.85 μm; gold sulfur sensitization; contains blue photosensitive dye) and 0.88 g of yellow coupler (Y-1) and 0.015 g of 2.5-di -0 in which t-octylhydroquinone (referred to as HQ-1) was dissolved
, a layer containing 44 g of DOP (dioctyl phthalate).

Layer 3: Layer containing 0.7 g of gelatin.

Layer 4: 1.25 g of gelatin, 0.32 g of green-sensitive silver chlorobromide emulsion (silver chloride composition: 99.5 mol%; cubic crystal;
average particle size 0.38 μm; total sulfur sensitization;
1) and a layer containing 0.2 g of DOP in which 0.015 g of [1Q-1 was dissolved.

Layer-5: A layer containing 0.35 g of DBP (dibutyl phthalate) in which 1.28 g of gelatin and 0.08 g of IIQ-1 and 0.5 g of ultraviolet absorber (UV-1) were dissolved. .

Layer-6: 1.4 g of gelatin, 0.25 g of red-sensitive silver chlorobromide emulsion (the chemically enhanced emulsion described above).

0.50 g of the following exemplified cyan coupler ((, -1) and 0
．． A layer containing 0.18 g of DOP in which 0.2 g of HQ-1 was dissolved.

Layer-7...1.0g gelatin, and 0.032g
HQ-1 and 0.14 g of DBP dissolved in 0.2 g of ultraviolet absorber (UV~1).

Layer 8: Layer containing 0.5 g of gelatin.

In addition, H-1 was used as a hardening agent in layers 1, 3, 5. and 8 were added in an amount of 0.017 g per 1 g of gelatin.

(Left below) Yellow coupler (Y-1) I Magenta coupler (M-1) Cyan coupler (C-1) rp Ultraviolet absorber V-X Using the coated sample, sensitometric evaluation was performed by the method shown below. Ta.

[Sensitometry and reciprocity law failure evaluation] Each sample was exposed to white light through an optical wedge using a photometer (model KS-7 manufactured by Konishiroku Photo Industry Co., Ltd.) (according to Example-1). , the following processing was performed. Then, PDA-65? for the treated sample. The reflection density of the sample was measured using a W meter (manufactured by Konishiroku Photo Industry Co., Ltd.) through a red filter. The measurement values were processed in accordance with Example-1.

(Processing process) Temperature Time color development 33℃±0.3℃ 90 seconds bleach fixing 33℃±0.3℃ 90 seconds stabilization
Dry at 30-346°C for 90 seconds 60-80°C for 60 seconds [Color developer] Pure water 8QQml Ethylene glycol 10ml 1N, N-diethylhydroxylamine log Potassium chloride
2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30g fluorescent brightener (4,4'-
Diaminostilbendisulfonic acid derivative) 1g Add water to bring the total amount to 11, and adjust to p) 110.08.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (
40%? 9? &) 27.5m 1 Adjust the pHL to 1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1.
Set to 1.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 g Water was added to bring the pH to 11, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide. 0
Adjust to.

The obtained sensitometry results are shown in Table-3.

(Margins below) Table 3 From Table 3, 3 (T r (
III) If only CNi) is added and the amount is increased, the sensitivity variation (S*) will certainly become smaller, but the gradation variation (γ*) will increase, which may pose a practical problem. I understand. (Samples 15-21).

On the other hand: + (I r (ill) Ce
Samples 22 to 27 of the present invention, which used both b) and inorganic sulfur, had smaller sensitivity fluctuations and lower sensitivity than emulsions containing no inorganic sulfur when the same amount of 3 (Ir (III) C1,) was added. Since the key fluctuation is also small, the reciprocity law failure characteristics are clearly improved.

It has also been found that with the configuration of the present invention, sensitivity fluctuations due to reciprocity failure can be freely controlled without gradation fluctuations. This is a great advantage in controlling the color balance of each layer in multilayer color photosensitive materials.

Example 4 Using the same emulsion as that used in Example 3, a sensitized emulsion was prepared by changing the chemical sensitization recipe in the chemical sensitization step as follows.

(However, the iridium compound is 6×10-”mol/Ag×
Formulation A: After adding 5B-5, inorganic sulfur and chloroauric acid in this order, chemical sensitization was started by adding sodium thiosulfate, and during chemical sensitization, a red-sensitive sensitizing dye was added, and further A prescription in which 5B-5 (second time) is added when chemical sensitization is stopped.

Formulation B: In Formulation A, red-sensitizing dye and 5B-5 (
A formulation in which inorganic sulfur (second time) is further added during the period of addition (second time).

Formulation C: A formulation in which inorganic sulfur was added at a time between the addition of red-sensitivity dye and 5B-5 (second time) in Formulation A.

Formulation D: Formulation A in which sodium thiosulfate is not added.

Formulation E: A formulation in which inorganic sulfur is added after the chemical sensitization process is completed in Formulation A.

Note that the amount of each additive added was substantially the same as the amount of addition described in Example-3. However, the amount of inorganic sulfur added is 3.5×10″/Ag×mol.

Furthermore, the chemical sensitization process includes an optimal ripening process.

Emulsions of formulations A-H were processed in the same manner as described in Example-3 and their reciprocity failure characteristics were investigated.

The results are shown in Table-4.

Table 4 From Table 4, it can be seen that non-yellow sulfur is effective even if it is added in portions during the chemical sensitization process or added at the end of sensitization. (Sample No. 28, 29, 30) or the absence of an unstable sulfur compound such as sodium thiosulfur in chemical sensitization does not impair the effects of the present invention.

(Sample No. 31).

On the other hand, in formulations in which inorganic sulfur was added after the end of chemical sensitization, the reciprocity law failure characteristics were significantly degraded, indicating that the addition position of inorganic sulfur is important in achieving the effects of the present invention. Understood. (Sample No. 32) [Effects of the Invention] As explained above, the silver halide photographic material of the present invention has excellent reciprocity law failure characteristics with small sensitivity fluctuations and almost no gradation fluctuations. It has a remarkable effect, especially when applied to photosensitive materials for printing.

Applicant: Agent Konishiroku Photo Industry Co., Ltd.
Patent Attorney Miki Nakajima Yudo
Yu Kuramochi15f1162ζ-12!11
1” Name change *: *(-ya) Procedure Neho 36 (voluntary) May 13, 1988 Director General of the Patent Office Kunio Ogawa 1, Indication of the case 1988 Patent Application No. 160216 2, Invention Name of Silver Halide Photographic Light-sensitive Material 3, Relationship with the person making the amendment Case Representative of patent applicant Keio Ide 4 Address of agent 2-42-1 Kabukicho, Shinjuku-ku, Tokyo 160
No. 1 5. Date of amendment order (voluntary) 7. Contents of amendment 1) The scope of claims will be corrected as shown in the attached sheet.

2) Correct "not to comply" in the first line of page 2 of the specification to "not to comply".

3) "The purpose is...
``includes, and'' is corrected as follows.

"The above object is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion contained in at least one of the silver halide emulsion layers contains an iridium compound, and 4) "Capri" in the second line from the bottom of page 7 of the specification is corrected to "r fog."

5) "Not formed" on page 8, line 8 of the specification is corrected to "not formed."

6) "Orthorhombic system" on page 9, line 2 of the specification is changed to "orthorhombic system"
Correct.

7) On page 10, line 17 of the specification, "chemical sensitizers, such as" is corrected to "chemical sensitizers include, for example."

8) "Sulfur sensitizer" on page 11, line 12 of the specification is corrected to "sulfur sensitizer."

9) "Sulfur sensitization" on page 11, line 17 of the specification is corrected to "sulfur sensitizer."

10) "Represented by the general formula [S]...may be combined" in the second line from the bottom on page 34 to the second line from the bottom on page 35 of the specification.
is corrected as follows.

“Combination of two or more types of compound [S], or compound [S]
It may be combined with other stabilizers or antifoggants. 11) "Steryl dye" on page 36, line 4 of the specification is corrected to "styryl dye."

12) In the specification, page 41, line 5, "contain" is corrected to "add".

13) "5°C" on page 49, line 3 of the specification is corrected to "50°C".

14) 'I)Al)J' on page 49, line 15 of the specification
Corrected by AgJ.

15) In Table 1 on page 51 of the specification, "Additional amount of inorganic sulfuric acid (mol/Agx mol)" at the top of the second column from the right is changed to "Additional amount of inorganic sulfur (mg/AgX mol)". ” is corrected.

16) The structural formula of (H-1) described on page 52 of the specification is corrected as follows.

17) "Phenomenon" in the first line from the bottom of page 53 of the specification is corrected to "development."

18) "Adjustment" in the second line of page 57 of the specification is corrected to "preparation."

19) In the specification, page 57, line 9, "silver chloride" is corrected to "auric chloride."

20) "Previous layer" on page 59, line 10 of the specification is corrected to "blue feeling."

21) In page 60, line 14 of the specification, "become a layer" is corrected to "become a layer".

22) On page 64 of the specification, second line from the bottom, “30 to 340°C
" should be corrected to "30-34℃."

23) In Table 3 on page 67 of the specification, dIr(I
II) "mol/Agx mol" under the added amount in the Cu al column, and rmg/Ag under the added amount in the inorganic sulfur column.
x moles" respectively.

24) “Non-negative sulfur” in the fourth line from the bottom of page 70 of the specification is replaced with “
Corrected to ``Inorganic sulfur.''

(Attachment) The scope of claims is amended as follows.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in the silver halide emulsion layer contains an iridium compound and the chemical sensitization of the silver halide emulsion is stopped. A silver halide photographic material characterized in that it is produced in the presence of inorganic sulfur before the completion of the process.