JPH02230233A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain photographic characteristics of a high contrast negative gradation by using a stable developing soln., by incorporating a specific compd. into silver halide photographic emulsion layers. CONSTITUTION:The compd. expressed by formula I is incorporated into the photographic emulsion layers. In the formula I, both A1 and A2 are a hydrogen atom or one thereof is the hydrogen atom and the other is a sulfonyl group, etc.; Y denotes an aliphat. group substd. with formula II, arom. group. In the formula II, R1 denotes a hydrogen atom, aliphat. group, arom. group, etc.; L1 denotes -O-, -S-, etc.; Ra denotes a hydrogen atom, aliphat. group, etc. X denotes the group expressed by formula III. In the formula III, X1 and X2 respectively denote a hydrogen atom, alkyl group, etc. The photographic characteristics of the high contrast negative gradation are obtd. by the stable developing soln. in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is directed to a silver halide photographic material that provides extremely high contrast negative images, highly sensitive negative images, good halftone image quality, or for directly forming positive photographic images. The present invention relates to a silver halide photographic material containing a novel compound as a nucleating agent for silver halide. (Prior Art) Adding a hydrazine compound to a halogenated photographic emulsion or developer is disclosed in U.S. Pat.
No. 227,552 (using hydrazine as an auxiliary developer to obtain a direct positive color image), No. 3,386,83
No. 1 (contains β-monophenyl hydrazide of aliphatic carboxylic acid as a stabilizer for halogenated IK! material), No. 2,419,975, and the book written by Mees, The
Theory of Photographic Process (Th
e Theory of the Photography
hic Process) 3rd edition (I966) 28l
It is known for pages etc.

Among these, US Pat. No. 2,419,975 in particular discloses that a high-contrast negative image can be obtained by adding a hydrazine compound. The patent specification states that by adding a hydrazine compound to a silver chlorobromide emulsion and developing it with a developer with a high pH of 12.8, extremely high-contrast photographic characteristics with a gamma (r > 10) can be obtained. However, strong alkaline developers with a pH close to 13 are unstable and easily oxidized by air, and cannot withstand long-term storage or use.

Ultra-high contrast photographic characteristics with gamma exceeding 10 are negative images,
Either a positive image or a halftone image (
It is extremely useful for photographic reproduction of continuous Vt-tone images or reproduction of line drawings by dot image).For such purposes, conventionally, the content of chloride was set to exceed 50 mol%, preferably 75 mol%. Using a silver chlorobromide photographic emulsion, the effective concentration of sulfite ions is extremely low (usually 0.
1 mol/l! A method of developing with a hydroquinone developer (see below) was commonly used. However, due to the low concentration of sulfite ions in the developer in this method, the developer is extremely unstable and cannot be stored for more than 3 days. Furthermore, all of these methods require the use of a silver chlorobromide emulsion with a relatively high silver chloride content, and therefore it is not possible to obtain high clarity. Therefore, there has been a strong demand for using a highly sensitive emulsion and a stable developer to obtain ultra-high contrast photographic characteristics useful for reproducing halftone images and line drawings.

U.S. Patent Nos. 4,224,401 and 4.168,97
No. 7, No. 4,243.739, No. 4,272,614
No. 4,323,643 discloses a silver halide photographic emulsion that uses a stable developer and provides extremely high-contrast photographic characteristics. It has been found that it has some drawbacks.

In other words, these conventional hydrazines are known to generate nitrogen gas during the development process, and these gases collect in the film and form bubbles that damage the photographic image. The leakage into other photographic materials can have a negative impact on other photographic materials. It has been known to increase the molecular weight of nucleating agents to make them diffusion resistant as a means of preventing them from leaking into the developing solution, but conventional nucleating agents that are diffusion resistant have problems with stability over time. I've come to understand something.

That is, when a coating solution containing a nucleating agent is aged, precipitates are formed in the coating solution, deteriorating the filterability, and furthermore, changing the photographic performance.

In addition, these conventional hydrazines cause an undesirable phenomenon of black spots due to contagious development as well as a remarkable increase in contrast, which is a serious problem in the photolithography process. Black spots are, for example, black spots that occur in areas that should be undeveloped between halftone dots, and they increase over time, especially when the sensitive material is stored at high temperatures, or due to fatigue of the solution over time. , due to a decrease in sulfite ions, which are generally used as preservatives, and an increase in pH Ia, they occur frequently and significantly reduce the commercial value as a photolithographic printing material. Therefore, great efforts have been made to improve these black spots (for example, Japanese Patent Application Laid-open Nos. 62-275247 and 63-87).
(e.g., the use of a hydrazine compound having a nitrogen-containing heterocycle as described in No. 15, etc.) However, since improving black dots is often accompanied by a decrease in brightness and gamma (T), it is necessary to maintain high contrast sensitivity and It has been desired to develop a silver halide photographic material having photographic properties with fewer black spots.

In addition, when these conventional hydrazines are required in large quantities for sensitization and high contrast, or when particularly high sensitivity is required in terms of the performance of the sensitive material, other sensitization techniques (such as chemical sensitization) may be used. (e.g., increasing particle size, adding exacerbation-promoting compounds such as those described in U.S. Pat. No. 4,272,606 and U.S. Pat. No. 4,241,164) Increased strength and increased strength may occur over time. Therefore, there has been a desire for a compound that can reduce the generation of bubbles and leakage into the developer, has no problems with stability over time, and can provide extremely high-contrast photographic properties with the addition of a very small amount. ．． Also, U.S. Patent No. 4,385,
No. 108, No. 4,269,929, No. 4,243,7
No. 39 describes that extremely high contrast negative gradation photographic properties can be obtained by using hydrazines having substituents that are easily adsorbed to silver halide grains. Among the hydrazine compounds, those specifically mentioned in the above-mentioned known examples have the problem of causing desensitization over time during storage. Therefore, it was necessary to select a compound that would not cause such problems.

On the other hand, there are various direct positive photography methods, including a method in which silver halide grains that have been fogged in advance are exposed to light in the presence of a freezing agent, and then developed, and a method in which photosensitive nuclei are formed inside the raw silver halide grains. The most useful method is to develop the silver halide milk in the presence of a nucleating agent after exposing it to light. The present invention relates to the latter. Silver halide emulsions that mainly contain photonuclear nuclei inside the silver halide grains and in which latent images are mainly formed inside the grains are called internal latent image type silver halide emulsions. They can be distinguished from the silver halide grains that form the latent image.

A method of directly obtaining a positive image by surface developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent, and a photographic emulsion or light-sensitive material used in such a method are known.

In the above-mentioned method for obtaining a direct positive image, the nucleating agent may be added to the developer, but by adding it to the photographic emulsion layer or other appropriate layer of the luminescent material, it can be adsorbed onto the surface of the silver halide grains. Better inversion characteristics can be obtained when The nucleating agent used in the above method for obtaining a direct positive image is disclosed in U.S. Pat.
8.982, and the hydrazides and hydrazine compounds described in U.S. Pat. No. 3,227.552, U.S. Pat. No. 3,615.615
No. 3,719,494, No. 3,734,738
No. 4.094.683 and No. 4,115.12
No. 2, British Patent No. 1.283,835, JP-A-523
Heterocyclic quaternary salt compounds described in U.S. Pat. No. 426 and U.S. Pat. No. 52-69613, U.S. Pat.
．． No. 031,127, No. 4,139.387, No. 4,
245.037, 4255.511 and 4,
276,364, a thiourea-bonded acylphenylhydrazine compound described in British Patent No. 2,012,443, etc., and a heterocyclic thioamide described in U.S. Patent No. 4,080,207 as an adsorption group. compound, a phenylacylhydrazine compound having a heterocyclic group having a mercabuto group as an adsorption type described in British Patent No. 2,011,397B, and a nucleating compound described in U.S. Patent No. 3,718.470. Aggravating dye having a substituent in its molecular structure, JP-A-59-200,230, JP-A-59-212
, No. 828, No. 59-212, 829, [Research
Disclosure J (Research Dis
Hydrazine compounds are known as described in J. Closure, No. 23510 (November 1953). However, all of these compounds have insufficient activity as nucleating agents, and those with high activity have insufficient storage stability, or their activity fluctuates between the time they are added to milk and the time they are applied. It has been found that there are drawbacks such as deterioration of MW when added in an even larger amount.

In order to solve these shortcomings, Japanese Patent Application Laid-Open No. 179-179, 1986
No. 34, No. 61-170,733, Patent Application No. 60-20
No. 6.093, No. 60-19,739, No. 60=11
Adsorption type hydrazine derivatives described in No. 1,936, JP-A-62-130,361, JP-A-62-178.2
46, U.S. Pat. No. 4,686,167, etc., or JP-A-6
Hydrazine derivatives having a modifying group as described in No. 2-270948 and JP-A No. 63-29,751 have been proposed, but all of them improve the stability of the developing solution (in other words, they increase the stability of the developing agent). (to prevent deterioration)
The nucleating activity may be insufficient in response to requests to lower H, shorten development processing time, or reduce storage stability due to changes in developer composition (e.g. pH, sodium sulfite, etc.). There were also negative effects such as leakage into the developing processing solution. (Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a halogen-based compound that can obtain photographic characteristics of extremely sharp negative gradations with a gamma exceeding IO using a stable developer. An object of the present invention is to provide a silver photoluminescent material.

A second object of the present invention is to provide highly active hydrazines that can provide desired extremely sharp negative gradation photographic properties even in a low 1)H developer with a small amount added without adversely affecting photographic properties. An object of the present invention is to provide a negative-working silver halide photographic material containing the following. A third object of the present invention is to provide a negative-working silver halide photographic material that exhibits ultra-high contrast photographic properties and has fewer black spots. A fourth object of the present invention is to provide a direct contrast type silver halide photographic light-sensitive material containing highly active hydrazines that can provide excellent reversal characteristics even in a low pH developer. A fifth object of the present invention is to provide a silver halide photographic material whose photographic properties vary little due to changes in developer composition. A sixth object of the present invention is to provide a silver halide photographic material that is easy to synthesize, contains hydrazines, and has good storage stability over time. A seventh object of the present invention is to provide a silver halide photographic material whose emulsion has good stability over time and whose activity fluctuations are small during the production of the sensitive material. (Means for Solving the Problems) The objects of the present invention are to provide a silver halide photographic material having at least one silver halide photographic emulsion layer, in which the photographic emulsion layer or at least one other hydrophilic colloid is This was achieved by containing at least one compound represented by the following general formula (I) in the layer. General formula (I) A. A. (In the formula, A, , A and yo are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group or {C}-Re (in the formula, R
．． represents an alkyl group, an alkenyl group, a ryol group, an alkoxy group, or an aryloxy group, and n is 1 or 2.
represents. ). Y is the following general formula (a) or (
b) represents an aliphatic group or an aromatic group substituted with b).

represents the general formula (a) or a heterocyclic group, and X1 and X2 are mutually linked R,
-L, -C-N I R. General formula (b) R. -SCh NH (In general formula (a), R represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and L represents -0-, -S-
, or one N-; R. , R. R. ' represents a hydrogen atom, an aliphatic group or an aromatic group.

In the general formula (b), R2 represents an aliphatic group, an aromatic group or a heterocyclic group. ) X represents a group represented by the general formula (n) or (I[[). General formula (n) X1 N/Xz (wherein, X1 and X2 are each hydrogen atom, alkyl group,
An alkenyl group, aryl group, or amino group may be combined to form a ring. ) General formula (III) 0-X, (wherein, X is a hydrogen atom, an alkyl group, an alkenyl group,
Represents an aryl group or a heterocyclic group. )) General formula (I) will be explained in detail below. In the general formula (I), AI and AI are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms, and arylsulfonyl groups (preferably phenylsulfonyl groups or Hammett's substituent constants having a sum of −0
．． phenylsulfonyl group substituted so as to be 5 or more), {C}-. R. (RO is preferably a linear, branched, or cyclic alkyl group, alkenyl group, or aryl group having 30 or less carbon atoms (preferably a phenyl group, or a group whose sum of Hammett's substituent constants is -0.5 or more). ), alkoxy groups (e.g., ethoxy groups), aryloxy groups (preferably monocyclic groups such as phenyl groups), and these groups may have a substituent. Examples of the group include the following.These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups, azilamino groups, sulfonylamino groups, ureido groups,
Urethane group, ryoryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, aryloxycarbonyl group, acyl group, alkoxy Examples include a carbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a nitro group, an alkylthio group, an arylthio group, and the like. ), and the sulfonyl groups represented by A+ and At specifically represent those described in US Pat. No. 4,478,928. A hydrogen atom is most preferable as A+ and Ax.

In general formula (I), the aliphatic group represented by Y is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by Y is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group.

Y is preferably an aromatic group or a group represented by general formula (C). General formula (C) Yl 廿c = c? 7fc 2C de 11 Rc1 Rc
Rc3Rc (wherein, Y represents an aromatic group or a nitrogen-containing heterocyclic group, R% to Re4 each represent a hydrogen atom, a halogen atom, or an alkyl group, and Y1 and R, 1 to RC4 are may have a substituent. r and S are 0
It also represents 1. ) Y is more preferably an aromatic group, particularly an aryl group. Y may be substituted with a substituent. In addition to the substituents represented by general formulas (a) and (b), examples of substituents include the following, and these groups may be further substituted. For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group, These include alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups, nitro groups, alkylthio groups, and arylthio groups.

These groups may be linked to each other to form a ring if possible. Moreover, Y can contain one or more of general formula (a) or (b). Next, in the -S formula (a), the aliphatic group represented by R1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R1 is a monocyclic or bicyclic aryol group, such as a phenyl group or a naphthyl group.

R. The heterocycle is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, 0, or S atoms, and these may be monocyclic or may include other rings. It may form a fused ring with an aromatic or heterocycle. The petero ring is preferably a 5- or 6-membered aromatic heterocyclic group, such as a pyridine group, an imidazolyl group, a quinolinyl group, a penzimidazolyl group, a birimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, or a penzthiazolyl group. Preferably, those that include R1 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted. For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group, Alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulbonamide groups, nitro groups, alkylthio groups, arylthio groups, etc. These groups may be linked to each other to form a ring if possible. R in general formula (a). and R. ' (L is N-
) aliphatic R. The radicals are straight-chain, branched or cyclic alkyl, alkenyl or alkynyl groups.

R. and R. The aromatic group represented by l is a monocyclic or bicyclic aryl group, such as a phenyl group. R. and R. ' may be substituted with a substituent.

Examples of the substituent include those listed as the substituent for R in general formula (a).

Also, R1 and R-, R+ and R. l and Rll and R.
l may be linked to each other to form a ring if possible.

R1 and B. As I, a hydrogen atom is more preferable.

The aliphatic group represented by R2 in Formula 1a (b) is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group, preferably having 1 to 30 carbon atoms, particularly one having a carbon number of 1 to 20. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein.

For example, methyl group, (-butyl group, n-octyl group, t-
Examples include octhyl group, cyclohexyl group, hexenyl group, pyrrolidyl group, tetrahydrofuryl group, and n-dodecyl group.

The aromatic group is a monocyclic or bicyclic aryol group, such as a phenyl group or a naphthyl group. The heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, and may be a single ring or may be combined with another aromatic ring or a petro ring. A condensed metal ring may be formed. Preferred petero rings are 5- to 6-membered aromatic heterocycles, such as pyridine rings, imidazolyl groups, quinolinyl groups, penzimidazolyl groups, pyrimidinyl groups, pyrazolyl groups,
Examples include isoquinolinyl group, penzthiazolyl group, and thiazolyl group. R8 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl basis,
These include ryoloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, and carboxyl group. In the general formula (n), X,
-propyl group, n-octyl group, allyl group, benzyl group, iso-propyl group, cyclohexyl group, etc.), alkenyl group (e.g. propenyl group, etc.), aryl group (e.g. phenyl group, etc.), amino group (e.g. amino group, A methylamino group, etc.) or a heterocyclic group (eg, a pyridyl group, etc.) are preferred. Furthermore, XI and X8 may be linked to form a ring, in which one or more heteroatoms (for example, oxygen atoms,
It may be cyclized to form a saturated or unsaturated heterocycle containing a sulfur atom, a nitrogen atom, etc., such as a pyrrolidyl group, a biperidyl group, a morpholino group, and the like.

Further, X, , Xt may have a substituent, and as the W substituent, for example, the substituents listed for Y1 can be applied.

In the general formula (I[+), probyl group, cyclohexyl group, etc.)
Alkenyl groups (e.g. propenyl groups, etc.), aryl groups (
For example, phenyl group, naphthyl group, etc.) or heterocyclic group (eg, biridyl group, etc.) are preferred. Further, X may have a substituent, and examples of the substituent include those listed for Y. Further, X or Y preferably contains a ballast group which is commonly used in immobile photographic additives such as couplers.

The ballast group is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the general formula (r) from diffusing into other layers or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, It consists of a combination of one or more of ether groups, thioether groups, amide groups, ureido groups, urethane groups, sulfonamide groups, etc. More preferred as the ballast group is a ballast group having a substituted benzene ring, and particularly preferred is a ballast group having a benzene ring substituted with a branched alkyl group.

More preferably one R, -Ll -C-N group and R. The RtsoNH group is substituted at the O or P position relative to the hydrazino group. Specific examples of compounds represented by the general formula (+) are shown below.
However, the present invention is not limited to the following compounds. ■-1. I 2. I 4. ■ 9. ■ 11. CHs C 0 CF s ■-5. ■-6. ■-7. I-8. 1-13. 1-14. 15. "C.H..r-21.CF蕩1-19.[-24. The compounds of the present invention can be synthesized by various methods.

When X in general formula (I) is represented by general formula (III), for example, the corresponding hydrazine compound (Y-NHN
A compound as shown in the general formula (■) with dioxane,
The reaction is carried out in a suitable solvent such as benzene or DMF in the presence of a base, or it can be synthesized by simply heating.

General formula (IV) (In the formula, X3 is defined in the general formula (III), and Z represents a halogen atom, a phenoxy group, etc.) Furthermore, as another method, a method using a transesterification reaction, etc. is used. You can also. When X is represented by the general formula (■) in the general formula (I), -C can be synthesized by reacting the corresponding alkoxalylhydrazine derivative with an amino compound as shown below. O O (In the formula, YXAl, A2, X1, Typical methods for synthesizing compounds will be explained using synthetic examples. Synthesis Example 1 Synthesis of Compound 1-15 30.7 g of 4-nitrophenylhydrazine and 150 mj of diethyl oxalate! 1 on a water bath at about 80°C.
The mixture was heated and stirred for hours. After cooling, 50+ liters of isoprobyl ether was added to the reaction solution to precipitate crystals.

The obtained crude crystals were recrystallized from a mixture of ethyl acetate and benzene to obtain 39.8 g of 1-ethoxalyl-2-(4-nitophenyl)hydrazine.

Next, 25.0 g of this nitro compound was mixed with 30 ml of ethanol.
0ml, dioxane 200mj! After dissolving in a mixed solvent, 20 g of 10% palladium on carbon was added and catalytic reduction was carried out in a conventional manner to obtain 19.7 g of 1-ethoxalyl-2-(4-aminophenyl)hydrazine. 1.7 g of this amine compound was dissolved in 10 rrl of N,N-dimethylformamide, and then 2 ml of triethylamine
．． 1 ml was added and cooled to -5°C. Add to this 4- (2
．． 5.8 g of 4-di-tert-pentylphenoxy)-1-butylsulfonyl chloride was dissolved in 10 ml of acetonitrile, and this solution was added dropwise. During this time, the liquid temperature is 0.
The mixture was cooled and stirred so as not to exceed ℃. After stirring for 1 hour at 0° C., the mixture was poured into ice water and extracted with ethyl acetate.

The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was refluxed. The concentrate was separated and purified by silica gel column chromatography to obtain compound ■-1.
1.9g of 5 was obtained.

When incorporating the compound of the present invention into a photographic emulsion layer or a hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (alkali hydroxide or tertiary amine is added as necessary). (You may add it to make salt and dissolve it)
, may be added to a hydrophilic colloid solution (for example, a silver halide emulsion, an aqueous gelatin solution, etc.) (at this time, the pH may be adjusted by adding an acid or alkali as necessary).

The compounds of the present invention may be used alone or in combination of two or more. The amount of the compound of the present invention added is preferably /X/0-5 to jX/0'' mole per 7 moles of silver halide, and more preferably from !xIO-5 mole to /xIO-2 mole, when combined An appropriate value can be selected depending on the properties of the silver halide emulsion.

The compound represented by the general formula (I) of the present invention can form a negative image with high contrast when used in combination with a negative emulsion.

On the other hand, it can also be used in combination with an internal latent image type silver halide emulsion. The compound represented by the general formula (I) of the present invention is preferably used in combination with a negative emulsion to form a negative image with high contrast.

When used to form a high-contrast negative image, the average grain size of the silver halide used is preferably fine (for example, 0.7μ or less), particularly preferably 0.jμ or less. There is basically no limit to the particle size distribution, but
Monodisperse is preferable, and monodisperse herein means that the particle group is composed of particles whose weight or number of particles is at least within 10 liters of the average particle size. .

Silver halide grains in photographic emulsions are cubic, octahedral, diamond/
．． regular like dihedron, l≠hedron
), or may have irregular crystals such as spherical or tabular crystals, or a composite of these crystal shapes.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

The silver halide emulsion used in the present invention contains cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. in the process of forming silver halide grains or physically ripening them. Good too.

The silver halide used in the present invention is IO-8 per mole of silver.
~/0=silver haloiodide prepared in the presence of mol of iridium salt or its complex salt, and in which the silver iodide content on the grain surface is larger than the average silver iodide content of the grains When an emulsion containing such silver haloiodide is used, photographic properties with higher sensitivity and higher gamma can be obtained.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and rhodium. A specific example is U.S. Patent No. 2, ggr, ot
No. o, British Patent No. tII, 0/t, etc. As sulfur sensitizers, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates,
Thioureas, thiazoles, rhodanines, etc. can be used.

In the above, it is preferable to use iridium salt or rhodium salt before the completion of physical ripening in the production process of the silver halide emulsion, especially during grain formation.b0In the present invention, the silver halide emulsion layer is No., special request 1986
It is preferable to include two types of monodisperse emulsions with different average grain sizes as disclosed in No. 2.320rt from the viewpoint of increasing the maximum density (Dmax), and the small-sized monodisperse grains are chemically sensitized. This is preferred, and the most preferred chemical sensitization method is sulfur sensitization. The large size monodisperse emulsion does not need to be chemically sensitized, but it may be chemically sensitized. Generally, dog-sized monodisperse particles are not subjected to chemical sensitization because they tend to produce black spots, but when chemical sensitization is carried out, it is particularly preferable to apply the chemical sensitization shallowly to the extent that black spots do not occur. Here, "shallow application" means that chemical sensitization is performed by shortening the time, lowering the temperature, or suppressing the amount of chemical sensitizer added compared to chemical sensitization of small-sized particles. There is no particular limit to the sensitivity difference between large-sized monodispersed emulsions and small-sized monodispersed emulsions, but Δ7! 0 as ogE. /~
/,0, preferably O. 2-0. 7, it is preferable that the large size monodisperse emulsion is higher.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative, and adding sulfite ions to 0./J-mol/! pH including above/0. ! ~/． This is obtained when processing using the developer of No. 2.3.

The average grain size of the small-sized monodisperse grains is not more than a factor of 0, preferably not more than a factor of 10, of the average size of dog-sized monodispersed silver halide grains. The average grain size of the silver halide emulsion grains is preferably o. o1μ～/,0μ
Preferably 0. /μ～o. Preferably, the average particle size of dog-sized and small-sized monodisperse particles is within this range of 3-μ.

In the present invention, when two or more emulsions of different sizes are used, the coating silver amount of the small-sized monodisperse emulsion is preferably UO to Tao wt4, more preferably I'm at to-rowts.

In the present invention, monodispersed emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into separate layers.

When introduced in separate layers, it is preferred that the large emulsion be in the upper layer and the small emulsion in the lower layer.

The total amount of coated silver is /t/77"~rr
/m2 is preferred.

The photosensitive material used in the present invention includes Japanese Patent Application Publication No. Sho! ! one! Ko06θ No. 4t! The sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described on pages 1 to 3 can be added. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that does not have a photosensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization can be found in Research Disclosure/Volume 76/7tu3 (Published in December 2015), Page λ3, J. It is described in the section.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as penzothiazolium salts, nitroindazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, amino} l) Azoles, penzothiazoles, nitropenzotriazoles, etc.; mercaptozelimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially hiro-hydroxy substituted (l, 3, Ja
, 7) tetrazaindenes), pantaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonate acid, benzenesulfonate amide, etc. can be added. Among these, preferred are penzotriazoles (eg !-methyl-benzotriazole) and nitroindazoles (eg !-nitroindazole). Further, these compounds may be included in the treatment liquid.

As a development accelerator or a nucleation infection development accelerator suitable for use in the present invention, JP-A-Sho! 3-77≦lt issue, j41-37732 issue, same! 3-l. 37/33 issue, 60-/1703 Hiro O issue, same Otsu O1/μ2! In addition to the compounds disclosed in No. 1 and the like, various compounds containing N or S atoms are effective.

The optimum addition amount of these accelerators differs depending on the type of compound, but OXIO ~ 0. jf/fi2, preferably j. OXI0 3 ~0. It is desirable to use it within the range of /f/m2.

The photographic material of the present invention may contain a desensitizer in the photographic emulsion layer or other hydrophilic colloid layer.

The organic desensitizer used in the present invention is defined by its polarographic half-wave potential, ie, the redox potential K determined by polarography, and the sum of the polar anodic potential and the cathodic potential is positive.

A polarographic method for measuring redox potential is described, for example, in US Pat. No. J,10/,307.

The organic desensitizer preferably contains at least one water-soluble group, and specific examples include a sulfonic acid group, a carboxylic acid group, and a sulfonic acid group. , triethylamine, pi,
4-lysine, morpholine, etc.) or alkali metals (eg, sodium, potassium, etc.).

As an organic desensitizer, the patent application No. J of Sho 1/-Kor6 Tata R! General formula (Illll[)~ described on pages ~ 72]
Those represented by (V) are preferably used.

The organic desensitizer in the present invention is 1c in the silver halide emulsion layer.
/． OX/0' ~/+OX/0
'Mo/l//m2, especially /. O×/0-7~/, O×
Preferably, IO-5 mol/2yt2 is present.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers that have a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and dyes that are resistant to safelight light when handled as bright-room sensitive materials. In order to increase safety, dyes with substantial light absorption mainly in the region of JrOnm-&00nm are used.

These dyes are added to the emulsion layer depending on the purpose, or they are added together with a mordant to the upper part of the silver halide emulsion layer, that is, to the non-light-sensitive hydrophilic colloid layer which is far from the silver halide emulsion layer with respect to the support. It is preferable to use it by fixing it.

It depends on the molar absorption coefficient of the UV absorber, but usually IO
-2t/m2 to /ta/m2 range? added. Preferably jO1n9 to 100 /fi2.

The above ultraviolet absorber can be used in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, propanol, etc.)].
, acetone, methyl cellosol, etc., or a mixed solvent thereof] and added to the coating solution.

As the ultraviolet absorber, for example, a penzotriazole compound substituted with an aryl group, a ≠-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a penzoxazole compound, and an ultraviolet absorbing polymer can be used.
1 Specific examples of ultraviolet absorbers are given in US Patent J,! J.J.
, 7 free issue, 3.37≠, 7P≠ issue, 3.3!2,
tlrl issue, JP-A-4'A-. No. 27rg, US Patent J
, 706, 103, same j, 707, . No. 373, same g, Og 3.22, same j, 700, Hiro! No. 3,
≠Tata, No. 762, West German Patent Application Publication/, 3≠7, Ir
It is described in tJ issue etc.

Filter dyes include oxonol dyes, hemioquinol dyes, styryl dyes, merocyanine dyes, citanine dyes and azo dyes. In order to reduce residual color after development, dyes that are water-soluble or decolorized by alkali or sulfite ions are preferred.

Specifically, for example, U.S. Pat. Virazolone oquinol dye as described in U.S. Pat. diarylazo dyes described in U.S. Patent No. J,4123,207, U.S. Pat. merocyanine dyes described in U.S. Pat. No. 3,111rt, 197, U.S. Pat.
1u, merocyanine dyes and oxonol dyes described in U.S. Patent No. J,7/I,u72, U.S. Pat.
The enaminohemiokinol dyes described in No. J/ and the British Patent No. srt. t, tota issue, same no. 1, /77, a
xy issue, Tokukai Sho'AI-4! /No.30, Dokoro Tatata 6
No. 20, Guter/lμhiro 2θ No. 2, U.S. Patent No. 2,13
3.1172, No. 3, /III, /1r7, No. 3, /77,071, No. 3,2 Ko7, /j7, No. 3, J'llO,! ．． 1'7, same No. 3. Yo7r, 7
The dyes described in No. 0g, No. 3, TJR3, No. Oj are used.

The dye can be used in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, pro/de-nol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof].
It is added to the non-photosensitive hydrophilic colloid layer coating solution of the present invention after being dissolved in .

The specific amount of dye used is generally 10 27 m2 ~
/ 9 7 m2, especially IO-32/m2~O,j
? /m2 can be found.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts, aldehydes, C formaldehyde,
glutaraldehyde, etc.), N-methylol compounds (
dimethylol urea, etc.), activated vinyl compounds (/, J,
j-triacryloyl-hexahydro-s-1 riazine, l,3-vinylsulfonyl-2-pro, R nornato), active halogen compound (J. Koichi dichloro-t-
Hydroxy s-! J azinato), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization. In particular, the surfactant preferably used in the present invention is Tokko Sho! These are polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent No. 1-91112. When used as an antistatic agent,
Fluorine-containing surfactants (see U.S. Patent No. μ.
λ0/,! rt issue, JP-A-Sho+o-tort. T-ta issue, same! Particularly preferred is the Tar7da Yoyogu.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. be able to.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of the compound having an acid group include polymers or copolymers having organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid as repeating units. Regarding these compounds, Japanese Patent Application No. 10-≦A/72, same to-
T! #73, tO-/t3&'jtt, and 6
0-/ta! T! ! You can refer to the description in the specification. Among these compounds, particularly preferred is ascorbic acid as a low molecular compound, and as a high molecular compound, an acid such as acrylic acid %/ff-(!: having λ or more unsaturated groups such as divinylbenzene) is particularly preferable. It is a water-dispersible latex of a copolymer made of crosslinkable monomers.

In order to obtain ultra-high contrast and high-sensitivity photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or US Pat. It is not necessary to use a highly alkaline developer close to the pH/J described in No. K, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0. /j mol/l or more, pH
/0. ! ~lco. 3, especially pHi/. 0~/j. A sufficiently ultra-high contrast negative image can be obtained using a developer of 0.

The developing agent used in the developer used in the present invention is not particularly limited, but it preferably contains dihydroxybenzenes, and cyhydroxybenzenes and l-phenyl. A combination of 3-virazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used. The developing agent is usually 0.0
jmol/l~0. Preferably, it is used in an amount of t mol/l. Also, dihydroxy《benzenes and l-7enyl-3
- When using a combination with virazolidones or p-aminophenols, the former is added at a concentration of 0.0jmol/l to 0.0jmol/l. !
mol/l, the latter as o, ot mol/! It is preferable to use the following amounts.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfite is O. Hiromol/E or more, especially O. ! It is preferably mol/E or more.

The developing solution of the present invention contains JP-A-Sho! as a silver stain preventive agent. t-λ
≠, the compound described in No. 3μ7 can be used. As a solubilizing agent added to the developer,
Compounds described in No. 74t3 can be used. Furthermore, as a pH buffering agent used in the developer,
Compounds described in 4tj No. 3 or patent application Sho t/-28'
, 701 can be used.

The compound represented by the general formula (I) can be used in combination with a negative emulsion in a high-contrast sensitive material as described above, and can also be combined with an internal latent type silver halide emulsion. state In this case, general formula (I)
The compound represented by is preferably contained in the internal latent image type silver halide emulsion layer, but may be contained in the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer.

Such a layer may have any function, such as a colorant layer, an intermediate layer, a filter layer, a protective layer, an anti-halation layer, etc., as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. It may also be a layer with layers.

The content of the compound represented by the general formula (I) in the layer is such that when the internal latent image type emulsion is developed with a surface developer, a sufficient maximum density (for example, silver concentration of /.0 or more) is obtained. It is desirable that In practice, the appropriate content can vary over a wide range as it depends on the properties of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but Approximately O. per mole of silver. The range from oozmg to zoomg is practically useful;
Preferred is from about 0.0/HI9 to about/O per mole of silver.
It is o1ng. When it is contained in a hydrophilic colloid layer adjacent to an emulsion layer, it may be contained in the same amount as above for the amount of silver contained in the same area of the internal latent image type emulsion layer. The definition of the internal latent image type silver halide emulsion is described in the upper column of page io of Japanese Patent Application Laid-Open No. 70733 and British Patent No. There is.

Preferred internal latent image emulsions that can be used in the present invention include:
Patent Application No. 67-2!3716 Specification No. λ! Page/line g~
Preferred silver halide grains are described on page 37, line C, of the same specification, page 37, line 3 to page 3, line //.

In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyani/dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopowocyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. These sensitizing dyes include, for example, Japanese Patent Application Publication No. 2003-100000, Tar No. 4, Tar No. These include the cyanine dyes and merocyanine dyes described in No. 9-170, tJt and JJJl, No. 73ta.

The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, it can be developed with a developer containing a color image-forming coupler.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 776μ3 (/971 1 month) ■-D and 776 μ3 (/971 month) /I Month).

Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler.

In the present invention, it is preferable to use a two-equivalent yellow coupler, and typical examples include an oxygen atom elimination type yellow coupler or a nitrogen atom elimination type yellow coupler. α-piparoylacetanilide couplers have excellent color fastness, especially light fastness, while α-penzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indazolone or cyanoacetyl coupler! - Virazoloazole couplers such as pyrazolone and virazolotriazoles are mentioned. ! The -pyrazolo/type coupler is preferably a coupler in which the 31st position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and coloring density of the coloring dye.

As the leaving group for the two-equivalent yo-villamelon coupler, the nitrogen atom leaving group described in U.S. Pat. The arylthio group described in /, rta No. 7 is particularly preferred. Also European Patent No. 7
The pyrazolone coupler having a pallast group described in No. 3,636 can provide high color density.

As a birazoloazole coupler, U.S. Patent No. 3,
372. The virazolobenzimidazoles described in Tata, preferably US Pat. No. 3,72! , pyrazolo[z,t-C)C/,J,μ]triazoles described in OA7, Research Disclosure 2II220 (/
Ta? Virazolotetrazoles and Research Disclosure Co4tλ30” (/9!
≠ year t month). Imidazo C described in European Patent No. 7IP, 74t/ from the viewpoint of low yellow side absorption of coloring dye and light fastness.
/, 2-b'l pyrazoles are preferred, pyrazolo[l,r-b,3
[i,2,ge]triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, preferably the naphthol-based couplers described in U.S. Pat. US Patent No. I
I,0! ．． 2, Co/No. 2, same No. μ, l Hiro J, Jfj No.
The same No. 1 Hiro, 221r, 233 and the same No. 1 Hiro, Kota t, 2
A representative example is the oxygen atom dissociating type two-equivalent naphthol coupler described in No. 00. Further, specific examples of phenolic couplers include U.S. Patent Nos. Co, 36, Takota, U.S. Patent Nos. Ta r, r. : It is written in the zt issue etc. Cyan coupler is robust against humidity and temperature.
A typical example of a phenolic cyan coupler, which is preferably used in the present invention and has an alkyl group equal to or higher than an ethyl group at the meta-position of the phenol nucleus, is described in US Pat. No. 3,772,002. These include -diacylamino-substituted phenolic couplers and phenolic couplers having a phenylureido group at the co-position and an acrulamino group at the first position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and uncoupler, it is preferable to use a colored coupler in combination with a color sensitive material for photographing.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Pat. A specific example of a magenta coupler is given in No. 70, and also in European Patent No. t,! No. 70 and West German Application No. 3,23≠,! No. 33 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 44,010,2ll. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,/73 and U.S. Pat.
, No. 212.

The various couplers used in the present invention can be used in combination of two or more types in the same photosensitive layer, or in two or more different layers of the same compound, in order to satisfy the characteristics required for the photosensitive material. It is also possible to introduce more than one.

Typical usage amounts for color couplers range from 0.00/mol to 1 mol/mol of photosensitive silver halide, preferably from 0.0/mol to 0.0/mol for yellow couplers.
! Mol, magenta coupler has a noise of 0.003 (I)
．． J moles, and 0.00 to 0 for cyan couplers.
．． It is 3 moles.

In the present invention, developing agents such as hydroxybenzenes (e.g. hydroquinones), aminophenols, 3-virazolidones, etc. may be contained in the emulsion or in the light-sensitive material. The emulsion is
It can also be used to obtain transferred images of dye image-providing compounds (colorants) for color diffusion transfer processes that release diffusible dyes in response to development of silver halide. There are many known colorants for use in color diffusion transfer methods.
Among these, the use of a type of coloring material (hereinafter abbreviated as DRR compound) that is initially non-diffusible but cleaves through a redox reaction with the oxidation product of the developing agent (or electron transfer agent) to release a diffusible dye. is preferred, and among those, DRR compounds having an N-monosubstituted sulfamoyl group are preferred. Particularly preferred for use in combination with the nucleating agent of the present invention are US Pat.
osj, ext. II, Or. ! , J/λ and I
DRR compounds having an 0-hydroxyarylsul7-amoyl group as described in No. I, 336, jj, etc., and redox cores as described in JP-A No. Sho J-3-/u9,32r. It is a DRR compound having When used in combination with such a DRR compound, the temperature dependence particularly during treatment is significantly reduced.

Specific examples of DRR compounds include those listed in the above patent specifications, as well as maze/ta dye image-forming materials such as/
-Hydroxy-2-tetramethylenesulfamoyl μ
1 [3'-Methyl-Hiro'(2"-Hydroxy-μ"-Methyl-!"-Hexadecyloxyphenylsulfamoyl)-Phenylazo]-naphthalene, yellow dye image-forming substance toshi/-Phenyl-3-Cyanop (
，! ///Hiroichi tert-bentylphenoxyacetami/)-7enylsulfamoyl]phenylaso)-j-pyrazolone and the like.

Details of color couplers that can be preferably used in the present invention are described in the same specification, page 33, line lr to page 4LO, last line.

After imagewise exposure using the light-sensitive material of the present invention, after or during fogging treatment with light or a nucleating agent, pH//. It is preferable to form a positive color image directly by carrying out color development, bleaching and fixing treatment with a surface developer of J or less. More preferably, the pH of this developer is in the range of /l, 0-/0.0.

The fogging process in the present invention is the so-called "light fogging method".
Either of the method of applying a second exposure to the entire surface of the photosensitive layer called "chemical heating method" and the method of developing in the presence of a nucleating agent called "chemical oxidation method" may be used. Development may be carried out in the presence of a nucleating agent and fogging light. Further, a photosensitive material containing a nucleating agent may be fog-exposed.

Regarding the light turnip method, the above-mentioned patent application Sho J/-λJrJ7
The nucleating agent that can be used in the present invention is described in the same specification from page 6, line 6 to page 67, line λ of the specification. , especially the general formula (N
-/) and [N-2] are preferably used. Specific examples of these are given in the same specification No.! 6~! ! (N-I-/) to [N'-I-/O:l described on page t3-6t of the same specification and [:N-II-/] to C described on pages t3 to 6t of the same specification
N-II-72] is preferred.

Regarding the nucleation accelerator that can be used in the present invention, see Section t of the same specification.
This is described in page r, line 11 to page 7l, line 3. Particularly, as a specific example of this, (A-/1 to
The use of (A-/j) is preferred.

Regarding the color developer used in the development of the photosensitive material of the present invention, it is described in the same specification from page 7≠line to page 7.2, line 2. As a specific example of the color developing agent, p-phenylenediamine compounds are preferable (typical examples thereof include 3-methyl-guamino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, -Methyl-≠-amino-N-ethyl-N-(β-hydroxyethyl)aniline, 3-methyl-l-amino-N-ethyl-N-methoxyethylanilJ
and their salts such as sulfates and hydrochlorides.

In order to directly form a positive color image using the light-sensitive material of the present invention by a color diffusion transfer method, a black-and-white developer such as a phenidone derivative can also be used in addition to the above-mentioned color developer.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process in a single bath bleach-fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method of bleaching followed by bleach-fixing may be used, or a method of performing fixing followed by bleach-fixing may be used. An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention. Additives used in the bleaching solution or bleach-fixing solution of the present invention are described in Japanese Patent Application No. Shoj/-32≠62. Pages 22-3
A variety of compounds described on page 0 can be used. After the desilvering step (bleach-fixing or fixing), treatments such as water washing and/or stabilization are performed. It is preferable to use softened water as the washing water or stabilizing liquid. Examples of the water softening treatment include a method using an ion exchange resin or a reverse osmosis device as described in Japanese Patent Application No. Sho t/-/3/632. Specific methods for these are as follows:
-/3/63λ is preferably carried out.

Furthermore, as additives used in the water washing and stabilization steps, various compounds described in detail on pages 30 to 3t of Japanese Patent Application No. 3'21It2 can be used.

The smaller the amount of replenisher in each treatment type, the better. The amount of replenisher is O. Preferably 7 to θ times, more preferably 3
~30 times.

The present invention will be further explained with reference to Examples below. Example-1 4XIO per mole of silver in an aqueous gelatin solution kept at 50°C
−'Mole of iridium hexachloride (I [
A cubic monodisperse emulsion with an average grain size of 0.25 μm and an average silver iodide content of 1 mol % was prepared by maintaining the average grain size at 7.8.

No chemical augmentation was performed. 5,5'-dichloro-9-ethyl-3.3' was added to these silver iodobromide emulsions as a sensitizing dye.
Sodium salt of bis(3-sulfobrovir)oxacarpocyanine, 4-hydroxy-6-methyl-1.3.3a,7-tetrazaindene as stabilizer, dispersion of polyethyl acrylate, polyethylene glycol, 1.
3-vinylsulfonyl-2-probanol and Table-1
The compound of the present invention shown in 1 was added and coated on polyethylene terephthalate haze at a silver content of 3.4 g/rd. Gelatin is 1.8g/n? Met.

Gelatin 1. 5g/rrr
, polymethyl methacrylate particles (average particle size 2.5μ)
A layer containing 0.3 g/nf of the following surfactants was applied.

Surfactant? H C O○C, ■{l, SO. Na C. F. ,So■ N C H z C O O
KC3H? 2.5■/, { As a comparative example, instead of the compound of the present invention, compounds A, B,
Samples using C, D and E were prepared. Examples of those compounds are shown in Table-1.

These samples were exposed to 3200°K tungsten light through an optical wedge, developed with the following developer at 34°C for 30 seconds, fixed, washed with water, and dried.

The photographic properties obtained are shown in Table 1.

[Developer - ■]

Hydroquinone SO. o
gN-methyl-p-aminophenol 0.3g4-
Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone Sodium hydroxide 18.0g Boric acid 5 4. 0 g Potassium disulfite 110.0 g Disodium ethylenediaminetetraacetate
1. Og potassium bromide
lO. O g5-methylbenzotriazole 0.4g2-mercaptobenzimidazole 5-sulfonic acid 0.3g3-(5-
merkabutotetrazole) Sodium benzenesulfonate 0.28N-n-
Butyldiethanolamine 15.0g Sodium toluenesulfonate 8.0g Add water to 11
Adjust pH to 11.6 (add potassium hydroxide) pH 11
．． 6 Table 1 *1 Sensitivity: Based on the anger level (log E) of Comparative Example-1, expressed as the difference from it. Therefore, for example, +1.0 means 1.0 in log E compared to blank. It represents 0 times higher motivation, that is, 10 times higher motivation.

*2 gradation (γ): This is the slope of the straight line connecting the point of density 0.3 and the point of density 3.0 on the characteristic curve. The larger the value, the higher the contrast.

*3 dot quality: w4 dot quality is visually evaluated on a 5-level scale, with "5" representing the best quality and "1" representing the worst quality.

As a halftone original for plate making, a halftone product Quality "5" and "4" are practical, "3" is poor, but barely practical Yes, "2" and "1" are not practical. It is a halftone dot of excellent quality.

*4 Black spots: Black spots are evaluated on a five-point scale by microscopic observation, with "5" representing the best quality and "l" representing the worst quality. ``5'' or ``4'' is practical, ``3'' is poor but barely practical, and ``2'' or ``1'' is impractical. Comparative Compound A Comparative Compound C The above results show that when the compounds of the present invention are used, significantly high sensitivity and contrast are obtained, and both halftone quality and black spots are improved. Example-2 4X per mole of silver in an aqueous gelatin solution kept at 50'C
In the presence of 10-' moles of iridium hexachloride (I[[)potassium and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added over a period of 60 minutes, while maintaining PAg at 7.8. , average particle size 0
．． Cubic monodisperse papillae were prepared with a diameter of 28μ and an average silver iodide content of 0.3 mol%. This emulsion was desalted by the flocculation method, and then 40 g of inert gelatin per mole of silver was added and kept at 50'C as a sensitizing dye of 5.5'-dichloro-9-ethyl-3. 3'-bis(
3-sulfoprovir) oxacarbocyanine and 1i
The mixture was added to a 10-3 mol Kl solution per 11 mol, and the temperature was lowered after 15 minutes. This emulsion was redissolved at 40°C.
0.02 mol/II mol of methylhydroquinone and 1.0 mol/II mol of hydrazine derivatives of the present invention or comparative examples shown in Table 2. Add OX10-' mol/Ag mol, and then add 5
-Methylbenzotriazole, 4-hydroxy-1.3
, 3a. 7-tetrazaindene, the following development accelerator (a)
, (mouth), and a dispersion of polyethyl acrylate at 0.
4g/r/, and 13.4g of silver on a polyethylene terephthalate support (I50μ) with a waterproof undercoat N (0.5μ) made of vinylidene chloride copolymer, with the addition of the following compound (c) as a gelatin hardener. /n? It was applied so that

(a) CzHs (mouth) (c) 0H? Hz =CHSOzCHxCtlCHzSO■C
H=CH. On top of this, 1.5 g of gelatin was added as a protective layer.
m, polymethyl methacrylate particles (average particle size 2.5μ
)0.3g/n? , a layer containing the following surfactant was applied: Surfactant [Developer-1] C H C O O Ch H +sSOl+Na C s F I? S O z N C H x
C O O K 2. 5 111g/m
(l H, [1] Evaluation of high contrast performance These samples were exposed to 3200'K tungsten light through an optical wedge, developed with the following developer at 34°C for 30 seconds, fixed, washed with water, and dried.

The obtained photographic sensitivity and gradation are shown in Table 2. When the nucleating agent of the present invention was used, high sensitivity and high contrast were obtained. [2] Evaluation of photographic performance with exhausted developer FC660F automatic processor for plate making (Fuji Photo Film [
1! %l) was filled with the above-mentioned developer -2, and developed at 34° C. for 30 seconds under the following three conditions, followed by fixing, washing with water, and drying.

(A) Immediately after the temperature of the developer filled in the automatic processor reaches 34°C, development processing is performed. (Development with fresh solution). CB) Perform development processing using the solution left in the automatic processor filled with developer solution for 4 days. (Development with air fatigue solution)
.

(C) After filling the automatic developing machine with developer, use Fuji Film Gl? ANDEX GA-100 film 50.8
cax61. Exposure is carried out so that 50% of the area is developed in a size of Ocm, 200 sheets are processed in one day, and development processing is carried out using the same solution that is repeated for 5 days. Developing solution per 1 sheet processed -■
Replenish 100cc of. (Development using large-volume processing fatigue solution)
.

The photographic properties obtained are shown in Table 2. In terms of processing running stability, it is desirable that the photographic properties obtained with CB) and (C) are no different from those of (A).

As can be seen from the results in Table 2, when the nucleating agent of the present invention is used, there is little variation in photographic sensitivity even when the developer is exhausted.

Sensitivity: Based on blank sensitivity (IogE),
Show the difference from that. Therefore, for example, -1.0 means 1.0 lower in log E compared to blank, that is, 10 times lower.

** Gradation (G): density 0.3 point and 3.0 on the characteristic curve
is the slope of the straight line connecting the points.

The higher the value, the stronger the contrast. represent

Ichimoto△Sto^: Sensitivity when developed with air fatigue solution (S
．． ) and the sensitivity (SA) when developed with a fresh solution * Umbrella rate book △SC-A: Difference between the sensitivity (SC) when developed with a large-volume processing fatigue solution and the sensitivity (SA) when developed with a fresh solution ) Difference Example-3 5.0% per mole of silver was added to an aqueous gelatin solution kept at 50°C. OX
] CI' moles of (NHJ3R h Cl&, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in the presence of Cl&, and gelatin was added after removing the soluble salts by methods well known in the art without chemical ripening. 2-methyl-4-hydroxy-1.3.3a,7-tetraazaindene was added as a stabilizing agent to the emulsion.The emulsion was a monodisperse cubic emulsion with an average grain size of 0.15 .mu.m.

To this emulsion, a hydrazine compound was added as shown in Table 3, polyethyl acrylate latex was added in a solid content of 3 Qwt% based on gelatin, and a hardening agent and 1,3-vinylsulfonyl-2-propanol were added. , and coated on a polyester support at an Agl of 3.8 g/l.

Gelatin was 1.8 g/m. Gelatin 1.5g/n as a protective store on top of this? And as a matting agent,
Polymethyl methacrylate particles (average particle size 2.5μ) 0
．． 3 g/d, and a protective layer containing the following surfactant, stabilizer, and ultraviolet absorbing dye as coating aids was coated and dried. Surfactant C I{ C O O Cb H +sSO1Na C. F+tSOz NCH! COOK 2.5
(1)/I1 {CsH stabilizer thioctic acid 2.1 (2)/d Ultraviolet absorbing dye The photographic properties obtained are shown in Table 3.

From the results in Table 3, it can be seen that higher contrast is obtained with the sample of the present invention than with the sample of the comparative example.

In addition, as in Example 2, the photographic performance was tested using a fatigued developer, and as shown in Table 3, the samples of the present invention had the following properties:
Fluctuations were small, showing favorable results.

This sample is Dainippon Screen Seimei-shitsu printer p
-601 through an optical wedge, developed at 38° C. for 20 seconds, fixed, washed with water, and dried.

Claims (1)

[Scope of Claims] It is characterized by having at least one silver halide photographic emulsion layer, and containing a compound represented by the following general formula (I) in the photographic emulsion layer or at least one other hydrophilic colloid layer. A silver halide photographic light-sensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.) R_0 represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and n represents 1 or 2), and Y represents an aliphatic group substituted with the following general formula (a) or (b). group, aromatic group. General formula (a) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ General formula (b) R_2-SO_2NH- (In general formula (a), R_1 is a hydrogen atom, an aliphatic group, an aromatic group. represents a group group or a heterocyclic group, and L_1 is -O-, -
Represents S-, or ▲There are numerical formulas, chemical formulas, tables, etc.▼, and R_a and R_a' represent a hydrogen atom, an aliphatic group, or an aromatic group. In general formula (b), R_2 represents an aliphatic group, an aromatic group or a heterocyclic group. ) X represents a group represented by general formula (II) or (III). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1 and may be linked to each other to form a ring.) General formula (III) -O-X_3 (wherein, X_3 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group))