JPH0220856A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the negative picture having very high contrast and high sensitivity and the good dot picture quality of the title material by incorporating a hydrazide or a compd. having a ring structure which is ring-opened with a nucleophilic attack, in the photosensitive material. CONSTITUTION:The part or the whole of the hydrazine compd. which is ordinary used for forming a negative picture having a high contrast or a direct reversal picture, is substituted with the hydrazide or a compd. having the ring structure capable of forming an anion of a conjugate base which is ring-opened with the nucleophilic attack. The compd. having the ring structure is exemplified by the compd. shown by formula I. In the formula, R1 is an aliphatic or an aromatic group which may be substd., R2 is hydrogen atom or a substituting group, D is C=O or C=S group or C=NH group which may be substd., SO, SO2 or N O group, etc., E is oxygen or sulfur atom. Thus, the photographic characteristics of the photosensitive material, such as the very high contrast and the negative gradation are obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is a silver halide 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 material containing a novel compound as a nucleating agent for silver halide.

(Prior Art) The addition of hydrazine compounds to silver halide photographic emulsions and developing solutions is disclosed in US Pat. No. 3,730.

No. 727 (developing solution combining ascorbic acid and hydrazine), 3. Cocoa, No. 552 (using hydrazi/ as an auxiliary developer to obtain a direct positive color image), No. 3
°, 3rt, rJi No. (contains β-7menophenyl hydrazide, an aliphatic carboxylic acid, as a stabilizer for silver halide sensitive materials), Rhiro/Ri, Ri No. 7j, and Mies (M
The Theory of Photographic Process (The Theory of Photographic Process)
tographicProcess) 3rd edition (2011), page 2r1, etc.

Among these, in particular, U.S. Patent No. λ, Hiroki et al.

77! No. 1, it is disclosed that high-contrast negative images can be obtained by adding a hydrazine compound.

In the same patent specification, a hydrazine compound is added to a silver chlorobromide emulsion, and /2. It is stated that when developed with a high pH developer such as r, extremely high-contrast custom photographs with a gamma (γ) of over 10 can be obtained. However, the pH/
A strong alkaline developer close to 3 is unstable and susceptible to air oxidation, and cannot withstand long-term storage or use.

Ultra-high-contrast photos with a gamma exceeding /θ are custom-made for negative images,
Halftone images useful for printing and plate making (
It is extremely useful for photographic reproduction of continuous tone images or reproduction of line drawings. Conventionally, for this purpose, a silver chlorobromide photographic emulsion with a silver chloride content of about 0 mol%, preferably more than 73 mol%, is used, and the effective concentration of sulfite ions is kept extremely low (usually 0 mol%). ,
A method of developing with a hydroquinone developer containing imol/11.1 mol/1. 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 line drawings.

The present inventors have disclosed that U.S. Pat.
/Jr, No. 477, No. II, No. 2113.739, No. 27, No. J/G, No. 4t, ! ,23,Ag3
No. 1, etc., disclosed silver halide photographic emulsions that use stable developers and provide extremely high contrast negative photographic properties, but it has become clear that the acylhydrazine compounds used in these emulsions have several drawbacks.

In other words, these conventional hydrazines are known to emit nitrogen gas during the development process, and these gases tend to collect in the film and form bubbles, damaging the photographic image. It leaks into the developing processing solution and has an adverse effect on other photographic materials.

In addition, these conventional hydrazines are required in large quantities for sensitization and high contrast, and other sensitization techniques (such as chemical Compounds that enhance sensitization, increase particle size, and promote sensitization are described in U.S. Patent Nos.μ, 7, tθ2 and Dohiro, KO≠l, /l. When used in combination with (e.g.), there are cases where sensitization and enhancement over time during storage generally occur.

Therefore, there is a need for an additive that can reduce the generation of air bubbles and leakage into the developing solution, has no problems with stability over time, and can provide extremely high-contrast photographs with the addition of a very small amount. was.

Mata, U.S. Patent No. T, T, 3 IRT, IOR, Doko 2
-6, Takota, Dohiro, 2413.73, it is possible to obtain extremely high-contrast negative gradation photographic properties by using hydrazines having substituents that are easily adsorbed to silver halide grains. However, among the hydrazine compounds having adsorbent groups, those specifically mentioned in the above-mentioned known examples have a problem of causing desensitization over time during storage.

Therefore, it was necessary to select a compound that would not cause this problem.

On the other hand, there are various direct positive photography methods, including a method in which silver halide grains are fogged in advance, 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 the silver halide grains and mainly form latent images inside the grains are called internal latent image type silver halide emulsions, and are mainly formed on the surface of the grains. They can be distinguished from l.silver halide grains on which latent images are formed.

A method of directly obtaining a positive image by surface-developing an internal A-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. There is.

In the above method for obtaining a direct positive image, the nucleating agent may be added to the developer, but it can be added to the photographic emulsion layer or other strong layer of the light-sensitive material so that it is adsorbed onto the surface of the silver halide grains. Better inversion characteristics can be obtained when

The nucleating agent used in the above method for obtaining a direct positive image is disclosed in US Pat. ! tJ, 7rJ-No. 21
The hydrazine compound described in Yo J'J', Ri J'2, and the hydrazine compound described in U.S. Pat. No. 3.2.27,652, U.S. Pat. '
6/! ,t/! No., 3,7/ri, Datahiro No., 3,7
3μ, No. 73r, same≠.

Ori<t, A13 Obi Dohiro, //! , /22, British Patent No. 1,213. lrj! No., Tokukai Akira! 2-3≠2
The heterocycle No. pR described in No. r2-12AlJ
Chloride, U.S. Patent No. 030゜225, Dohiro, 0
3/, /Core issue, Dohiro, 13ri, No. 317, Same 11,2
1Aj, OJ No. 7, same.

2j1, 1/l No. Okobi Dohiro, 27t, Jt4 No.

Thiourea-bound acylphenylhydrazine compounds described in British Patent No. British Patent No. 2,0/l
, a phenylacylhydrazide/compound having a heterocyclic group having a mercapto group as an adsorption type described in J27B, and a substituent with a nucleating effect described in U.S. Patent No. 3.7/1,4170 in the molecular structure. The sensitizing dye inside, published by Tokukai Sho!
Tar No. 200, 230, same! ? -212, r, No. 21,
Same jter 2/, 2, 1.2 issue, Re5earchpi
Hydrazine compounds described in sc 1osure magazine, No. 23rio (/1953/77) are known.

However, all of these compounds have insufficient activity as nucleating agents, and those with high activity have insufficient storage stability, and 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 more types are added.

In order to solve these drawbacks, JP-A-60-179.7
No. 34, No. 61-170,733, Patent Application No. 60-20
No. 6,093, No. 60-19,739, No. 60-11
Adsorption type hydrazine derivatives described in No. 1.936, or JP-A-62270-948, JP-A-63-29
Hydrazine derivatives having specific groups such as those described in No. 751 have been proposed, but in order to further improve storage stability, the hydrazide moiety that is easily oxidized should be changed to a stable structure, and the hydrazide structure should be changed during development. Alternatively, there was a need for a way to quickly generate the conjugate base.

C. Problems to be Solved by the Present Invention] Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent storage stability and is capable of obtaining photographic properties of extremely high contrast negative gradation. That's true.

A second object of the present invention is to provide a direct positive silver halide photographic material with excellent storage stability.

[Means for solving problems]

The object of the present invention is to open a part or all of the hydrazine compound, which has been conventionally used to form high-contrast negative gradation or direct reversal images, by undergoing nucleophilic attack and converting it into hydrazide or its conjugate base. This was achieved by replacing a certain anion with a compound having a cyclic structure.

Preferred examples of compounds having this cyclic structure include compounds represented by the following general formula (1).

General formula (1) [wherein R3 represents an optionally substituted aliphatic group or aromatic group, R3 represents a hydrogen atom or a substituent,
D is C-0, C=NH, S which may be substituted with C=S
o, So, , N→0, or optionally substituted P
(0) represents H, and E represents O or S. In the general formula (1), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. In addition, this alkyl group is an aryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

The aromatic group represented by R1 in the general formula (+) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group, and the aryl group or unsaturated heterocyclic group of R3 may be substituted. Typical substituents include linear, branched, or cyclic alkyl groups (preferably carbon 1 to 20 carbon atoms), aralkyl groups (preferably monocyclic or bicyclic alkyl moieties having 1 to 3 carbon atoms), alkoxy groups (preferably carbon atoms of 1 to 20 carbon atoms), substituted amino groups ( an amino group (preferably substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably one having 2 to 30 carbon atoms),
Examples include a sulfonamide group (preferably having 1 to 30 carbon atoms) and a ureido group (preferably having 1 to 30 carbon atoms).

The alkyl group represented by Rt in general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, or phenyl group.

The aryl group is preferably a monocyclic or bicyclic aryl group, such as one containing a benzene ring. This aryl group is, for example, a halogen atom, an alkyl group, a cyan group,
It may be substituted with a carboxyl group, a sulfo group, etc.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

A monocyclic group is preferable as the aryoloxy group, and examples of the substituent include a halogen atom.

The amino group is an unsubstituted amino group and a carbon number of 1 to 10
An alkylamino group or an arylamino group is preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an alkoxycarbonyl group, which may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R2, when G1 is a carbonyl group, preferred are a hydrogen atom, an alkyl group (e.g.
methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.),
Aralkyl group (e.g. 0-hydroxybenzyl group etc.)
, aryl group (e.g., phenyl group, 3.5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4
-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

As the substituent for R1, in addition to the substituents listed for R1, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, and a yanitro group can also be used.

Also, R2 splits the E-C-R1 part into the remaining molecules,
It may be one that causes a cyclization reaction to produce a cyclic structure containing the atom of the E-C-R1 portion, and specifically, one that can be represented by general formula (a). .

General formula (a) Ra ZI In the formula, Zl is a group that nucleophilically attacks the carbon atom bonded to E and can split the E-C-R3-z+ moiety from the remaining molecules, and R8 With one hydrogen atom removed, Zl makes a nucleophilic attack on the carbon atom l bonded to E, and a cyclic structure can be generated by the carbon atoms R1 and ZI bonded thereto.

More specifically, when the hydrazine compound produced from the compound of general formula (1) generates the next reaction intermediate by oxidation etc., ZI easily nucleophilically attacks the bonded carbon atom, resulting in R, -N= A group that can split N-C-R, -Z R, -N=N group from G+, specifically OH, SH or NHRa (Ra is a hydrogen atom, an alkyl group, an aryl group, CORs or - so
w R5 and R3 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), or may be a functional group that directly reacts with G such as C0OH (here, OH, S H , NHR4, -COOH may be temporarily protected so that these groups are generated by hydrolysis with an alkali, etc.) Or -C-R6, -C-R6 (R1 and Rt are hydrogen atoms, (representing an alkyl group, alkenyl group, aryl group, or heterocyclic group) can react with a carbon atom bonded to El by reacting with a nucleophile such as a hydroxyl ion or a sulfite ion. It may be a functional group such as

Furthermore, the ring formed by the carbon atoms R3 and Z bonded to E is preferably 5- or 6-membered.

Among those represented by formula (a), preferred are those represented by general formulas (b) and (C).

General formula (b) In the formula, Rh' to Rb' are a hydrogen atom, an alkyl group (preferably one having 1 to 12 carbon atoms), an alkenyl group (preferably one having 2 to 12 carbon atoms), or an aryl group (preferably one having 2 to 12 carbon atoms). 6 to 12 carbon atoms), and may be the same or different. B is an atom necessary to complete a 5-membered ring or 6-membered ring which may have a substituent, m and n are 0 or 1, and (n+m) is 1 or 2.

Examples of the 5- or 6-membered ring formed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

ZI has the same meaning as general formula (a).

General formula (e) C3 +N±1-÷CRc 'Rc'' Child Z+Rc in the formula
'%Rc' represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different.

Rcl represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p represents 0 or 1, q is 1
- represents 4.

Re', Re'' and Rc' may be bonded to each other to form a ring as long as the structure allows Zl to make an intramolecular nucleophilic attack on the carbon atom bonded to E.

Rc'%Rc'' is preferably a hydrogen atom, a halogen atom, or an alkyl group, and Rc3 is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is 1, p represents 1 or 2; when q is 2, p represents O or 1; when q is 3, p represents 0 or 1; Or when 3, C
Rc′ and Rc” may be the same or different.

2 has the same meaning as general formula (a).

R1 or R6 in general formula (1) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

Ro or R2 in the -S formula (1) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
．． No. 347, JP-A-59-195.233, JP-A No. 59-195.
200゜231, 59-201,045, 59
-201.046, 59-201.047, 5
9-201.048, 59-201,049, JP-A-61-170.733, JP-A-61-270,744
No. 62-448, patent application No. 62-67.508,
Examples include groups described in No. 62-67.509 and No. 62-67.510.

Preferred examples of the optionally substituted C═NH substituent represented by D include alkyl, aryl, alkoxy,
Aryloxy, hydroxy, and oxyl (-〇)
Particularly preferred are substituted or unsubstituted alkyl groups having 1 to 18 carbon atoms, substituted or unsubstituted phenyl groups having 6 to 18 carbon atoms, and 1 to 18 carbon atoms.
Examples include a substituted or unsubstituted alkoxy group having 6 to 18 carbon atoms, a substituted or unsubstituted phenoxy group having 6 to 18 carbon atoms, and a hydroxy group.

Preferred examples of the optionally substituted substituent of P(0)H represented by D include alkyl, aryl, alkoxy, and aryloxy, particularly preferably substituted or unsubstituted groups having 1 to 18 carbon atoms. an alkyl group having 6 to 18 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, and a substituted or unsubstituted phenoxy group having 6 to 18 carbon atoms. It will be done.

Particularly preferred as D is C=0 or C=S, and particularly preferred as E is 0.

Specific examples of compounds represented by formula -a are shown below. However, the present invention is not limited to the following compounds.

l-1) ■-2) ■ ■ -5) ■ ■ Cz 11 s ■ ■ CHzC) lzcHzsH ■ -N ! -25> ■ ■ tHs Js tL;sll++ +-31) ■ ■ ■ +-34) l In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCHDISCLO5URE
Item23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
80.207, 4,269.929, 4.27
No. 6.364, No. 4,278,748, No. 4,385
, No. 108, No. 4,459.347, No. 4,560,
No. 638, 4. No. 478.928, British Patent 2,0
11,391B, JP-A-60-179734, JP-A No. 62
-270,948, 63-29,751, JP-A-61-170.733, JP-A-61-270,744,
No. 62-348, No. 217.310, Patent Application No. 61-
No. 175.234, No. 61-251,482, No. 61
-268,244, 61-276.283, 6
2-67.528, 62-67゜529, 62
-67.510, 62-58.513, 62-
No. 130,819, No. 62-143,467, No. 62
-166.117 can be used.

Next, a method for synthesizing the compound represented by the general formula (1) of the present invention will be explained by giving a synthesis example.

Synthesis example Compound! Synthesis of -30 To 30 g of 2-(4-aminophenyl)-1-formylhydrazine, 300 m7 of N,N-dimethylacetamide and 70 @l of triethylamine were added and dissolved, and the mixture was cooled to -10°C. 40 g of phenyl chloroformate was added dropwise to this over 30 minutes. During this time, the liquid temperature rose to 5°C.

Then triethylamine 60- was added and 3-(2,5-
Di-opentylphenoxy)propylamine 58.3
g was added thereto, and the mixture was stirred at 60°C for 1 hour. After the reaction solution was cooled to room temperature, 900 m7 of 0.5 molar hydrochloric acid was added and extracted with ethyl acetate. After ethyl acetate was distilled off, the residue was treated with silica gel chromatography (eluent: ethyl acetate-chloroform 1:2) to obtain a small amount of crude crystals of compound T-30. This was recrystallized from acetonitrile and 1.2g
Compound 1-30 was obtained.

Melting point 156-157°C The compound represented by the general formula (1) of the present invention is a hydrazine compound represented by the following general formula (a), the general formula (a) R+ NHNHCRx [wherein R1, R2, and E are general Representing a group with the same meaning as the definition in formula (r)] Synthesis by reacting a compound represented by the following general formula (b) in the presence of a base such as triethylamine, preferably a strong base with a pKw of 9 or more. I can do it.

General formula (b) Lg-D-Lg' [The characters in the formula represent the same groups as defined in general formula (1), and Lg and Lg' represent groups that can be eliminated as anions.] Lg and Lg' Examples include halogen atoms such as C1, Br, and 1, sulfonato groups such as PhSO3, azolyl groups such as imidazolyl, and arylthio or alkylthio groups such as PhS.

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

The compound of the present invention may be used alone or in combination of two or more, or may be used in combination with a hydrazide generated by ring opening of the compound of the present invention. The amount of the compound of the present invention to be added is preferably lXl0-'~5 per mole of silver halide
X I O-'' mol, more preferably 2X10-'mol-1X10-' mol. An appropriate value can be selected depending on the properties of the silver halide emulsion to be combined.

The compound of the present invention (for example, a compound represented by the general formula (RI)) can form a high-contrast negative image when used in combination with a negative emulsion.On the other hand, when used in combination with an internal latent image type silver halide emulsion, It is preferable that the compound of the present invention, for example, the compound represented by general formula (I), be used in combination with a negative emulsion to form a negative image with high contrast.

When used to form a negative image with high contrast, the average grain size of the silver halide used is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less. jμ or less is preferable. There is basically no limit to the particle size distribution, but
Monodispersity is preferred. Monodisperse here means at least that much in terms of weight or number of particles! This means that particles are composed of a group of particles whose size is within ±μθ of the average particle size.

Silver halide grains in photographic emulsions are cubic, octahedral, diamond/
-Regular, such as a hedron or a dihedron
It may have irregular crystals such as spherical or tabular crystals, 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.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

The silver halide used in the present invention is 1O-8 per mole of silver.
It is a silver haloiodide which is prepared in the presence of ~10 moles of iridium salt or its complex salt, and whose silver iodide content on the grain surface is higher than the grain average silver iodide content.

When an emulsion containing such a silver haloiodide is used, photographic properties with a high sensitivity layer and high 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, noradium, rhodium, etc. Specific examples are U.S. Patent Tsutsuko, 4t gr, o
No. to, British Patent No. TL♂, No. 07, etc. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, extreme sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines 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, especially during grain formation.

In the present invention, the silver halide emulsion layer is manufactured by Japanese Patent Application No. 60-4!
It is preferable to include two types of monodisperse emulsions with different average particle sizes as disclosed in Japanese Patent Application No. 1986-23.20, Tata No. The 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 monodisperse particles are not subjected to chemical sensitization because they tend to generate black spots, but when chemical sensitization is carried out, it is particularly preferable to apply the chemical sensitization shallowly to the extent that black spots do not occur. Here, "shallow application" means that chemical sensitization is performed for a shorter time than chemical sensitization of small-sized particles, at a lower temperature, and by reducing the amount of chemical sensitizer added. be. There is no particular limit to the sensitivity difference between large monodisperse emulsions and small monodisperse emulsions, but Δlog
E is 0, /~/, θ, preferably O, ko~o,
It is preferable to use a large size monodispersed emulsion.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative and adding sulfite ions to O6/! It is obtained when processing using a developer having a pH of 10,j to 72.3 and containing mol/1 or more.

The average grain size of the small-sized monodisperse grains is below the average size of the large-sized silver halide monodisperse grains, preferably 10 times or less. The average grain size of the silver halogenide emulsion grains is preferably from 0.02μ to 0.02μ.
μ is more preferably 0. /mu~O0! It is preferable that the average particle size of large size and small size monodisperse particles is included in this range.

In the present invention, when two or more types of emulsions of different sizes are used, the coating silver amount of the small size monodisperse emulsion is preferably 1.0% with respect to the total coating silver amount. Lo-Owt person, more preferably! I am in charge of O~rOwt.

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

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

In addition, the total amount of coated silver is /? / I7!2~!
9/m2 is preferred.

The photosensitive material used in the present invention includes JP-A-77-! 20! No. 0 μ! The sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described on pages 1 to 3 can be added. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that 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 (
Research Disclosure) / Volume 76 /
7J4! J (published in December 1971), page 23, section 5.

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 benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, indithiazoles, nitrobenzotriazoles, mercazotopyrimidines; mercazototriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly μm hydroxy-substituted (/, J, Ja, 7
) Tetrazaindene U), pentaazaindene G;
Many compounds known as antifoggants or stabilizers can be added, such as benzene sulfonic acid, benzene sulfinic acid, benzene sulfonic acid amide, and the like. Among these, preferred are benzotriazoles (e.g., !-methyl-benzotriazole)
and nitroindazoles (eg!-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 include JP-A-3-77J/Otsu, Ibid. Hiro-37732, same! 3-137/33, same to
-iaoJao issue, same! O-/4ri! In addition to the compounds disclosed in No. 1, various compounds containing N or S atoms are effective.

The optimum amount of these accelerators to be added differs depending on the class 11 compound, but 1. oxlo-3~o,! f/m2, preferably z, 0X10-3 to 0. It is desirable to use it within the range of /f/m2.

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

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

A polarographic method for measuring redox potential is described, for example, in US Patent No. 3,10/307.

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

As organic desensitizers, compounds of the general formula (II[l to (V
) is preferably used.

The organic desensitizer in the present invention is K1 in the silver halide emulsion layer.
．． 0x10-8~/, 7~2 in Ox10-'%, especially /
, 0 yen, 10-7 to/, O x 10-5 mol/m2 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 spectral absorption maximum in the intrinsic sensitivity range of silver halide, and dyes that are resistant to safelight light when handled as bright-room sensitive materials. In order to increase safety, dyes with substantial light absorption mainly in the region of 3 J' Onm- to 600 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.

Although it varies depending on the molar absorption coefficient of the ultraviolet absorber, it is usually 10
It is added in a range of 97-2 to /li/fi2. Preferably it is 60m9 to 00m97m2.

The above-mentioned ultraviolet absorber can be dissolved in a suitable solvent [eg, water, alcohol (eg, methanol, ethanol, pronominol, etc.), acetone, methyl cellosolve, 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 ≠-thiazolidone compound, a benzopheno 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 are given in US Patent j, jJJ.

7 tag issue, 313/Hiro, 7 Rihiro issue, 3.3jx, t
ri issue, Tokukai Sho! J-271'41, U.S. Patent J, 7
0! , Za03, J, No. 707,371, G, 04
L! , No. 22, 3,700. Hiro! J issue, same 3. Hirotata, No. 762, West German Patent Application Publication/, 417,163
It is written in the number 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, pyrazolone oxonol dyes described in U.S. Patent No. λ, 27μ, 7r, U.S. Patent No. 2. Diarylazo dyes described in U.S. Patent No. 3. ≠JJ, No. 207, same No. 3.3g≠Hiro? 7
The styryl dyes and butadienyl dyes described in US Patent No. J,! 27. Jr. 3, U.S. Pat. No. 3.1 Art, 197, U.S. Patent No. 3. Jju, J
flA No. 3. 'yir, merocyanine dye and oxonol dye described in Ko 72, US Patent No. 3.27t
.

Enaminohemioxonol dyes described in J4/ issue and British Patent No. tru, to2, British Patent No. 1,177, ≠ Utah, Japanese Patent Publication No. 7RRT3O, Japanese Patent Publication No. 7RRT3O, Patent No. 620,
Same≠ter//ulA20, US Patent No. 2. ! 33.
Hiroshi No. 71, same No. J, iar.

ir'y issue, same number 3. /77.071, same No. 3゜21
A7, No. 127, same No.! , 1110. ♂r7, same number 3
．． ! 7J-, No. 7041, No. 3. Goodbye 3. Ri Oj issue,
The dye described in is used.

The dye can be prepared in a suitable solvent [e.g. water, alcohol (e.g. methanol, ethanol, propatool, etc.), acetone,
Methyl cellosolve, etc., or a mixed solvent thereof] and added to the coating solution for a non-photosensitive hydrophilic colloid layer of the present invention.

The specific amount of dye used is generally 10 2 /m 2 ~/
5'/~2, especially /09/m2~0.

Z? A preferred amount can be found in the range of 7 m2.

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

For example, chromium salts, deldehydes, (formaldehyde,
geltalaldehyde), N-methylol compound (
dimethylol urea, etc.), active vinyl compounds (/, j,
j-1 lyacryloyl-hexahydro-5-triazine, l,3-vinylsulfonyl-copro/ξnornato), active halogen compound 1z, tA-dichloro-6-hydroxy-5-triazine, etc.), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (such as development acceleration, high contrast, etc.). 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! ! -2≠/2 These are polyalkylene oxides having a molecular weight of too or more described in Publication No. 2. When used as an antistatic agent, a fluorine-containing surfactant (for details, refer to U.S. Pat.
, 20/, No. 116, JP-A No. 6 O-IQrty, J.
P-74tJrl1) is particularly preferred.

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

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

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Compounds with acid groups include organic acids such as salicylic acid, acetic acid, ascorbic acid, acrylic acid, maleic acid, etc.
Mention may be made of polymers or copolymers having acid monomers such as tarlic acid as repeat units. Regarding these compounds, Patent Application No. 1986-66/7. −
Reference may be made to the descriptions in the specifications of trr'y No. 3, trr'y 60-/, t31J-, and trr'y JO-/9yo-6. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and acid monomers such as acrylic acid and crosslinking monomers having two or more unsaturated groups such as divinylbenzene as high molecular compounds. It is a water-dispersible latex of copolymer.

In order to obtain photographic characteristics of ultra-high contrast and high sensitivity using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or US Patent No. 2.4! ri, ri7! The pH listed in the issue is 1! 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 sulfite ions as a preservative at a concentration of 0. /jmol/! Including above, pH
1O,j-/ko, 3, especially p)(//,D~/2,0
A sufficiently high contrast negative image can be obtained using this developer.

The developing agent used in the developer used in the present invention is not particularly limited, but it preferably contains dihydroxybenzenes, since it is easy to obtain good halftone quality, and dihydroxybenzenes and l-phenyl are preferred. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used. The developing agent is usually O,
OS child OS mole 0. Preferably it is used in an amount of r mol/E. Also, dihydroxybenzenes /-phenyl-
When using a combination with 3-pyrazolidones or p-amino-phenol, the former is O0O! Mol/lNOl
It is preferred to use the latter in an amount of up to 0,0 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 is O1 mol/! In particular, two or more O,S morphs are preferred.

The developing solution of the present invention contains JP-A-6-1 as a silver stain preventive agent.
The compound described in μ, j #7 can be used. Patent application 1986-109 as a solubilizing agent added to the developer.
Compounds described in No. 7 Ko No. 3 can be used. Further, as a pH buffering agent used in the developer, JP-A No. 2006-23-1999. Compounds described in Kou No. 33 d or Patent Application No. 1973/-, 2J',
Compounds described in No. 701r can be used.

The compound represented by the general formula (I) can be used in high contrast sensitive materials in combination with negative emulsions as described above, and can also be used in combination with internal latent image type silver halide emulsions. Let's talk about. In this case, the general formula rI)
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 antihalation layer, etc., as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. You can.

The content of the compound represented by general formula (I) in the layer is such that when the internal latent image type emulsion is developed with a surface developer, it provides a sufficient maximum density (for example, a silver concentration of 0 or more). It is desirable that the amount is sufficient. 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 about 00 oosmg to roomg per mole of silver is useful in practice;
Preferably, it is about o, o1mg to about 10Q per mole of silver.
It is m9. 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 emulsions, see Japanese Patent Application Laid-Open Publication No. 7073.3, page 1, top column, and British Patent No. 1, or 2, O! It is described in Publication No. 7, pages 1f to 20.

Preferred internal latent image emulsions that can be used in the present invention include:
Patent Application No. 1986-Colo 3716 Specification No. Preferable silver halide grains are described in page 31, line 3 to page 3, line 1 of the specification box, line Z to page 37, line 2.

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, oquinol dyes, hemioquinol dyes, etc. can be used. These sensitizing dyes include, for example, JP-A-Sho! Tar μO1 Otsu 3g issue, same! Day I10. tJt issue and 39-
Cyanine dyes and merocyanine dyes described in No. 31,739 are included.

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

Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided in Research Disclosure (RD)/714! j (December 1971) ■-D
It is described in the patent cited in Section 1 and Try17 (January 1, 2015).

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 ye a-cazole, and representative examples thereof include an oxygen atom elimination type ye a-coupler or a nitrogen atom elimination type yellow coupler. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as yoichi pyrazolone and pyrazolotriazoles. The j-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with a 7-arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.

As a leaving group for a two-equivalent pyrazolone coupler, U.S. Patent Tube μ, J10. Particularly preferred are the nitrogen atom leaving groups described in US Pat. No. V, 311°R. Also, European patent cylinder 73
, No. 636, the pyrazolone coupler having a pallast group can provide a high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
372,229, preferably the pyrazolo[s,1-cl(/,2.μ)] triazoles described in U.S. Pat. Examples include pyrazolotetrazoles described in Hirokoko O (/Ir4c, June 2013) and pyrazolopyrazoles described in Research Disclosure 2H3o (/Ir4c, June 2013). European Patent No. 11 and 74 (Imidazo (/
, J-b) Pyrazoles are preferred, and European patent cylinder 1/
Pyrano a (/.

r-b](l,cot'') triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers; US Pat. .

The naphthol couplers described in λri No. 3, preferably U.S. Pat. xt No. 2, same No. DA.

/176, Jri No. 6, 2-equivalent naphthol couplers of the oxygen atom separation type described in Kou No. 1.2, No. 233 and Kou No. 2, No. 6.200 are listed as representative examples. ra, ru. Further, specific examples of phenolic couplers are given in U.S. Patent No. 2. JJ Ri, No. 929, No. 2. IrO/, 1
No. 71, same No. x, 772. /Ju issue, same No. 2. ryz,
It is described in rλ6, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention;
A typical example is U.S. Patent No. J, 772.00-
Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group in the meta-position of the phenol nucleus, described in No. 2
．． It has a j-diacyl amino substituted phenolic coupler and a phenylureido group at the co-position and! These include phenolic couplers having an acylamino group at the - position.

In order to correct unnecessary absorption of short wavelengths possessed by dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing.

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 Pat.

No. 237 and British Patent No. 2. /Koyo, a specific example of a magenta coupler is shown in No. 170, and a European patent case t, j7
No. 0 and Tori German Application Publication No. 3.23 Hiro.

No. 533 describes specific examples of yellow, maze/red or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 20 and No. g, oro.

It is described in issue 2//. Specific examples of polymerized magenta couplers are given in British Patent No. 2,102. No. 73 and US Pat. No. 367.222.

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

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably yellow couplers with IdO,0/no (,
o, r mole, 0. for magenta coupler. OOJ Na-shi0
．． 3 mol, and o, oox or 0 for cyan couplers
．． It is 3 moles.

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

The photographic emulsion used in the present invention is subjected to appropriate development processing in combination with a dye image-providing compound (c coloring material) for color diffusion transfer that releases a diffusible dye in response to development of silver halide. It can also be used later to obtain a desired transferred image on an image-receiving layer. 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, DR having an N-substituted sul7amoyl group
R compounds are preferred. Particularly preferred for use in combination with the nucleating agent of the present invention are US Pat. J/Co issue and μ, 336. DRR compounds having an 0-hydroxyarylsulfamoyl group as described in No. J2λ, etc., and JP-A-ShojJ-/4! the law of nature.

It is a DRR compound having a redox core as described in No. 321. When used in combination with such an RR compound, the temperature dependence particularly during treatment is significantly small.

Specific examples of DRR compounds include those listed in the above-mentioned patent specifications, as well as magenta dye image-forming materials.
-Hydroxy-cochtramethylenesulfamoyl-u
-(J'-Methyl-Hiro'-(2"-Hydroxy-≠"-
Methyl! "-hexadecyloxyphenylsulfamoyl)-phenylazo]-naphthalene, yellow dye image-forming substance h/-phenyl-3-cyano-, got
Hiro””;-tert-:methylphenoxyacetamino)-phenylsulfamoyl]phenylaso)-! - Examples include pyrazolone.

For details of color couplers that can be preferably used in the present invention, refer to Section 3 of the same specification! They are written on pages lr line to a0 page last line, respectively.

After imagewise exposure using the light-sensitive material of the present invention, after or while carrying out oxidation treatment with light or a nucleating agent, pH/1. It is preferable to form a positive color image directly by performing color development, bleaching and fixing treatment with a surface developer of r or less. The pH of this developer is /l.

More preferably, the range is o-io, o.

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

Regarding the Hikari Kabushi method, the above-mentioned patent application No. 4/-, 2!37
/ are described on page 7, line ψ to page j of the specification box, and regarding the nucleating agent that can be used in the present invention, see the specification box ≠
It is described on page 7, line O to page t7, line λ, especially the general formula C.
Preference is given to using compounds represented by N-/:l and [N-λ]. A specific example of these is the statement box! (N-I-/E~[:N-l-10] described on pages 6-1 and [:N-I[-/'']~ described on pages 63-JJ of the same specification)
(N-In-l) is preferably used.

Regarding the nucleation accelerator that can be used in the present invention, see Box t of the same specification.
It is described in page r, line 1 to page X, page 71, line 3, and a specific example of this is (A-/) described in page 6 to page 70.
~(A-/J) is preferably used.

The color developing solution used in the development of the photosensitive material of the present invention is described in the same specification, box 71, line ψ to page 72, especially aromatic primary amine color developing agent. As a specific example, p-phinidinediamine type compounds are preferable, and representative examples thereof include 3-methyl-Hiro-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3-methyl- Hiro-amino-N-ethyl-N
Examples include -(β-hydroxyethyl)aniline, 3-methyl-guamino-N-ethyl-N-methoxyethylaniline, and salts thereof such as sulfates and hydrochlorides.

In order to directly form a positive color image by a color diffusion transfer method using the light-sensitive 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.

Bleaching is carried out at the same time as fixing, using a one-bath bleach-fixing process.
or may be performed individually. 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. Additives used in the bleaching solution or bleach-fixing solution of the present invention include those described in Japanese Patent Application No. Sho t/-3jVt1, pages 22 to 3.
A variety of compounds described on page 0 can be used. After the desilvering step (bleach-fixing or fixing), treatments such as water washing and/or stabilization are performed. It is preferable to use softened water as the washing water or stabilizing liquid. Examples of the water softening treatment include a method using an ion exchange resin or a reverse osmosis device as described in Japanese Patent Application No. Sho g/-/3/632. These specific methods are described in Tokugan Sho J/
It is preferable to carry out the method described in the specification of No. -/J/lJ-.

Further, as additives used in the water washing and stabilization steps, various compounds described in Japanese Patent Application No. 1983-32 Hiroshi≦2, pages 3 to 36 can be used.

It is preferable that the amount of replenisher in each treatment step be as small as possible. The amount of replenisher is 0.00% relative to the amount of prebath brought in per unit area of the photosensitive material. /-50 times is preferable, more preferably 3
~30 times.

(Example) Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example-1 4XI per mole of silver in an aqueous gelatin solution kept at 50°C
In the presence of O-' moles of potassium iridium(III) hexachloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were added simultaneously over 60 minutes, during which PA
By keeping g at 768, a cubic monodisperse emulsion with an average grain size of 0.25 μm and an average silver iodide content of 1 mol % was prepared. No chemical sensitization was performed. 5,5°-dichloro-9-ethyl-3,3 was added to these silver iodobromide emulsions as a sensitizing dye.
Sodium salt of °-bis(3-sulfoprobyl)oxacarbocyanine, 4-hydroxy-6- as a stabilizer
Methyl-1,3,3a,7-chitrazaindene, polyethyl acrylate dispersion, polyethylene glycol,
1.3-vinylsulfonyl-2-, propatool and the compounds of the present invention shown in Table 1 were added and tl! Coating was carried out at a rate of 3.4 g/rrr. Gelatin is 1.8g/rrr
Met.

On top of this, as a protective layer, gelatin 1.5g/rrr, polymethyl methacrylate particles (average particle size 2.5μ) 0.
A layer containing 3 g/% of the following surfactants was applied:

CHzCOOCaHIx CHCOOCJ+3 03Na 37 ■/rrr CJ+tsOJcHzcOOK 2.5■/GoCcoH1 As a comparative example, instead of the compound of the present invention, JP-A-63-2
Compounds -A and -B described in 9751.

Samples were prepared using C and compounds -D and -E. Examples of those compounds are shown in Table-1.

These samples were exposed to tungsten light at 3200'' through an optical wedge and an ND filter with an optical density of 1.5, developed with the following developer at 34°C for 30 seconds, fixed, washed with water, and dried.

The photographic properties obtained are shown in Table 1. It can be seen that when the compound of the present invention is used, it is possible to stably maintain high-contrast photographic characteristics even under severe storage conditions.

[Developer-1] Hydroquinone 50.0g N-methyl-p-aminophenol 0.3g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone Sodium hydroxide 18.0g Boric acid
54.0g potassium sulfite
110.0g Disodium ethylenediaminetetraacetate 1.0g Potassium bromide 10.0g 5-methylbenzotriazole 0.4g 2-mercaptobenzimidazole-5-sulfonic acid 0.3g 3-(5-
Mercaptotetrazole) Sodium benzenesulfonate 0.2gN-n-
Butyljetanolamine 15.0g Sodium toluenesulfonate 8.0g Add water to 11
1j! Adjust pH to -11.6 (add sodium hydroxide) pH
11.5 Comparative compound Shiri, cut Example-2 5.0X per mole of silver in an aqueous gelatin solution kept at 40°C
After simultaneous mixing of aqueous silver nitrate and aqueous sodium chloride solutions in the presence of 10-'M of (N Ha'') s Rh Cl &, gelatin was added after removal of soluble salts by methods well known in the art. In addition, 2-methyl-4-hydroxy-1,3,3 is added as a stabilizer without chemical ripening.
a, 7-thitraazaindene was added. This emulsion was a cubic monodisperse emulsion with an average grain size of 0° and 18 μm.

The hydrazine compound and polyethyl acrylate latex shown in Table 3 were added to this emulsion at a solid content of 3Qw for gelatin.
t% and 1,3-vinylsulfonyl-2-propertool was added as a hardening agent, and 3.
．． It was applied so that the Ag amount was 8 g/rrf. Gelatin was 1.8g/+Yr. A layer of gelatin (1.5 g/I) was applied thereon as a protective layer.

This sample has Dainippon Screen side Meisho printer P
-607, exposed through an optical wedge, treated with the developer of Example 1 at 30°C for 20 seconds, fixed, washed with water, and dried.

The photographic properties obtained are shown in Table 2.

The compound of the present invention provides high contrast with a small amount, and can maintain favorable photographic properties even under severe storage conditions.

Comparative Compound F Example 3 A multilayer color photosensitive material NαA having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

N2υi (Layer structure) The composition of each layer is shown below. Does the number mean the amount of coating per m2? It is expressed as For silver halide emulsions and colloidal silver, the coated amount in terms of silver is expressed as 2, and for spectral sensitizing dyes, the amount added is expressed in moles per 7 moles of silver halide.

Support polyethylene laminate paper [white pigment (Ti02) and bluish dye (including clusters in polyethylene on the 87th layer side)] 87th layer silver halide emulsion A O62 and spectral sensitizing dye (EXSS-/) t, oxto 'Spectral sensitizing dye (ExSS-2) t, l x l0-5 gelatin /, // Cyan coupler (ExCC-/) o, Conocyan coupler (Ex
CC-2) o, , 2 with ultraviolet absorber (E
xIJV-i) o, /7 solvent
(EXS-/) o, 23p1'JJ regulator (
Ex, GC-/) o, o 2 stabilizer
(ExA-/) Nucleating accelerator (ExZS-/) Nucleating agent (ExZK/) 82nd layer gelatin color mixing inhibitor solvent solvent 83rd layer silver halide emulsion A Spectral sensitizing dye (ExSS-J) Gelatin magenta coupler (ExMC-/) Color image stabilizer (ExSA-/) Solvent (ExS-J) Development regulator (ExGC-/) Stabilizer (ExA-/) Nucleation accelerator (ExZS-7) Nucleating agent (ExZK- /) 817th layer (ExKB-/) (ExS-/) (ExS-,2) o, oot 3.0xIO' r, 0xlO-5, Hiro 1, Ori, 10, /O 0,23 3,0x10 '/, 0! o,it O,+20 0,+2 j O,OX o,oot 2.7X10' /,μ×10-4 Gelatin Color Mixing Preventer Solvent Solvent Ej Layer Colloidal Silver Gelatin Color Mixing Preventer Solvent Solvent EJ Layer No. Ehiro 27th layer silver halide emulsion same as layer A Spectral sensitizing dye (ExSS-J) Gelatin yellow coupler (ExYC-/) Solvent (ExS-2) Solvent (ExS-≠) (ExKB-i) (ExS-/) (ExS-, 2) (ExKB-/) (ExS-/) (ExS-2), tI7, 0! , 0! ,O3,Ori,4! ri, 03, 03. 03 O, Gu Q Hiroshi, 2×10' ko, /7 0, j 1 0, +20 0.20 Development control agent (ExGC-i) o, o
g stabilizer (ExA-/) o,
o o l Nucleation accelerator (EXZS-/) j,
oxlo' nucleating agent (ExZK-/)
y, xxlo 5th Elr layer gelatin 0. jhiro ultraviolet absorber (ExUV-,2) 0,2/solvent
(ExS-<<) o, o rth E
Layered gelatin 1. Acrylic modified copolymer of polyvinyl alcohol (denaturation degree/7) o,/7 liquid paraffin 0.0! Latenx particles of polymethyl methacrylate (average particle size 1.rμm11) o, or B1 layer gelatin r, 70 In addition to the above composition, gelatin hardening agent ExGK-/
and surfactant were added.

Silver halide emulsion A A wet aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate are mixed with 3 μm dimethyl-/,3-thiazoline-λ-thione and 0.37 lead acetate per mole of O1!7. While vigorously stirring the gelatin aqueous solution containing
They were simultaneously added at sz 0c over a period of about 5 minutes to obtain a monodisperse silver chlorobromide emulsion with an average grain size of about 0.2 μm (silver bromide content≠0 mol). 93 per mole of silver in this emulsion! rm9
Chemical sensitization treatment was carried out by adding 100 m of sodium thiosulfate and 20 m9 of chloroauric acid (1I hydrate) and heating at s'C for 10 minutes.

Using the thus obtained silver chlorobromide grains as cores, they were further grown by further IAO treatment in the same precipitation environment as the first time, and finally had an average grain size of O.

A monodisperse core/shell silver chlorobromide emulsion with a diameter of 1.5 μm was obtained.

The coefficient of variation in particle size was approximately 10%.

3. Sodium thiosulfate was added to this emulsion in an amount of 3 mg per mole of silver. Add jmQ amount of chloroauric acid (Kohsui salt), and add tO
A chemical sensitization treatment was performed by heating at aC for 50 minutes to obtain an internal latent image type halogenated i-emulsion A.

Compounds used to prepare the samples (ExCC-1) Cyan coupler α (ExCC-2) Cyan coupler (EX?VIC-/) Magenta coupler' (ExYC-
/) Yellow coupler C7! (ExSS-Il,) Spectral sensitizing dye (ExS-/) Solvent (ExS-2) Solvent (ExSS-/) Spectral sensitizing dye (ExSS-2) Spectral sensitizing dye (ExSS-J) Spectral sensitizing dye ( ExS-J) Solvent l:l mixture (volume ratio) (ExS-Hiro) Solvent (ExUV-/) Ultraviolet absorber (ExKB-/) Color mixing inhibitor (ExGC-/) H Development regulator fil: f21: f3+ Noyo 2♂: Ri mixture (
Weight ratio) (ExUV-2) Ultraviolet absorber above fl): 121: 13+, 2:R:r mixture (weight ratio) (ExSA-/) Color image stabilizer (ExA-/) Stabilizer l-hydroxy- Yo, wo-trimethylene-13, Ja,
7-chitrazainde/ (ExZS-/) Nucleation accelerator Co(3-dimethylaminopropylthio)-yo-mercaptol, 32μm thiadiazole hydrochloride ExZK-/G) Nucleating agent ExGK-/) Gelatin hardening agent/-Okin- 3! - Dichloro 3-) Lyazine sodium salt treatment step A Bleach-fixing water washing ■ 30 seconds 30 seconds r I 0C The method of replenishing the washing water is to replenish it to the washing bath ■ and lead it to the overflow i of the washing bath ■ and the pilot bath ■. A countercurrent replenishment system was adopted.

[Color developing solution]

diethylenetriaminepentaacetic acid l-hydroxyethylidene- /,/-diphosphonic acid diethylene glycol benzyl alcohol sodium bromide sodium chloride sodium sulfite N,N-diethylhydroxy Ruamine 3-methyl-kuamino-N -ethyl-N-(β-meta (sulfonamide ethyl) One aniline potassium carbonate Mother liquor o, zy O,j? r, o? 10.07 0,! 2 0.72 λ, 02 3, jri t, o 30.09 p) (／　0　　、!O pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 1002 Sodium bisulfite 10? Iron ethylenediaminetetraacetate t, toy (1) ammonium.
λ hydrate ethylenediaminetetraacetic acid coj7 sodium dihydrate λ-mercapto/, 3. 0. j? Add ψ-triazole pure water to 10 ooml pH7
-O pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Pure water was used.

Here, pure water is water in which the concentrations of all cations other than hydrogen ions and all anions other than hydroxide ions in tap water have been removed to 1 ppm or less by ion exchange treatment.

Multilayer color photosensitive material tlkl-8 was prepared in the same manner as sample ThA except that the nucleating agent (ExZK-1) was changed to the compound listed in Table 3.

The sample prepared in this way was heated for 50 minutes in an oxygen atmosphere.
After leaving it at 60% humidity for 3 days, wedge exposure (1/1
0 seconds, IOCMS), processing step A was performed, and cyan color image density was measured.

The results obtained are shown in Table 3.

Comparative Compound ■ Table 3 Shihzuh The amount of nucleating agent added is 11kLl, 5.2, 6.3, and 7.4
and 8 were made equal moles.

Samples 1 to 4 using the nucleating agent of the present invention are Comparative Example 5
The maximum image density (Dmax) was lower and more preferable than those of Samples 1 to 8. Similar results were obtained for magenta density and yellow density.

EXAMPLE Each layer was coated on a polyethylene terephthalate transparent support in the following order to prepare a photosensitive element cup/~fl'.

(1) U.S. Unilateral License No. 3. (3,02/rrL2)/TrL2/rrL2 (θ (O.

The following magenta DRR compound 4Jo, ayo? ), diethyl laurylamide (0,IO?), 2. ! - di-t-butylhydroquino, 0074t9/rrt2), and gelatin 74y/m2).

H13C6N-C5HtaCee ca) (13 x: y=yoO:SO and a mordant layer containing gelatin (3,0 P/m2).

(2) Titanium oxide! o S'/m2 and a white reflective layer containing gelatin 2°09/m2.

(3) A light shielding layer containing carbon black, 2.70 ri/rrL2 and gelatin r, 7o9/7!2.

(5) The internal latent is a type emulsion (according to the amount of silver/, Hiro P/771
2), a nucleating agent shown in Table 3 containing a green sensitizing dye (/, rim9/m2) and! - a green-sensitive internal m-image type direct positive iodobromide emulsion (2 mol % silver iodide) layer containing (antadecyl-hydroquinone-sodium cosulfonate (o, / / 97 m2)).

(6) A layer containing gelatin (o, 4'5'/m2).

Processing was carried out by combining the above photosensitive elements/~g with the following elements.

Treatment liquid The treatment liquid with the above composition was added to 0. ♂2 each was filled into containers j that can be destroyed by pressure.

Cover sheet Polyacrylic acid (70% by weight aqueous solution with a viscosity of / , 000 cp) /j? /m2 and acetyl cellulose (tooy
Hydrolyzes with acetyl cellulose to form ≠2 acetyl groups) 3, ♂? / m 2 and a copolymer of styrene and maleic anhydride (composition (mole) ratio, styrene = maleic anhydride = approximately tou4to, molecular weight! 10,000) o.

A cover sheet coated with , +ri/rn2 was prepared.

Forced deterioration conditions Two sets of the above photosensitive element plates/~g are prepared, and one set is stored in a refrigerator (r
'c), and the residual/group @ degree 3! 0C relative humidity 10
% and left at 7'C.

Processing process The above force/ζ-sheet and the above photosensitive sheet were placed one on top of the other, and the color test chart was exposed from the cover sheet side, and then the above processing solution was spread between the two sheets to a thickness of 7jμ ( The expansion was done with the help of a pressure roller). The treatment was carried out at 1.2°C. After processing, what is the green density of the image produced on the image-receiving layer through the transparent support of the photosensitive sheet? Measured after treatment/time by Macbeth reflection densitometer.

The results 1 are shown in Table f.

Dl-: Maximum density 3F of the positive image part of the product stored in the refrigerator,
Relative sensitivity at a density of 0°5 in the positive image area of a sample stored in a refrigerator (when SF of photosensitive element 1 is 100) s'': 5o°C, relative humidity 80%, density 0.5 in the positive image area of a sample left for 4 days. 5 relative sensitivity (when SF of Photosensitive Element 1 is 100) As is clear from the above results, Photosensitive Elements 3 to 6 to which the nucleating agent of the present invention was added were higher than those made by the conventional method. It can be seen that there is less change in sensitivity when the photosensitive material is aged than in the example photosensitive element.

Example 5 In carrying out the present invention, the following emulsion X was prepared.

Emulsion 75° contained
Silver nitrate corresponding to 1/8 mol was added to an aqueous gelatin solution (pH=5.5) of C over 5 minutes while stirring well to obtain a spherical AgBr monodisperse with an average particle size of about 0.14 μm.

To this emulsion, 20 mg of sodium thiosulfate and 2 Q mg of chloroauric acid (tetrahydrate) were respectively added per mole of silver halide, the pH was adjusted to 1.5, and the pH was adjusted to 7
The core emulsion was chemically sensitized at 5°C for 80 minutes, and then a silver nitrate aqueous solution (containing 7/8 mol of silver nitrate) and a potassium bromide aqueous solution were added at the same temperature under well-stirred conditions. , while maintaining the silver electrode potential at which regular octahedral particles grow, were simultaneously added for 40 minutes to allow shell growth, resulting in monodispersed octahedral cores with an average particle size of approximately 0.3 μm.
A sheal type emulsion was obtained. This emulsion was washed with water and desalted in a conventional manner, then heated and dissolved, the pH was adjusted to 6.5, and 5 mg of sodium thiosulfate and 5 mg of chloroauric acid (4 hydroxide) were added per mole of halogenated i. salt) and 7
After aging at 5° C. for 60 minutes, the shell surface was chemically sensitized to finally obtain an internal latent image type monodispersed octahedral core-shell emulsion (emulsion X). As a result of measuring the grain size distribution of this emulsion from electron micrographs, the average grain size was 0. 30μ
m, coefficient of variation (average particle size x 100/standard deviation) is 10%
Met.

Panchromatic sensitizing dye 3.3'-diethyl-9 was added to the above emulsion
- After adding 5 mg of methyl thiocarbocyanine per mole of silver halide, the exemplified compound (1
-48) (1-19) (121) and comparative compound -EX
ZK-1 was added in the amount shown in Table 5, and IX 10-3 moles of Compound-D as a nucleation accelerator were added per mole of 2 halides, and silver was deposited on a polyethylene terephthalate support. It was coated in an amount of 2.8 g/rd, and a protective layer consisting of gelatin and a hardener was simultaneously coated thereon to prepare a direct positive photographic material sensitive to red light.

After leaving the above photosensitive material in an oxygen atmosphere at 50'C and 60% humidity for 3 days, IKW tungsten lamp (color temperature 2854) was used.
@K) Exposure was performed for 0.1 seconds using a photosensitive needle through the steps.

Next, an automatic developing machine (Kodak Proster r
Processor)
Developing was performed at 38° C. for 18 seconds using a Plus processing solution (developing solution pH 10.7), followed by washing with water, fixing, washing with water, and drying using the same developing machine.

The maximum density (Dm) of the direct positive image of each sample obtained in this way
ax ), minimum density (Dmin) and relative sensitivity were measured and the results in Table 5 were obtained.

As is clear from the results in Table 5, exemplified compound l-48
The sensitive materials using the nucleating agents of , l-19, and -21 can withstand harsher storage conditions and exhibit superior reversal properties than the sensitive materials using the comparative compound ExZK-1, which is a control nucleating agent. It can be seen that the sensitivity is high.

Comparative compound ExZK 1 Display of incidents name of invention Procedural amendment Patent Application No. 770 of 1988 Silver halide photographic material person who makes corrections Relationship with the incident

Claims (2)

[Claims] (1) A silver halide photographic light-sensitive material characterized by containing a compound having a cyclic structure that undergoes nucleophilic attack to open the ring and become an anion that is hydrazide or its conjugate base. (2) A silver halide photographic material containing a compound represented by the following general formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents an optionally substituted aliphatic group or aromatic group, R_2 represents a hydrogen atom or a substituent, and D represents ■ C=O, ■C=S, may be substituted■
C=NH, SO, SO_2, N→O, or optionally substituted P(O)H, and E represents an oxygen atom or a sulfur atom. ]