JPH02196235A - 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 constituting the silver halide photographic sensitive material to have at least one silver halide photographic emulsion layer and incorporating a specific compd. into the emulsion layer or other hydrophilic colloid layer. CONSTITUTION:The silver halide photographic sensitive material has one silver halide photographic emulsion layer. The compd. expressed by general formula I is incorporated into the emulsion layer or at least one other hydrophilic colloid layer. In formula I, A1 and A2 are both hydrogen atoms, or either of them is a hydrogen atom and the other is a sulfonyl group or a compd. expressed by formula II. G is a sulfonyl group or sulfoxy group expressed by formula III or 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, -L- is -O-, -S- or -N-, each of Ra, Ra' is a hydrogen atom, aliphatic group or aromatic group and R is nitrogen-contg. heterocyclic residual group.

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 sharp negative images, highly sensitive negative images, and good halftone image quality, or to direct positive images. The present invention relates to a silver halide photographic light-sensitive material that forms a photographic image, and particularly relates to a photographic light-sensitive material containing a novel compound as a nucleating agent for silver halide.

(Prior art) Adding a hydrazine compound to a silver halide photographic emulsion or developer is known in US 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-thousonophenyl hydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials), No. 2, 4
19.975, The Theory of Photographic Ink Process by Mees (The T
theory of Photographic Pro
cess) 3rd edition (I966), 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 hydrazine compound.

The patent specification states that when a hydrazine compound is added to a silver chlorobromide emulsion and the emulsion is developed with a developer having a high pH of 12.8, the gamma (r) exceeds 10, resulting in a high-contrast photograph. It is stated that the characteristics can be obtained. However, the pH
A strong alkaline developer with a value close to 13 is unstable due to air oxidation 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 dot 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 over 75 mol%, and develop it with a hydroquinone developer with an extremely low effective concentration of sulfite ions (usually 0.1 mol/l or less). It was used in However, with this method, the concentration of sulfite ions in the developer is low, so
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 is a strong need to use a highly sensitive emulsion and a stable developer to obtain ultra-high contrast photographic properties 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, etc., disclose silver halide photographic emulsions that use stable developing solutions and provide extremely high-contrast photographic characteristics, but the acylhydrazine compounds used therein are 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, these conventional hydrazines are required in large quantities for sensitization and high contrast, and when particularly high sensitivity is required in terms of the performance of the photosensitive material, other sensitization techniques (such as chemical When used in combination with compounds that enhance sensitization, increase particle size, or add compounds that promote sensitization as described in U.S. Pat. Generally, sensitization and enhancement blurring may occur over time during storage.

Therefore, there is a need for a compound that can prevent 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. Ta.

Also, U.S. Patent Nos. 4,385.108 and 4.269
．． No. 929 and No. 4,243,139 describe that extremely high-contrast negative 1111m photographic properties can be obtained using hydrazines having substituents that are easily adsorbed to silver halide grains. Among these hydrazine compounds having an adsorptive group, 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 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.

As the nucleating agent used in the above method for obtaining a direct positive image, US Pat.
8,982, and 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. 4,115,122
No., British Patent No. 1,283.835, JP-A-52-3
Heterocyclic quaternary salt compounds described in U.S. Patent No. 426 and U.S. Pat.
, No. 031,127, No. 4,139.387, No. 4,
245.037, 4゜255.511 and 4
, 276.364, thiourea-bonded acylphenylhydrazine compounds described in British Patent No. 2,012,443, and heterocyclic thioamides described in US Patent No. 4,080,207. ! A phenylacylhydrazine compound having a heterocyclic group having adsorption type mercap) M as described in British Patent No. 2,011,397B, U.S. Patent No. 3,718,47
Sensitizing dye having a substituent having a nucleating effect in its molecular structure as described in No. 0, JP-A No. 59200.230, No. 5! J-
No. 212,828, No. 59-212,829, Re5
search I) Isclosure magazine No. 23510
Hydrazine compounds described in (November 1953) are 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 60-20
No. 6,093, No. 6019.739, No. 6 (I-11
Adsorption type hydrazine derivatives described in No. 1,936, hydrazine derivatives having a heteroaromatic ring residue in the molecule described in JP-A-62-275247, or JP-A-62-275247.
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)
Do you want to lower H, shorten development processing time, or reduce dependence on changes in developer composition (for example, pH 5 sodium sulfite, etc.)? However, there have been disadvantages such as insufficient nucleation activity or adverse effects due to leakage into the developing 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 10 using a stable developer. An object of the present invention is to provide a silver 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 properties even in a low pH developer with a small amount added without adversely affecting the photographic properties. An object of the present invention is to provide a negative-working halogenated plate photographic material.

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

A fourth object of the present invention is to provide a silver halide photographic light-sensitive material containing hydrazines that can be easily synthesized, has excellent storage stability, and has good stability over time.

A fifth object of the present invention is to provide a silver halide photographic light-sensitive material whose emulsion has good stability over time and whose activity fluctuations are small during the production of the light-sensitive material.

(Structure of the Invention) The present invention provides a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer. This was achieved by containing at least one compound represented by the following shipman (I) in the layer.

- Shipman (I) In the formula, A+ and At are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group, an aryl group, an alkoxy group, or an aryloxy group, and l is 1 or 2. represents a sulfonyl group, a sulfoxy group, an oxy group, ) represents a thiocarbonyl group or an iminomethylene group.

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

General formula (→ 1! Y-L-C-N- RゎIn formula (a), Y represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and L represents 10--- S- or -N
-, R,, R,' represents a hydrogen atom, R1 represents an aliphatic group or an aromatic group.

R represents a nitrogen-containing heterocyclic residue.

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

- In Shipman (I), A, Ao is a hydrogen atom, carbon number is 2
0 or less alkylsulfonyl groups and arylsulfonyl groups (preferably phenylsulfonyl groups or straight-chain, branched phenylsulfonyl groups of 30 or less so that the sum of Hammett's substituent constants is -0.5 or less) a cyclic or cyclic alkyl group, alkenyl group, aryl group (preferably a phenyl group, or a group whose sum of Hammett's substituent constants is −0
.

5 or more phenyl groups), alkoxy groups (such as ethoxy groups), aryloxy groups (preferably monocyclic groups such as phenyl groups), etc., and these groups have substituents. Examples of substituents include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, thunoid groups, urethane groups, and aryloxy groups. group, sulfur moyl group,
Carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group or carboxyl group, alkyl or aryoloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonyl group Examples include amide group, sulfonamide group, nitro group, alkylthio group, and arylthio group. ), and Ah, A
The sulfonyl group represented by h is specifically described in U.S. Pat.
, 478,928.

As Ah, Ax, hydrogen atoms are most preferable 7-Funenin (
+) Among the groups represented by G, preferably -C
− is.

In the general formula (H, the aliphatic group represented by X is a straight chain,
It is a branched or cyclic alkyl group, alkenyl group or alkynyl group.

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

Preferred as X are aromatic groups and groups represented by (2).

General Niyama) RL R1 Ri! R: (wherein, X represents an aromatic group or a nitrogen-containing heterocyclic group, R A and R g are each a hydrogen atom, a halogen atom,
or represents an alkyl group, and X and RA to rB may have a substituent if possible. r and S do not represent O or 1. ) X is more preferably an aromatic group, and particularly preferably an aryl group.

X may be substituted with a substituent. As substituents,
- In addition to the substituents represented by shipman (δ), examples 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, These include alkyl and aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carbonamide groups, sulfonamide groups, dil.4 groups, alkylthio groups, arylthio groups, and the like.

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

Also, X can include one or more general formulas (darkness).

In the general formula (in the river, the aliphatic group represented by Y is a straight chain,
It is a branched or cyclic alkyl group, alkenyl group or alkynyl group.

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

The heterocycle of Y 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. The heterocycle which may form a condensed ring with an aromatic or heterocycle is preferably a 5 to 6 aromatic heterocycle, such as a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group. , pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group,
Those containing a benzthiazolyl group are preferred.

Y may be substituted with a substituent, and the substituent is
Examples include: These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, monosubstituted 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 when possible.

R1 and R,' in the general formula fat (L is N-
The aliphatic group R1 represented by ) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

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

1 of R and R1' may be substituted with a substituent.

Examples of the W substituent include those listed as substituents for Y in the -line formula fat.

Also, Y and R, , Y and R, □ and R1 and R.

may be connected to each other to form a ring, if possible.

More preferably, R and R1' are hydrogen atoms.

In general formula (I), 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 an N substituent,
A quinolyl group, an isoquinol group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazonilyl group, a cinnolinyl group, or a buteridinyl group, and examples of its substituents include an alkyl group, an aryl group, a halogen atom, a substituted amino group, a cyano group, an acylamino group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a combination thereof.

Further, X or R preferably contains a ballast group 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 (I) 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 an ether group, a thioether group, an amide group, a ureido group, a urethane group, a sulfonamide group, etc. More preferred as the ballast group is a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

■ −3゜ More preferably, the Y　-L　-C-N- group is hydra R.

It is substituted at the 0-position or P-position with respect to the dino group.

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

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

■ 4゜ 6゜ ■ −7゜ ■ 11° \ ■ 8゜ ■ 12° ■ 9゜ ■ 14° ■ 10° H3 Fff 15° ■ 19° ■ 20° 1-17° OC,U.

! 21゜18゜■ 22゜23゜The hydrazine derivative of the present invention can be obtained by treating the corresponding known formylhydrazine 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. It was synthesized by

(Synthesis Example...Synthesis of Compound 1) was distilled off and 1'iv was prepared using silica gel chromatography to obtain the desired product. (Yield: 13.7 g) The chemical structure was confirmed by nmr spectrum, IR spectrum, and elemental analysis.

Other compounds were synthesized in the same manner.

Concentrated hydrochloric acid (4 ad) was added to a mixture of methanol (50 M) and stirred at room temperature overnight. After completely distilling off the volatile components under reduced pressure, acetonitrile (80 m), DMF (2,0 ad)
), pyridine (8d) was added, followed by picolinic acid chloride hydrochloride (5.2g). After stirring overnight at room temperature, the volatile components of the compound of the present invention were added to the photographic emulsion layer again under reduced pressure.
Contained in the hydrophilic colloid layer (~meluni:
After dissolving the compound of the present invention in water or a water-miscible organic solvent (if necessary, an alkali hydroxide or a tertiary amine may be added to form a salt and dissolving), a hydrophilic colloid solution (
For example, when adding to silver halide emulsions, gelatin in water, etc.), add acid or alkali depending on the pressure required. >pH may be adjusted).

The compounds of the present invention may be used alone or in combination of two or more. The amount of the compound ρ added in the present invention is preferably 1 mole of silver halide per 1 mole of silver halide/xIO-" to 10" mole, more preferably 10 mole to 10 mole of silver halide to be combined in the silver halide emulsion. An appropriate value can be selected according to the properties of

The compound represented by formula (I) of the present invention can form a high-contrast negative image 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 high contrast negative image.

When used to form a negative image with high contrast, the average grain size of the silver halide used is preferably fine grains (for example, 67 μm or less), particularly 11CO, 1 μm or less. It is preferable that the particle size distribution is basically unlimited or monodisperse. Here, monodisperse means that at least 1% of the particles are composed of particles having a size within 10 vOtIp of the average particle size.

Silver halide grains in photographic emulsions are cubic, octahedral, 'A
' Regular (regul) like dihedron, /4C-hedron
It may have a crystalline shape, or it may have an irregular shape, such as a spherical or tabular shape.
It may have a crystalline form or a composite form of these crystalline forms.

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

In addition to the formation of silver halide grains, the silver halide emulsion used in the present invention also contains cadmium salt,
A sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, etc. may be coexisting.

The silver halide used in the present invention is 10-8 molar silver per mole of silver.
It is a silver haloiodide prepared in the presence of ~10-5 moles 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. When an emulsion containing such a haloiodide steel is used, photographic characteristics 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. You can.

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, /l radium, and rhodium. Specific examples include U.S. Patent Tsutsuko, 41ul,
No. 060, British Patent No. 6/f, 0/, etc. 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 case, 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, particularly during grain formation.

In the present invention, the silver halide emulsion layer is
In that it is the highest concentration (DMAX) to increase the number of single -dedicated (DMAX) increase (DMAX), as the average particle size, which is disclosed in the issue of / 9, TO O -F, 1.208, is disclosed in the issue. Preferably, the small-sized monodisperse grains are chemically sensitized, and the method of chemical sensitization is most preferably sulfur sensitization.The large-sized monodisperse emulsion does not need to be chemically sensitized, but They may be sensitized.Large-sized monodisperse particles are generally not chemically sensitized because black spots are likely to occur; however, when chemically sensitized, black spots are not generated.
It is particularly preferable not to apply the chemical sensitization shallowly (-).Here, "applying shallowly" means that the time for chemical sensitization is shorter than that of chemical sensitization of small-sized emulsions. This can be done by reducing the amount of chemical sensitizer added.There is no particular limit to the difference in sensitivity between large-sized monodispersed emulsions and small-sized monodispersed emulsions, but ΔallogE is 0, /-/, θ. , more preferably 1 to 0.7, and it is preferable that the value is higher for large-sized monodispersed emulsions.

Here, the sensitivity of each emulsion is determined by coating a hydrazine derivative on a support and applying 1-1 sulfite ion to 0. /j mol/1 or more and pH/θ, j~) of 2.63.

The average grain size of the small-sized monodisperse grains is less than or equal to the average size of the large-sized silver halide monodisperse grains, preferably less than or equal to 10 cm. The average grain size of the silver halide emulsion grains is preferably from 0.0.2μ to
Preferably θ is 0μ. It is preferable that the average grain size of the large size and small size monodispersed emulsions is within this range of /μ to O0 to μ.

In the present invention, when one or more types of emulsions with different sizes are used, the amount of coated silver of the small size monodisperse emulsion is preferably aO to 0 wt%, more preferably 1% by weight, based on the total amount of coated silver.
Preferably, it is 30 to 10wt4.

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 to have the dog size emulsion in the upper layer and the small size emulsion in the lower layer.

The total amount of silver coated is preferably 727 m2 to g27 m2.

The light-sensitive material used in the present invention contains sensitizing dyes (e.g., cyanine dyes, merocyanine dyes, etc.) described in JP-A No. 203θ, No. 100-17, page 17, for the purpose of increasing sensitivity. 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 and exhibits supersensitization. Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure/7A.
Vol. t7tv3 (issued February 1971), page 23, section J is highlighted.

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 benzodeazolium salts, nitroindazoles, chlorobenzimidazole p, bumobenzimidazoles, mercaptothiazoles, mercazotopenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro benzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines 7; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially μm human D-oxy substituted (/, j, Ja ,7)
Tetrazaindene M), -? Indenes, etc.;
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, henzenesulfonic acid, benzenesulfonic acid amide, and the like. Among these, preferred are benzotriazoles (e.g., j-methyl-bencitriazole)
and nitroindazoles (eg!-nitroindazole). Further, these compounds may be included in the treatment liquid f.

Suitable development accelerators or nucleating development accelerators suitable for use in the present invention include JP-A-33-77676, JP-A-773.2, JP-A-737133, and JP-A-6.
0-/410.3μθ No., same t.

-/41. In addition to the compounds disclosed in Rijri issue etc.
Various compounds containing N or S atoms are useful.

The optimum amount of these accelerators to be added varies depending on the type of compound (C, C, O x 10' to 0.J9/m2, preferably 1, O'X, lo-3 to 0./S'/ m2
It is desirable to use it within the range of .

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 the polarographic anodic potential and cathodic potential is positive.

For a method for measuring redox potential using a polarographic method, see, for example, US Patent No. ? ,, rol,, z (described in No. i7. The organic desensitizer button preferably contains at least one water-soluble group, and specifically Vr is a sulfonic acid group, a carboxylic acid group, a sulfonic acid group, etc. These groups may form salts with organic bases (eg, ammonia, pyridine, triethylamine, biharidine, morpholine, etc.) or alkali metals (eg, sodium, potassium, etc.).

As organic desensitizers, general formulas (ITI) to
Those represented by (V) are preferably used.

The organic desensitizer used in the present invention is contained in the silver halide emulsion layer.
. O×IO' ~/, 0X10"-ek/m2, especially t
, oxto-7~/, oxlo-s mol/yy12 is preferably 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 that further reduce photographic sensitivity, preferably ultraviolet absorbers that have a maximum spectral absorption in the intrinsic sensitivity range of halogenated complexes, and dyes that are resistant to safelight light when handled as bright-room sensitive materials. In order to increase safety, dyes having substantial light absorption mainly in the region of 3 f O (Im to l 00 nm) 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 varies depending on the molar absorption coefficient of the ultraviolet absorber, but usually /
0-2? It is added in a range of 7m2 to /9/rn2. Good Pusuke J 0119~j 001n9/m2
There is.

The above-mentioned ultraviolet absorber may be dissolved in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, pro/e-nol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] and added to the coating solution. Can be done.

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an oryl group, a μm thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, an oxoxazole compound, and an ultraviolet absorbing polymer can be used. .

Specific examples of ultraviolet absorbers are disclosed in U.S. Patent J, tJ, ? .

77≠ issue, 3.37≠, 72ψ issue, 3.3j, 2,
No. 611, JP-A No. 4tJ-, 27J'u, U.S. Patent J
, 70. ．． ! F, J'0yo issue, same J, 707, 3.7.
No. 3', 41. IO Hiro J',, No. 2.27, same J, 7
00, 4t11, same j, 41' Tata, 7J, 2, West German patent application publication/, J'≠7. It is described in the ItJ issue etc.

Filter dyes include oxonol dyes, hemioxonol 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. Patent No. 1,274t, 7? The pyrazolone oxonol dye described in U.S. Patent No. 1.
Diarylazo dyes described in U.S. Patent No. 3,4123,2O2, No. J, Jr4t,
41. styryl dyes and butadienyl dyes described in U.S. Pat. No. J'7, 327. ．． Merocyanine dye described in trJ, U.S. Patent No. 3゜$rt<, r5'7,
Same No. J, ITU, XRU No. J, 7/I, ≠7.2
Merocyanine dyes and 4' sonol dyes described in US Patent No. 3.97B.

/J Otsu/No. ((Enaminohemioxonol dye described and British Patent No.
ri issue, Tokukai Sho/J/nee 4. S”130, log 9-9
9/; UO No., Geter/14A4t20, U.S. Patent No. 2. J, 3.3. <t7.2, same No. J, /41-.

/(I'7, same number, ?, /77.071, same number, ?
.

, 24I7. /, No. 27, z3. t4t, o, ray
No. J, t7Jr, 7011, J, tJ
3. The dyes listed in Table 0, Number K, and Number K are used.

The dye can be used in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, pronominol, etc.),
.

The specific amount of dye used is generally lo-3 7m2--
/S'/m2, especially /0-3f/m2~θ
.

Preferred amounts can be found in the range J/7712.

The photographic light-sensitive material of the present invention may contain a hydrophilic hardener such as a chromium salt or an aldehyde.

(Formalde, geltaldehyde, etc.), N
-Methylol compound (dimethylol urea, etc.), active vinyl compound (/, J, J'-) lyacryloyl-hexahydro-5-triazine, /, 3-vinylsulfonyl-
λ-puo no'! Norna), active halo y 7 compounds (2, goudichlor-t-hydroxy-5-) riazine), mucohalogen acids, etc. may be used alone or in combination.

The thickness of the photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material produced using the present invention are as follows. Various surfactants may be included for various purposes such as high contrast, sensitization, etc. In particular, the surfactants preferably used in the present invention are
These are polyalkylene/oxides having molecules it, oθ or more as described in the above publication. Here, when used as an antistatic agent, a fluorine-containing surfactant C is used.
.

In the photographic light-sensitive material 1 of the present invention, which is particularly preferred, silica, magnesium oxide, polyamide, etc. are added to the photographic emulsion layer and other hydrophilic colloids 4 for the purpose of preventing adhesion. A matting agent such as methyl methacrylate may be included.

The universal emulsion of the present invention may contain a dispersion of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. For example, polymers whose monomer components are alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl C meth)acrylate, etc. alone or in combination, or in combination with acrylic acid, methacrylic acid, etc. can be used.

It is preferable that the silver halide emulsion layer and the other seven layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Compounds with acid groups include organic acids such as salicylic acid, acetic acid, and ascorbic acid, as well as acrylic acid, maleic acid,
Mention may be made of polymers or copolymers having acid monomers such as phthalic acid in combination with repeat units. Koi
Regarding the compound knowledge of I et al., patent application No. 7,
Similarly, the descriptions of θ-6J #7.3, o-it, yttX, and 60-/93611 can be referred to. The low molecular compound is ascorbic acid, and the high molecular compound is water dispersibility of a copolymer consisting of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It's latex.

K for obtaining ultra-high contrast and high-sensitivity photographic properties using the silver halide photosensitive material of the present invention is the conventional infectious developer and US Pat. No. 2,441? ,ri7. The car listed in No. 9g) HI3
It is not necessary to use a highly alkaline developer close to that of 100%, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains o, i, t mol/1 or more of sulfite ions as a preservative, and p
H10, j-/ko, 3, especially I) H//, 0-/, 2.
It is possible to obtain a sufficiently high-contrast negative image even with a zero developer.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable to include dihydroxybenzenes, as it is easy to obtain good halftone quality, and dihydroxybenzenes and diphenyl A combination of -3-pyrazolidone systems or a combination of dihydroxybenzenes and p-aminophenols may also be used. The developing agent is usually 0. O
Dihydroxybenzenes are preferably used in amounts of J mol/E to 03 g mol/l.
- When using a combination with pyrazolidones or p-amino-phenols, the pressure is 0°0j mol/l-0. ．．
．． It is preferred to use the latter in an amount of not more than t mol/β, the latter o, ot mol/l.

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 θ. It is preferably at least Hiromole/e, particularly at least 0.3'mol/β.

In the developing solution of the present invention, as a silver stain preventive agent, JP-A-Sho, 5-4.
−． 24t, Jl, No. 17 can be used. Patent application ShoA as a solubilizing agent added to the developer
D-10';', the compound described in No. 74'3 can be used. Further, as a pH buffering agent used in the developer, a compound described in Japanese Patent Application Kokai Sho, <0-5'J, No. 73 or a compound described in Japanese Patent Application Sho t/-j #:, No. 70 may be used. Can be done.

The compound represented by the general formula (I) can be used in combination with a negative-tone emulsion as described above in a high-contrast sensitive material f, and can also be combined with an internal latent image type silver halide emulsion. I will explain the aspects. In this case, the 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-ration layer, etc., as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. It may be a layer.

The content of the compound represented by general formula (I) in the layer,
It is desirable that the amount is such that when the internal latent image type emulsion is developed with a surface developer, a sufficient maximum density (for example, a silver concentration of 0 or more) is obtained. In practice, the appropriate content may vary over a wide range, depending on the properties of the silver halide emulsion used, the chemical structure of the nucleating agent, and the development conditions, or may vary over a wide range. Approximately θ per mole of silver.

A range of from about 0°01R9 to about 100η per mole of silver is preferred. 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. Regarding the definition of internal latent image type silver halide emulsion, see JP-A-6/-/7
Publication No. 0733, page 1O, top column and British Patent No. J, 01P
, Oj'7, pages /J' to KoO.

Preferred internal latent image emulsions that can be used in the present invention include:
Patent application Sho 1, 1-. 1tJ7/J Specification No. 1 page/4'
・Line - No. J/Page 2, with regard to preferred rogenated scissor particles, the same specification, No. 3/Page, 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. As the sensitizing dye, 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 include, for example, JP-A-Sho, 5'
? -tto, tJt No. 39-410, 636 and J'? -j, r, 739, cyanine dyes and merocyanine dyes are included.

The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, they can be developed with a developer containing a color image-forming coupler. Specific examples of these cyan, maze/yellow and yellow couplers that can be used in the present invention are given in Research Disclosure (RD)'/7.
t, 3 (ly-y, v year/February) ■ = D term and the same tr
yt7 (tsp7 year ii month) K is described in the cited patent.

Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, 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. The .alpha.-pivaloylacetanilide coupler has excellent color fastness and special pressure light fastness, while the .alpha.-benzoyl 7-t toanilide non-coupler provides a high color density.

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

As a leaving group for two equivalent pyrazolone couplers, US Patent No. V,! No. 10,6/R, or the nitrogen atom leaving group described in US Pat. No. 4, JJ-/.

The arylthio group described in No. 7 is particularly preferred.

Further, the pyrazolone coupler having a pallast group described in European Patent No. 77, JJ& can provide a high color density.

As a certain pyrazoloazole coupler, U.S. Patent No. 3
, 377.172, preferably the pyrazolo[s,1-C)(/,a,≠]triazoles described in U.S. Pat. No. 3,7λ,t,067, Research. Discology?-,2!12
2.0 (June I9117) and Research Day, fx closure, 2t
, t, 23o (t5Pru year is month). The imidazo(/, , 2-b:) pyrazoles described in European Patent No. 1/1/7G1 are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness. The pyrazolo[1°, r-b:)C1,,2,4L)) riazoles described in RTO are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, such as those described in US Patent No. 74L.

193, preferably the naphthol couplers described in U.S. Patent No. 4Z, 032. ．． No. 212, same! <c.

/44.4.3'? l, issue, same number t! ,,12. r,,
Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. ZJj and No. 200 of the same. Further, specific examples of phenolic couplers include U.S. Pat.
oi, i”yi No. 2,772,764, same No.
2. It is described in ryj, r, tt issues, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat.
Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus described in No. 772,00.2 1. These include z-, t-diacylamino-substituted phenolic couplers and phenolic couplers having a phenylureido group at the λ-position and an acylamino group at the 1-position.

In order to correct unnecessary absorption of short wavelengths by dyes produced from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for 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 US Patent No. 1t, Jtt.

No. 237 and British Patent No. 2. /23. A specific example of a magenta coupler is shown in No. J70, and European Patent No. 2+! ;,
j7i7 and West German Application Publication No.? ,,2J1. A.

No. 777 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. Patent No. j, IAj/,!
No. 20 and No. F, No. 070°211. Specific examples of polymerized magenta couplers are given in British Patent No. 2,10.2. /73 and U.S. Patent No. a, 3
1! ; 7.2r, No. 2 pressure is described.

In order to satisfy the characteristics required for the light-sensitive material, two or more types of couplers used in the present invention can be used together in the same layer of the photosensitive layer, or the same compound can be used in combination with different couplers. It is also possible to introduce more than one layer.

Typical usage amounts for color couplers range from o,ooi to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 00 for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.00 to 0.3
It is a mole.

In the present invention, hydroxybenzenes (e.g. hydroquinone), aminophenols 1, ? - A developing agent such as pyrazolidones may be included in the emulsion or in 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 in response to development of the silver agenide. It can also be used to obtain a desired transferred image on an image-receiving layer after development. 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. a, 03! ,'t21 issue,
41,013,312 and 1t, 336. ! ,2
．． DRR compounds having more 0-hydroxyarylsulfamoyl groups as described in No. 2, etc., and JP-A-Sho J'
It is a Dll(R compound) having a redox core as described in J-i4/-2゜321. When used in combination with such an RR compound, the temperature dependence particularly during treatment is significantly small.

Specific examples of DRP compounds include those described in the above-mentioned patent specifications, as well as magenta dye image-forming substances such as /-hydroxy-cortitra, methylenesulfamoyl-a-1:, ? '-Methyli'(2"-hydroxy-
Hiro"-methyl-j"-hexadecyloxyphenylsulfamoyl)-7enylazo]-su7talene, ie a-
The dye image-forming substance is l-phenyla-3-cyano-
Examples include .mu.m(2''g-tert=-:ethylphenoxyacetamino)-phenylsulfamoyl]phenylaso)-j-pyrazolone.

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

1. After imagewise exposure using the light-sensitive material of the present invention, after fogging treatment with light or a nucleating agent, or after treatment. It is preferable to form a positive color image directly by color developing, bleaching and fixing p) (//) containing an aromatic primary amine color developer using the following surface developer.The pH of this developer teeth//.

More preferably, it is in the range of O to io, o.

The fogging process in the present invention is the so-called "light fogging method".
Either of a method called "chemical fogging method" in which the entire surface of the photosensitive layer is subjected to second exposure to light, and a method called "chemical fogging method" in which development is performed in the presence of a nucleating agent 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 fogging method, the above-mentioned patent application No. 1-21371
The nucleating agent that can be used in the present invention is described in Section 5' of the same specification regarding the nucleating agent that can be used in the present invention.
It is written on page 6 line to page t7 line 2, especially - Sailor CN
-/) and [N-2] are preferably used. Specific examples of these include the same specification No. jt-J-,
(N-I-/) to [N-l-/D] described on page r and the same specification: to UN-II-/) to (N
-II-72] is preferably used.

Regarding the nucleation accelerator that can be used in the present invention, see the same specification No. 4.
J' page// line to page 7/, line 1. Particularly, as a specific example, (A-/
) to (A, -/J) are preferably used.

Regarding the color developer used in the development of the photosensitive material of the present invention, it is described in the same specification, line 4 J'μ, line 2, page 2, and especially aromatic primary amine type. As a specific example of the color developing agent, p-phenylenediamine compounds are preferable, and typical examples thereof include 3-methyl-guamino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3-methyl-guamino Examples include -N-ethyl-N-(β-hydroxyethyl)aniline, 3-methyl-μmamino-N-ethyl-N-methoxyethylaniline, and salts thereof such as sulfates and hydrochlorides.

In order to form a positive color image directly by color diffusion transfer using the photosensitive material of the present invention, 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 by bleach-fixing in a 1 cm bath, 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. In the bleaching solution or bleach-fixing solution of the present invention, an aminopolycarboxylic acid iron complex salt is used as a bleaching agent. 241. J, Specification No. 2,
2. Various compounds described on pages 2-30 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. As a method of water softening treatment, 6, patent application No. 1. /-/J/
Examples include a method using an ion exchange resin or a reverse osmosis device as described in No. 6.32. As specific methods for these, it is preferable to carry out all the methods described in the specification of %B Sho 61-i3i63 Yu.

Further, as additives used in the water washing and stabilization steps, various compounds described in Japanese Patent Application No. Sho J/-32 Gubuko, pages 30 to 36 can be used.

The smaller the amount of replenisher in each treatment step, the better. The replenishment amount is preferably 0.7 to 10 times, more preferably 3 times, the amount of prebath brought in per unit area of the photosensitive material.
~30 times.

Example 1 4X10 per mole of silver in an aqueous gelatin solution kept at 50°C
In the presence of −' molar potassium hexachloride (Ill) and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added for 60 minutes, during which pAg
By keeping the average particle size at 7.8, the average particle size is 0.28μ
A cubic monodisperse emulsion having an average silver iodide content of 10.3 mol % was prepared.

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 and 5°5'-dichloro-9 was added as a sensitizing dye.
-ethyl-3-3'-bis-(3-sulfobrovir)
Oxacarbocyanine and 104 moles of K per mole of silver
1 solution and allowed to stand for 15 minutes, then the temperature was lowered. This emulsion was redissolved at 40°C, and 0.02 mol/m mol of methylhydroquinone and 1.0×10-' mol/Ag of the hydrazine derivative of the present invention or comparative example shown in Table 1 were added.
5-methylbenzotriazole, 4-
Hydroxy-1,3,3a,7-tetrazaindene, the following development accelerators (a) and (b), and a dispersion of polyethyl acrylate at 0°4 g/rrr, and the following compound (c) as a gelatin hardening agent. was added and coated at a silver amount of 3.4 g/rrr on a polyethylene terephthalate support (I5f) 7r) having a waterproof undercoat layer (065μ) made of vinylidene chloride copolymer.

(b) tHs CHz ”' CH30zcHzcIIcHzsO*C
H=Clt as a protective layer on top of this gelatin 1. 5
g/rrr.

Polymethyl methacrylate particles (average particle size 2.5μ) 0
．． 3g/nf, coat a layer containing the following surfactant [Developer -
■〕 [2] Evaluation of photographic properties with exhausted developer Fill an automatic plate-making processor FG660 F 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 clothed.

Surfactant CHzCOOC6Hl5 CHCOOCbH+s 37+wg/rd S O3N a CaF Its O□N CHzC00KC2H?
2.5/dCI) 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 photographic sensitivity and gradation obtained are shown in Table 1. When the nucleating agent of the present invention was used, high sensitivity and high contrast were obtained.

Dry.

(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) Developing with the solution left in the automatic developing machine 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
Exposure so that 50% of the area is developed in a size of cm x 61.0 cm, process 200 sheets a day, and develop with the solution repeatedly for 5 days.Developer solution per sheet processed -■
Replenish 100ee.

(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 is expressed as the difference from the blank sensitivity (#ogE) as a standard. Therefore, for example, -1,0 means j! compared to the blank. ogE indicates 1.0 lower sensation, that is, 10 times lower sensation.

Honhon 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.

Δ3M-A: Difference between sensitivity (S,) when developed with air fatigue solution and sensitivity (Sl) when developed with fresh solution Δ5c-h: Sensitivity when developed with mass processing fatigue solution Difference between sensitivity (SA) when developing with (St) and fresh solution Example-2 5°0X per mole of silver in gelatin aqueous solution kept at 50°C
IO-'moles of (NHO)*Rh CI! After simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of b, gelatin was added after removing soluble salts using methods well known in the art, and 2- Methyl-4hydroxy-1,3,3a,7-
Chitraazaindene 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, polyethyl acrylate latex was added in a solid content of 30 wt% based on gelatin, l,3-vinylsulfonyl-2-propanol was added as a hardening agent, It was coated on a polyester support so that the Ag amount was 3.8 g/d.

Gelatin was 1°8 g/n (on top of this was 1.5 g/d of gelatin as a protective layer and as a matting agent.
Polymethyl methacrylate particles (average particle size 2.5μ) 0
．． 3 g/rd, and the following surfactant as a coating aid:
A protective layer containing a stabilizer and a UV absorbing dye was applied and dried.

Surfactant CHZCOOChHo CHCOOCh Hr 3 SO,, N a 37■/d CaF, ? SO! NCHICOOK C3H12,5■/d Stabilizer thioctic acid 2゜ 1■/M This sample was exposed to light through an optical wedge using Dainippon Screen Corporation's light room printer P-607 at 38°C and 20°C.
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 higher contrast can be obtained with the sample of the present invention than with the sample of the comparative example.

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.

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. ▼ (In the formula, R_0 represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and l_1 represents 1 or 2). G has ▲mathematical formulas, chemical formulas, tables, etc.▼ (m_1 represents 1 or 2), sulfonyl group, sulfoxy group, ▲mathematical formulas, chemical formulas, tables, etc.▼
(In the formula, R_1 represents an alkoxy group or an aryloxy group.), 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 L represents -O-, -S- , or ▲
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼, R_a, R
_a' represents a hydrogen atom, an aliphatic group or an aromatic group. R represents a nitrogen-containing heterocyclic residue.