JPH02196234A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain photographic characteristics with extremely hard negative tones having >10 gamma by use of a stable liquid developer by incorporating a specific compd. into a silver halide photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic sensitive material. CONSTITUTION:The compd. expressed by general formula I is incorporated into the silver halide photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic sensitive material. In formula I, A1 and A2 are both hydrogen atom, or either of them is hydrogen and the other is sulfonic group or a compd. expressed by formula II. G is a sulfonyl or sulfoxy group expressed by formula III or a thiocarbonyl group or iminomethylene group expressed by formula IV. X represents an aliphatic or aromatic group substituted with a group expressed by formula V, in which Y is a hydrogen atom, aliphatic group, aromatic group or heterocyclic group, Ra is a hydrogen atom, aliphatic group or aromatic group and R is nitrogen-contg. heterocylic residual group. In formula I, the sum of carbons in X, G and R is >=17.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to a silver halogen photographic light-sensitive material that provides extremely high contrast negative images, highly sensitive negative images, good halftone image quality, or direct positive photographic images. The present invention relates to a silver halide photographic light-sensitive material which forms a silver halide, and particularly relates to a photographic light-sensitive material containing a novel compound as a nucleating agent for silver halide.

(Prior art) The addition of a hydrazine compound to a silver halide photographic emulsion or developer is disclosed in U.S. Pat.
, 227,552 (using hydrazine as an auxiliary developer to obtain direct positive color images), 3.386.8.
No. 31 (contains β-mono-phenylhydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials), No. 2, 4
19.975, and The Theory of Photographic Process by Mees.
theory of Photographic Pro
cess) 3rd edition (1966), page 281.

Among these, in particular, US Pat. No. 2,419,975 discloses that a high-contrast negative image can be obtained by adding a cydrazine compound.

The patent specification states that by adding a hydrazine compound to a silver chlorobromide emulsion and developing it with a developer having a high I)H of 12.8, extremely high-contrast photographic properties with a gamma D) exceeding 10 can be obtained. It is stated that. However, a strong alkaline developer with a pH close to 13 is easily oxidized in the air and is unstable, so it 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 tone images (dot images) or reproduction of line drawings.

Conventionally, for this purpose, the content of silver chloride was set at 50%.
A common method is to use a silver chlorobromide photographic emulsion with a mol%, preferably more than 75 mol%, and develop it with a hydroquinone developer with an extremely low effective concentration of sulfite ions (usually 0.1 mol/11 or less). It was used in However, in this method, since the concentration of sulfite ions in the developer is low, 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 high sensitivity cannot be obtained. 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 vA images.

U.S. Patent No. 4.224.401, U.S. Patent No. 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 negative photographic properties, but how many acylhydrazine compounds were used in these? 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. This is because the leakage into other photographic materials has an adverse effect on other photographic materials.

It has been known to increase the molecular weight of a nucleating agent to make it diffusion resistant as a means of preventing it from leaking into the development processing solution. It turns out there is a problem. 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, 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 photosensitive material, other sensitization techniques (such as chemical sensitization) may be used. In general, when used in combination with compounds that promote sensitization (such as increasing the particle size, increasing the particle size, or adding compounds that promote sensitization such as those described in U.S. Pat. Nos. 4,272,606 and 4,241,164), Sensitization and enhancement blur may occur over time during storage.

Therefore, it is desirable to have a compound that can reduce the generation of such bubbles and leakage into the developer, has no problems with stability over time, and can provide extremely high contrast photographic properties even when added in a small amount. was.

Also, U.S. Patent Nos. 4,385,108 and 4.269
．． No. 929 and No. 4,243,739 describe that extremely high-contrast negative tone photographic properties can be obtained by using hydrazines having a 'y1 substituent that is easily adsorbed to silver halide grains. However, among these hydrazine compounds having adsorbent groups, those specifically mentioned in the above-mentioned known examples have a problem in that they cause 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 desensitizer, and then developed, and a method in which silver halide grains are exposed to light in the presence of a desensitizer and then developed, The most useful method is to develop the silver oxide emulsion in the presence of a nucleating agent after exposure. The present invention relates to the latter.

Silver halide emulsions that mainly have photosensitive nuclei inside 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 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 it may also be added to the photographic emulsion layer or other appropriate layer of the light-sensitive material so that it is adsorbed to the surface of the silver halide grains. Sometimes better inversion characteristics can be obtained.

The nucleating agent used in the above method for obtaining a direct positive image includes U.S. Pat.
8.982, and hydrazides and hydrazine-based 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. 4.115,122
No., British Patent No. 1,283,835, Japanese Patent Publication No. 5234
Heterocycle No. 4 described in No. 26 and No. 52-69613
class salt compounds, U.S. Pat. No. 4,030゜925, No. 4,
No. 031.127, No. 4,139.387, No. 4.2
45.037, 4゜25-5.511 and 4
, No. 276.364, British Patent No. 2.012,443, and the like. Silphenylhydrazine compounds, compounds having a heterocyclic thioamide as an adsorption group described in U.S. Pat. No. 4,080,207,
A phenylacylhydrazine compound having a heterocyclic group having a mercapto group as an adsorption type described in British Patent No. 2,011,397B, US Patent No. 3,718,470
JP-A-59200.230, JP-A No. 59200.230, JP-A-59200.230, JP-A No. 59-21
No. 2,828, No. 5!1212.829, flese
arch Disclosure magazine No. 23510 (1
A hydrazine compound described in (November 953) is known.

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 the emulsion and the time they are coated. It has been found that there are drawbacks such as deterioration of film quality when a larger amount is added.

In order to solve these drawbacks, JP-A-60-179.7
No. 34, No. 61-170, 733, Special Desire 6 (1-2
No. 06,093, No. 60-19,739, No. 60-1
Adsorption type hydrazine derivatives described in No. 11,936,
Hydrazine derivatives having a heteroaromatic ring residue in the molecule described in JP-A No. 62-275247, or modifying groups described in JP-A No. 61-270948, JP-A No. 63-29,751, etc. Hydrazine derivatives with Or, in response to the desire to reduce dependence on changes in developer composition (for example, pH 1, sodium sulfite, etc.), nucleating activity may be insufficient, or adverse effects may be seen due to leakage into the processing solution. There were negative effects.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a halogen compound that can obtain photographic characteristics of an extremely sharp negative gradation with a gamma exceeding 10 using a sufficient developing solution. An object of the present invention is to provide a silver oxide photographic material.

A second object of the present invention is to contain highly active hydrazines that can provide the desired extremely sharp negative gradation photographic characteristics even in a low pH developer with a small amount added without adversely affecting photographic characteristics. An object of the present invention is to provide a negative-working silver halide photographic material.

A third object of the present invention is to provide a direct positive silver halide photographic light-sensitive material containing highly active hydrazines that can provide excellent reversal characteristics even in a low p1 developer.

A fourth object of the present invention is to provide a silver halide photographic light-sensitive material that is easy to synthesize, contains a hydrazine, and has good storage stability over time.

The fifth object of the present invention is to ensure that the emulsion has good stability over time and is highly effective during the production of sensitive materials. An object of the present invention is to provide a silver halide photographic material with small l fluctuation.

(Structure of the Invention) An aspect of the present invention is that in a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, at least This was achieved by containing a compound represented by the symbol below - Shipman (]).

General formula (1) In the formula, AI and At are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group or +C+t, Ra (in the formula R
* represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and 1 does not represent 1 or 2.

G represents +C+e, (rtLi represents 1 or 2), sulfonyl group, sulfoxy group, P- (in the formula R
8 represents an alkoxy group or an aryl R+oxy group. ), represents a thiocarbonyl group or an iminomethylene group.

X represents an aliphatic group or an aromatic group substituted with the following -Shipman (a).

General formula (a)0 Y-(, -N- R1 Formula (where Y represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R1 represents a hydrogen atom, an aliphatic group, or an aromatic group; R represents a nitrogen-containing heterocyclic residue.

R represents a nitrogen-containing heterocyclic residue.

- In Shipman (1), the total number of carbon atoms of X, G and R is 17 or more.

Next, general formula (1) will be explained in detail.

- In Saito (1), AI and At are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms, and arylsulfonyl groups (preferably phenylsulfonyl groups or so that the sum of Hammett's substituent constants is -0.5 or more) (substituted phenylsulfonyl group), +C+trR- (Re preferably a linear, branched or cyclic alkyl group having 30 or less carbon atoms, an alkenyl group, an aryl group (preferably a phenyl group, or the sum of Hammett's substituent constants) (phenyl group substituted so that -0°5 or less), alkoxy group (for example, oxy group), aryloxy group (preferably a monocyclic group such as phenyl group), etc. These groups may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acyl)Lt amino group, and a sulfonylamino group. 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 or carboxyl group, alkyl or aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group, alkylthio group, arylthio group, and the like. ), and AI
, AI specifically represents those described in US Pat. No. 4,478,928.

As AI and Ax, a hydrogen atom is most preferable.

- Of the groups represented by G in Funato ([), -C- is preferred.

In the general formula (1), the aliphatic group represented by X is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

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

Preferred as X are aromatic groups and groups represented by the general formula (bl).

(General Niyama) (wherein, X represents an aromatic group or a nitrogen-containing heterocyclic group, R1-'-R: each represents a hydrogen atom, a halogen atom, or an alkyl group, (If possible, it may have a substituent. r and S represent 0 or 1.) X is more preferably an aromatic group, and particularly preferably an aryl group.

X may be substituted with a substituent other than the substituent represented by general formula (a). 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, aryol 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, Examples 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 when possible.

Further, X can include one or more of the general formula (al).

In the general formula ial, 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 7-aryl group. Examples include t-nyl group and naphthyl group.

As the heterocycle of Y, N, 0, and nu are 3 to 1 O-membered saturated or unsaturated heterocycles containing at least one S atom, and these may be monocyclic, and The -tsutero ring which may form a condensed ring with another aromatic or hetero ring is preferably a 5- to 6-membered aromatic hetero ring, such as a pyridine group, an imidazolyl group, a quinolinyl group, Those containing a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, and a penzthiazuryl group are preferred.

Y may be substituted with a substituent, and examples of W and ttA groups 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, 1/tan group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, etc. carboxyl group, alkyl and aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group,
Examples include sulfonamide group, nitro group, alkylthio group, and arylthio group.

These groups may be linked to each other to form a ring when possible.

The aliphatic group represented by R in the general formula (al) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

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

R1 device 1! ! It may be substituted with a group. Examples of the X substituent include those listed as the substituent for Y in -Funenin (11).

Moreover, Y and R may be connected to each other to form a ring, if possible.

More preferably, R1 is a hydrogen atom.

- In Funato (1), the nitrogen-containing heterocyclic residue represented by R is specifically a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, which may have a substituent,
A quinolyl group, an isoquinol group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinolinyl group, a cinnolinyl group, or a buteridinyl group, and examples of the substituents include an alkyl group, an aryol group, a halogen atom,
Examples include substituted amino groups, cyano groups, acylamino groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and combinations thereof.

Among them, an organic salt that provides sufficient molecular weight to substantially prevent the compound represented by formula (1) from diffusing into the tthi or processing solution;
It consists of a combination of one or more of an alkyl group, an aryl group, a heterocyclic group, an ether group, a 1,000-onythyl group, an amide group, a ureido group, a urethane group, a sulfonamide group, and the like. The ballast group is preferably one having 13 or more carbon atoms, more preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the compound represented by general formula (1) are shown below.

However, the present invention is not limited to the following compounds.

2゜■ 4゜9゜10゜■ 12゜CHl -5゜■ 7゜■ 8゜15゜1-16゜! 17°Ctlls The hydrazine derivative of the present invention was synthesized by treating the corresponding known polmylhydrazine with hydrochloric acid and then reacting it with the acid chloride of a predetermined nitrogen-containing heterocyclic carboxylic acid or sulfonic acid in the presence of pyridine.

(Synthesis example...Synthesis of compound 1) CF.

Concentrated hydrochloric acid (4-) was added to a mixture of Cυ0■ methanol (50m) and stirred overnight at room temperature. After completely distilling off the volatile components under reduced pressure, acetonitrile (80m), DMF (20id),
Pyridine (81 liters) was added followed by picolinic acid chloride hydrochloride (5.2 g).

After stirring overnight at room temperature, volatile components were distilled off again under reduced pressure.
By purifying with silica gel chromatography,
Obtained the object. (Yield 4.7g).

The chemical structure was confirmed by nmr spectrum, Ir spectrum, and elemental analysis.

Other compounds were synthesized in the same manner.

The compound of the present invention is incorporated into a photographic emulsion layer or a hydrophilic colloid layer (in this case, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary, an alkali hydroxide or a It may be added to a hydrophilic colloid solution (for example, silver halide emulsion, gelatin aqueous solution, etc.) by adding an acid or alkali as necessary. pH 1!! You can also adjust it)
,.

The compounds of the present invention may be used singly or in combination. The amount of the compound Ω added in the present invention is determined to be a suitable amount per mole of silver halide/Xlθ-5,...J.

X70-2 moles, preferably 2X10-5 moles/
X10 moles, and an appropriate value can be selected depending on the properties of the silver halide emulsion to be combined.

When the compound represented by the general formula (I) of the present invention is used in combination with a negative emulsion, it is possible to form a negative image with high contrast.

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 l-.

When the silver halide is used to form a high-contrast negative image, it is preferable that the average grain size of the silver halide used be fine (for example, 0.7 μm or less), particularly Ko, rμ or less. There are basically no restrictions on the particle size distribution, but it is preferable that it be monodisperse. Monodisperse herein means that at least 9j'lp of the particles are composed of a group of particles having a size within the average particle size of OtS in terms of weight or number of particles.

Silver halide powder in photographic emulsions is cubic, octahedral, and rhombic.
．． dihedron, ll/ is 5 regular like a hedron.
r) It may have regular crystals, it may have irregular crystals such as spherical or tabular, or it may have a composite shape 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.

Silver halide emulsions used in the present invention include cadmium salts, sulfite groups, lead salts, thallium salts, rhodium salts, complex salts thereof, iridium salts or complex salts thereof, during the formation of silver halide grains or during physical ripening. etc. may coexist.

The silver halide used in the present invention is 10-8 per 7 moles of silver.
It is made of silver haloiodide prepared in the presence of ~10' moles of iridium salt or its complex salt, and in which the silver iodide content on the grain surface is higher 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 total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, radium, and 0 dium. A specific example is U.S. Patent No.
No. to, British Patent No. 6it, oit, etc. fc. As the sulfur sensitizer, 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 an iridium salt or a rhodium salt before the completion of physical ripening in the silver halide emulsion manufacturing process and during the formation of K grains.

In the present invention, the silver halide emulsion layer is
m9? 281 class monodispersed emulsions with different average grain sizes as disclosed in Japanese Patent Application No. 1986-J, Japanese Patent Application No. 320Jljt are preferable from the viewpoint of increasing the maximum density (Dmax). The dispersed particles are preferably chemically sensitized, 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, large-sized monodispersed emulsions are not chemically sensitized because they tend to produce black spots, but when chemically sensitized, the emulsion is sufficiently 1 to prevent black spots from occurring.
It is especially preferable to apply IIC shallowly. Here, ``Shallow application'' means that chemical sensitization is performed by shortening the time compared to chemical sensitization of small-sized emulsions, or by reducing the amount of chemical sensitizer added at a lower temperature. There is no particular limit to the sensitivity difference between a large size monodisperse emulsion and a small size monodisperse emulsion, but Δ71ogE is 0, /~/, O1 is preferably 0.
．． 2 to 0.7, and the higher the value for large-sized monodispersed emulsions, the better.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative, and adding sulfite ions to Ool, j'mol/!
This is obtained when processing with a developer having a pH of <7°j-V/2·, J containing the above.

The average grain size of the small monodisperse grains is less than or equal to the 2θ width of the average size of the large monodisperse silver halide grains, preferably less than 10%. / The average grain size of the silver halide emulsion grains is preferably o, o coμ to /, 0
μ is more preferably 0. /μ~0. It is preferable that the average particle size of large size and small size monodisperse particles is not included in this range in Jμ.

In the present invention, the sizes are different. When two or more types of emulsions are used, the coating silver of a small-sized monodisperse emulsion is determined based on the total amount of coated silver.

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

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.

In addition, the total amount of coated silver is /? 7m2-r 9/
m2 is preferred.

For the purpose of increasing sensitivity, the photosensitive material used in the present invention includes Japanese Patent Application Laid-Open Publication No. 2002-120000, tj-j 2θjθ, No. Hiroshi, page ~! 3
Sensitizing dyes (for example, cyanine dyes, melonanine dyes, etc.) described on page 1 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 itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light but exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure.
) / 7 A% / 7G[J ( / 97g'year 7.2
Monthly issue) No. 1, ? It is described in section 5 of page ■.

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. Azoles such as benzothiazolium salts, nitroindacids, chlorobenzimidazoles, mobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles , nitrobenzotriazoles, etc.: mercaptovirimidines; mercaptotriazine M4; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4t-hydroxy substituted (/, J,,?a,
7) Tetrazaindenes), interazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides and the like. Among these, preferred are benzotriazoles (eg, j-methyl-benzotriazole) and nitroindazoles (eg, yo-nitroindazole). Further, these compounds may be included in the treatment liquid.

Development accelerators or nucleating and contagious development accelerators suitable for use in the present invention and 1- are described in JP-A No. 3-77iG/J-1, t'4'-J773, j3- /J7/J
J No., same to-/Hiro 03410, same t.

In addition to the compounds disclosed in No.-141962, etc., N
Alternatively, various compounds containing an S atom are effective.

These accelerators (2) The appropriate amount of R to be added differs depending on the flea of the compound, but it is preferably in the range of θ x 10' - θ, j2/m2, preferably in the range of θ x 10'''3 to θ, 12/m2. It is desirable to use it in

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, that is, the redox potential determined by polarography, and the sum of polarographic anodic potential and cathodic potential is positive.

A polarographic method for measuring redox potential is described, for example, in US Patent No. J, tO/, 307. The organic desensitizer preferably contains at least one water-soluble group, specifically a sulfonic acid group, a carboxylic acid group,
These groups include organic bases (
For example, it may form a salt with ammonia, pyridine, triethylamine, pyridine, morpholine, etc.) or an alkali metal (eg, sodium, potassium, etc.).

Examples of organic desensitizers include general formulas (III) to (V
) is preferably used.

The organic desensitizer in the present invention is V in the silver halide emulsion layer.
C,1,Oxlθ ~1.0X10-7m2, especially /,0x10-f~1. θ'x, 1 o-s mol/yn
It is preferable to ensure that there are two.

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. The filter dye may be a dye that further lowers the photographic sensitivity, preferably an ultraviolet absorber that has a spectral absorption maximum around the intrinsic sensitivity of silver halide, or a dye that is resistant to safelight light when handled as a bright room photosensitive material. In order to increase safety, dyes with substantial light absorption mainly in the region of JrOnm-600 nm are used.

These dyes can be added to the emulsion layer depending on the purpose, or they can be 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 further away from the silver halide emulsion layer with respect to the support. It is preferable to use it in a fixed position.

Although it varies depending on the molar absorption coefficient of the ultraviolet absorber, it is usually 10
-297m2~/S'/~2. Preferably F'i,, romy~tθQ II9 /
m2.

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

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an aryl group, a Hiro-thiacylidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used.

Specific examples of ultraviolet absorbers include US Patent J, jJJ.

7ri ψ, 3I3/ψI7ri μ, 3.3j, 2.
/, f1, JP A-, 27J "II", US Patent J, 70. j, IO, No. j, 707. J, 7.
No. 4t, θ4t, Kodori No. 3,7θθ,
Hirojj, same J, 4t? 7J, No. 2, West German Patent Application Publication/, j'447. It is described in No. 3 of t.

Filter dyes include oquinonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, shikunin 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, US Patent No. 2. ．． 27g, 7fJ
, U.S. Pat. No. 4, JJ4. Diarylazo dyes described in U.S. Pat. No. 3.41.2J, 207, No. J, jIr
4', the styryl dyes and butadienyl dyes described in Gu J'7, U.S. Patent No. 2. J”, 27., t, r3, U.S. Pat. No. 3.41, rt, r
yy issue, 3rd and 6th. t2, 2170: No. J, 7
/l:, the merocyanine dyes and oxonol dyes described in U.S. Pat. Enaminohemioxonol dyes described in No. 76°A7/ and British Patent No. JR,
No. 102, same No. 1. /77.41.29, Tokukai Sho GF
-jrJ/No. 30, No. 20 at the same Koro Tatata, same '7? −
1lt1. Guco θ, U.S. Patent No. 2. II3.4/7.
No. 2, same No. J, /lit.

/l'7 No. 3゜/77.071, No. 3゜24
17, /, 27th, same No. J, j410. rl nia,
Same No. J, J7. r,, No. 70≠, No. J, J, tJ,
The dyes described in No. 201, K are used.

The dye can be used in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, pro, 1-ol, etc.), acetone, methyl chloride, etc., or a mixed solvent thereof].
K is dissolved and added to the non-photosensitive hydrophilic colloid coating solution of the present invention.

The specific amount of dye used is generally 10 to 2 to 2 g.
/m2, especially in the range of /0-3 f/m2 to 0°1-7 m2.

The photographic light-sensitive 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 and aldehydes.

(Formalde, geltaldehyde, etc.), N
- Methylol compounds (such as dimethylol urea), active vinyl compounds (t, 3., r-1 acryloyl-hexahydro-s-triazine, l, 3-vinylsulfonyl-copronominol nato), active "" care compounds (
2,4' 9 chloro-ot-hydroxy-5-triazine), mucohalogen acids, etc. can be used alone or in combination with 1.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention, Ti is added as an additive to prevent static, improve slipperiness, emulsification and dispersion, prevent adhesion, and improve photographic properties. Various surfactants may be included for various purposes such as oxidation, sensitization, etc. In particular, the surfactant preferably used in the present invention is Tokko Sho J'! These are polyalkylene oxides having a molecular weight of 0θ or more and described in Publication No.-24L/2. When used as an antistatic agent, a fluorine-containing surfactant (for details, see US Pat.
r.

No.l72, same JP-74',! ! ', ') are particularly preferred.

The photographic material of the present invention may contain a matting agent such as silica, magnesium oxide, or polymethyl methacrylate in the photographic emulsion layer or other hydrophilic colloid layer 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 purposes such as improving dimensional stability. For example, we use polymers whose monomer components are alkyl (meth)acrylates, alkoxy acrylic (meth)acrylates, glycidyl (meth)acrylates, etc. alone or in combination, or combinations of these with acrylic acid, methacrylic acid, etc. I can be there.

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 compounds having acid groups include poly7- or copolymers having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and fucuric acid. Regarding these compounds, Japanese Patent Application No. 1986-74/72, to-
Al17.3, same 6θ-/13. ．． 1. tt number and the same θ-72! The description in Specification No. 15 can be referred to. Among these compounds, particularly preferred are low molecular weight compounds such as ascorbic acid, high molecular weight compounds (including acid monomers such as acrylic acid, and one or more unsaturated groups such as divinylbenzene). It is a water-dispersible latex of a copolymer made of crosslinkable monomers.

In order to obtain ultra-high contrast and high sensitivity photographic properties using the silver halide photosensitive material of the present invention, conventional infectious developing solutions or US Pat. No. 1.41. /ri, 97. ! pH/3V stated in No. r
It is not necessary to use a high alkaline developer close to C, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 5. sulfite ions as a preservative at θ. l! Contains mol/1 or more, p
) (10,, t-/, 2.J, especially pH/7.0 =/
A sufficiently ultra-high contrast negative image can be obtained using the iO developer.

The developing agent used in the developer used in the present invention is not particularly limited, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 7π phenyl-3-pyrazolidone are preferred since it is easy to obtain good halftone quality. In some cases, a combination of dihydroxybenzene and p-amine phenols is used. The developing agent is preferably used in an amount of usually 0.1'' mol/l. Also, dihydroxybenzenes and 7-phenyl-7?-pyrazolidones or p-amino-phenol are used. When using a combination with , it is preferable to use the former in an amount of σ.θj mol/l to (7,4' mol/l) and the latter in an amount of 0.0 t mol/e or less.

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, 4t mol/j or more, especially θ. jmol/1 or more is preferred.

In the developing solution of the present invention, as a silver stain preventive agent, JP-A-Sho, t4-
A compound using the compound described in Ju and Ju 7 pressure distribution can be prepared.

Patent application 1974=10, 741! as a solubilizing agent added to the developing solution! The compounds described in item j can be used. Furthermore, as a pH buffering agent for body fluids,
-23. The compound described in No. 33 or the patent application Sho t/-
2J 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 used in combination with an internal latent image 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 also 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, intermediate layer, filter layer, protective layer, or antihalation layer, as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. Good too.

The content of the compound represented by the general formula (Il in the layer is such that an internal latent image type emulsion is developed with a surface developer. Sometimes, a sufficient maximum density C, for example, at a silver concentration!, 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 A range of from about 0.00 mg to about 70 mg per 7 moles of silver is practically useful, and is preferably from about 0.0/119 to about 70 mg per mole of silver. When it is contained in the emulsion layer Vr and adjacent hydrophilic colloids, it may be contained in the same amount as above for the amount of silver contained in the same area of the inner m-type emulsion layer. Regarding the definition of internal latent image type silver halide emulsions, see JP-A/-/707JJ, page 10, top shelf, and British Patent No. 1,019. DJ'7 Publication No. 1 J' Page-2
It is written on page 0.

Preferred internal latent image emulsions that can be used in the present invention include:
Special application Sho A/-, 2. tJ7/,'; specification page 11/
1 from line 4 to page 31, line β. Regarding fine-sized silver halide grains, see page 3 of the same specification, line 3 to page 3.2.
It is written in the /th 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. Sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes,
Oxonol dyes, hemioxonol dyes, etc. can be used. These sensitizing dyes fcu, such as JP-A-Sho,
, t9-410. J J r issue, same! r9-Fil
), i! ;J+< issue, same, t? Cyanine dyes and merocyanine dyes described in No.-31, 7, and 3 are included.

The light-sensitive material of the present invention can 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)/7Jg3 (/7.1' years/J months)■=D
No. 4/1'7/7C July 1977).

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, representative examples of which include an oxygen atom elimination type yellow coupler or a nitrogen atom elimination type yellow coupler. α-pivaloyl acedoe = +7 do couplers have excellent color fastness, especially light fastness, while α-
Benzoylacetanilide couplers provide high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected couplers of indacylon type or cyanoacetyl type, preferably pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. As the j-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

As a leaving group for a two-equivalent j-pyrazolone coupler, US Pat. /θ, the nitrogen atom leaving group described in US Pat. No. 67P or the arylthio group described in US Pat. Further, the pyrazolone couplers having a pallast group as described in European Patent Nos. 7J and AJA can provide high color density.

As pyrazoloazole couplers, US Pat.
J7? , I Tata] benzimidazoles, preferably pyrazolo(j,/-c)[),z,e)) lyazoles as described in U.S. Pat. No. 3,727.067, Research Disclosure KodakokoO(l)
June 2013) Pyrazolotetrazoles described in VC and Research Disclosure 24t, 23θ (/?
Examples include pyrazolopyrazoles described in 1999 (month of 1999). Imidazo CI, 2-b) pyrazoles described in European Patent No. 1I, No. 74Z/ are preferred in terms of low yellow side absorption and light fastness of coloring dyes, and European Patent No. 1/1, No. 160- Pyrazolo (/.

, r-b) [:/,,2. Guttriazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected nanthole and phenol couplers, as described in US Patent I, 2.4'74'.

, No. 293, preferably U.S. Pat.

/416,39, same il/,,2.2f,,ZJ
No. J and the same No. p, 2ri 1. ,． A typical example is the oxygen atom dissociating type two-equivalent naphthol coupler described in No. 20θ. Further, specific examples of phenolic couplers include U.S. Pat.
J' (7/, No. 171, same No. J, No. 77.2./lj,
Same number, 2. It is written in the corner of the f5', t, JJ/; issue. A cyan coupler that is robust against humidity and temperature pressures.
A typical example of the phenol compound preferably used in the present invention is the one described in U.S. Patent No. J, 772,00.2.
- Phenolic cyan coupler having an alkyl group higher than the meta-positional pressure of the ethyl group 1.2. t-Diacylamino substituted phenolic couplers and! These include phenolic couplers that have a phenylureido group at the - position and an acylamino group at the first position.

In order to correct unnecessary absorption in the short wavelength region of dyes generated from maze/cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for pressure and photography.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in U.S. Patent No. G, J/A.

No. 237 and British Patent No. 2.12, an example of a Jr. 70 pressure magenta coupler is also shown in European Patent No.
J'70 and West German Application No. 3. ．． 27v.

J3. ? The issue includes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the specialty couplers described above may form diro- or more-polymerized polymers. Typical examples of polymerized tongue dye-forming couplers are disclosed in U.S. Patent No. 3. I/, t/
, zxo No. 1I, OfQ.

, No. 211. A specific example of a polymerized magenta coupler is a British patent tube! , lθJ, 773 and US Pat. No. 4', jA7. ．． 2! It is described in No.j2.

The various couplers used in the present invention can be used in combination of two or more types in the same layer of the photosensitive layer in order to adjust the properties required for the photosensitive material, or the same compound can be used in different combinations. It can also be introduced into two or more layers.

The standard usage amount of color couplers is in the range of 0.001 to 1 mole per mole of photosensitive silver halide, preferably θ, θ/ to Q for yellow couplers.
,! Mol, magenta coupler O+Oθ3 to 0,
3 moles, and for cyan couplers O1θθ1 to 0.
It is 3 moles.

In the present invention, developing agents such as hydroxybenzene (eg, dihydroginone), aminophenols, 3-pyrazolidones, etc. may be contained in the emulsion or the light-sensitive material.

The photographic emulsion used in the present invention can be used in combination with a dye image-providing compound (c colorant) for color diffusion transfer processes, which releases a diffusible dye at a temperature corresponding to the development of silver halide. It can also be used to obtain a desired transferred image on an image-receiving layer after processing. Many coloring materials are known for use in color diffusion transfer methods. It is preferable to use a type of colorant that is cleaved to release a diffusible dye (hereinafter abbreviated as DRR compound). Among them, D having an N-substituted sulfamoyl group
RR compounds are preferred. Particularly preferred for use in combination with the nucleating agent of the present invention is US Patent No. 4Z, 0! J, U, 2r No. 44,013. J/λ, Dohiro, JJA, J, 2.
DR,R compounds having an 0-hydroxyarylsulfamoyl group as described in No. 2, etc., and JP-A-Sho, t.
J-/Hiroshi.

,? The DRR compound having a redox core as described in No. 2, Vol. Like this'fx, DRR1
When used in combination with other compounds, the temperature dependence, especially during processing, is significantly reduced.

Specific examples of DRR compounds include those described in the above patent specifications, as well as magenta dye grain-forming substances.
-Hydroxy-λ-tetramethylenesulfamoyl-ku[3'-methyl-Hiro'-(,,!//-hydroxy-y~methyl-j"-hexadenyloxyphenylsulfamoyl)-phenylazo]-naphthalene Examples of yellow dye image-forming substances include l-phenyl-3-thiafuryC2''q///-di-tert-<methylphenoxyacetamino)-phenylsulfamoyl]phenylaso)-y-pyrazolone. .

Details of the color couplers that can be preferably used in the present invention are described in Mei No. M, page 33, line II to Hiro θ, page last line.

After imagewise exposure using the light-sensitive material of the present invention, after or while performing a fogging treatment with light or a nucleating agent, the pH of the material containing an aromatic primary amine color developing agent is below When the surface is subjected to color development, bleaching and fixing treatment using body fluids, it is preferable to directly form a positive color image using pressure. The pH of this developer.

More preferably, it is in the range of 0-10.0.

The turnip treatment in the present invention is the so-called "light turnip method"
Either of a method called "chemical fogging method" in which the entire surface of the photosensitive layer is exposed to second light, and a method called "chemical fogging method" in which development is performed in the presence of a nucleating agent may be used. The film may be developed in the presence of a nucleating agent and fogging light. Also,
A photosensitive material containing a nucleating agent may be fog-exposed.

Regarding the light fogging method, the above-mentioned patent application Sho&/-, 2, tJ
7/A specification, page 4/7 Hiroyuki to page 419, line j, and regarding the nucleating agent that can be used in the present invention, see 1. It is written on page t9, line 6 to page t7, line,
In particular, it is preferable to use compounds represented by -Funenin [N-/) and [N-,2:). Specific examples of these include (N-I-/) to rN-I described on pages j6 to sr of the same specification.
, 10] and (:N-1) described on pages z3 to zz of the same specification.
'I-7] to CN-ll-/, 2') are preferably used.

Regarding the nucleation accelerator that can be used in the present invention, see Section 7 of the same specification.
It is described in page 1// line to page 7/ line 3. Particularly, as a specific example, (A-/1 to page 7 o)
The use of (A-/, ?) is preferred.

The color developing solution used in the development of the photosensitive material of the present invention is described in the same specification on page 71, line 7-71, and in particular aromatic primary amine color developing solution. As a specific example, p-phene; diamine type compounds are preferable, and typical examples thereof include 3-methyl-μmamino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3-methyl-t -amino-N-ethyl-N
-(β-hydroxyethyl)aniline, 3-methyl-≠
Examples include -amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfate group and hydrochloride.

When directly forming a positive color image using the light-sensitive material of the present invention by a color diffusion transfer method, black and white developers such as phenidone derivatives can also be used in addition to the above-mentioned color developers.

After color development, the photographic emulsion layer is repeatedly 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 may be employed in which bleaching is followed by bleach-fixing, or a method in which fixing is followed by bleach-fixing. 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. As additives used in the bleaching solution or bleach-fixing solution of the present invention, various compounds described in Japanese Patent Application No. 7.2≠, No. 4.2, pages 1 to 30 are used. be able to. After the desilvering step C (bleach-fixing or fixing), washing with water and/or
Or perform processing such as stabilization. It is preferable to use softened water as the washing water or stabilizing liquid. As a method of water softening treatment, Tokugan Sho I! -/31632 discloses a method using an ion exchange resin or a reverse osmosis device for wiring. As a specific method for these, it is preferable to carry out the method described in Japanese Patent Application No. 1 Jl-/J/A3.2 Mei Mj.

Furthermore, additives used in the water washing and stabilization steps include Patent Application Sho GT-3, Y, 4 It, No. 2 Specification, page 30 = 3.
It is possible to use a variety of compounds as described on page 1.

It is preferable that the amount of replenisher that goes into each treatment step is small.

The amount of replenisher is preferably 0°/-j 0 times, more preferably 3-3a times the amount of pre-bath brought in per unit area of the photosensitive material.

Example 1 4X10 per mole of silver in an aqueous gelatin solution kept at 50°C
-' molar of iridium hexachloride (ITI) in the presence of potassium hexachloride (ITI) and ammonia, an aqueous solution of silver nitrate and potassium iodide potassium bromide were simultaneously added over 60 minutes while the pAg
By keeping 7.8, the average particle size is 0.28μ
A cubic monodisperse emulsion having an average silver iodide content of 110.3 mol % was prepared.

This N agent was desalted by the flocculation method, and then 40 g of inert gelatin per mole of silver was added and kept at 50°C and treated with 5°5'-dichloro-9 as a sensitizing dye.
-ethyl-3-3'-bis-(3-sulfobrovir)
Oxacarbocyanine and a 10-' mole of KI solution per mole of silver were added and allowed to cool for 15 minutes before cooling. This emulsion was redissolved at 40°C, and 0.02 mol/silver mol of methylhydroquinone and 1.0×10-' mol/A of the hydrazine derivative of the present invention or comparative example shown in Table 1 were added.
g mole and then 5-methylbenzotriazole, 4
-Hydroxy-1,3,3a,7tetrazaindene, the following development accelerators (a) and (b), and a dispersion of polyethyl acrylate at 0 and 4 g/rrf, and the following compound (c) as a gelatin hardening agent. was added, and an amount of silver of 3
．． It was coated at a concentration of 4 g/rtK.

tHs (b) (c) H CH, -CH5O□C[ItCIICHiSOzCH-
Gelatin 1.5g/nf as a protective layer on top of COx
, polymethyl methacrylate particles (average particle size 2°5μ)
0.3g/rt? , the next surfactant-containing layer was applied.

Surfactant CHtCOOCbHI2 CHCOOCb H+ s 311
1g / tdS OsN a C*F +tS OtN CHtCOOKCzHy
2. 5■/d(+) Evaluation of High Contrast Performance These samples were exposed to tungsten light at 3200° through an optical wedge, developed with the following developer at 34°C for 30 seconds, fixed, washed with water, and dried.

The resulting photographic sensitivity and gradation are shown in Table 1. When the nucleating agent of the present invention was used, high sensitivity and high contrast were obtained.

[Developer - ■]

[2] Evaluation of photographic properties with exhausted developer Fill an automatic plate-making processor FG66 OF type (manufactured by Fuji Photo Film ■) with the above developer -■, and perform 3 tests under the following three conditions.
It was developed at 4° C. for 30 seconds, fixed, washed with water, and dried.

(A) Immediately after the temperature of the developer filled in the automatic processor reaches 34° C., development processing is performed (development with fresh solution).

(B) 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, load Fuji Film GRANDEX GA-100 film with 50.8
emX61. Exposure is carried out so that 50% of the area of Oes size is developed, 200 sheets are processed in one day, and development processing is carried out using a solution that is repeated for 5 days. Developer solution per processed number of sheets ~ I
Replenish 100cc of.

(Development using large-scale processing fatigue solution), the obtained photographic properties are shown below.
Shown in 1. (B) and (C) in terms of processing running stability.
It is desirable that the photographic properties obtained in (A) and (A) be the same.As can be seen from the results in Table 1, when the nucleating agent of the present invention is used, even if the developer is exhausted, the photographic sensitivity remains the same. fluctuation is small.

Sensitivity It is expressed as the difference from the blank sensitivity (j!ogE) as a standard. Therefore, for example, -1.0 means that the IogE is 1.0 lower than the blank, that is, 10 times Indicates feeling low.

Nakamoto Gradation (G): Point of density 0.3 and point 3 on the characteristic curve.
It is the slope of the straight line connecting the 0 points. The larger the value, the higher the contrast.

Main ratio Δ5l-A: Difference between sensitivity (S,) when developed with air fatigue solution and sensitivity (S,) when developed with fresh solution Book ratio Δ5C-A: When developed with mass processing fatigue solution Difference between sensitivity (S,) and sensitivity (SA) when developed with fresh solution Example-2 5.0X per mole of silver in gelatin aqueous solution kept at 50℃
After simultaneous mixing of an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of 10-' moles of (NH4)sRhCz, soluble salts were removed, gelatin was added, and chemical ripening was performed using methods well known in the art. 2-methyl-4=hydroxy-1,3,3a, as a stabilizer without? - Tetraazaindene was added. This emulsion was a cubic monodisperse emulsion with an average grain size of 0.15 microns.

A hydrazine compound was added to this emulsion as shown in Table 2, 30 wt% of polyethyl acrylic 1/-latex was added as a solid content based on gelatin, and 1,3-vinylsulfonyl-2-propanol was added as a hardening agent. A tool was added to coat the polyester support so that the amount of Ag was 3.8 g/d. The gelatin was 1.8 g/n (1.5 g/n) on top of this as a protective layer and 0.5 g/n of polymethyl methacrylate particles (average particle size 2.5 μm) as a matting agent.
3 g/d, plus the following surfactants, stabilizers, and UV-containing dyes as coating aids! apply a layer,
Dry.

Surfactant CHzCOOC&HIi CHCOOCbH13 S O,N a CsF I? S OtN CHtCOOKC,H? Stabilizer thioctic acid 37■/- 2,5w/n (2,1■/n)
-6o'y, exposed through an optical wedge at 38℃20
Second development was performed, followed by fixing, washing with water, and drying.

The photographic properties obtained are shown in Table 2. From the results in Table 2, it can be seen that the samples of the present invention had higher
It can be seen that high contrast can be obtained.

In addition, as in Example 1, the photographic performance was tested using a fatigued developer, and as shown in Table 2, the samples of the present invention had the following properties:
Fluctuations were small, showing favorable results.

5OJ(C#H,)z 100■/d Procedural amendment 4. Subject of amendment: Specification column "Detailed description of the invention"

Claims (1)

[Scope of Claims] It has at least one silver halide photographic emulsion layer, and the photographic emulsion layer or other hydrophilic colloid layer has the following general formula (I).
A silver halide photographic material comprising a compound represented by: 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.▼ (In the formula, R_0 is an alkyl group, an alkenyl group, an aryl group, an alkoxy group,
or represents an aryloxy group, l_1 is 1 or 2
represents. ). G has ▲a mathematical formula, a chemical formula, a table, etc.▼(m_1 represents 1 or 2), a sulfonyl group, a sulfoxy group, ▲a mathematical formula, a chemical formula, a table, etc.▼(in the formula, R_1 is an alkoxy group or an aryloxy group) ), represents a thiocarbonyl group or an iminomethylene group. X represents an aliphatic group or an aromatic group substituted with the following general formula (a). General formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (a), Y represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R_a represents a hydrogen atom, an aliphatic group, or a heterocyclic group. Represents an aromatic group. R represents a nitrogen-containing heterocyclic residue. In general formula (I), the total number of carbon atoms of X, G and R is 17 or more.