JPH0990538A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material having adequate spectral sensitivity to laser beams to be used for exposure and high sensitivity and high Dmax in high illumination in a short time and small fluctuation of performance even in a long time storage and improved pressure resistance by incorporating a specified compound in an emulsion layer or another hydrophilic colloidal layer. SOLUTION: The photosensitive silver halide emulsion layer on a support contains flat silver halide grains having a silver chloride content of >=80mol% and principal faces (100) and an average aspect ratio of 2-5 and an average grain size of <0.5μm, and the emulsion layer or another hydrophilic colloidal layer contains at least one of compounds represented by formulae I and II and the like, and in the formulae I and II, Z is a C-X group; X is an alkyl or aryl group; M is H or a metal atom or the like; Y is a hydrophilic alkyl or aryl group; and each of R<1> and R<2> is, independently, a hydroxyl or hydroxyalkyl group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an ultra-high contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

2. Description of the Related Art In recent years, a scanner system has been widely used in the field of printing plate making. There are various types of recording apparatuses that have practically used the image forming method by the scanner method, and the light source for recording of these scanner type recording apparatuses is a glow lamp, a xenon lamp, a tungsten lamp, an LED, a He-Ne laser, an argon laser. And semiconductor lasers. Various characteristics are required for the light-sensitive materials used in these scanners, but especially 10 ⁻³
Even under such conditions, high sensitivity and high contrast are essential conditions because the exposure is performed in a short exposure time of -10 ^-7 seconds.

Further, spectral sensitization is usually performed in order to have wavelength suitability for various laser light sources. For example, the compound represented by the general formula (I) described in JP-A-7-43844 is suitable for spectral sensitivity mainly to He-Ne lasers, and the compounds represented by the general formulas (II) and (III) are Its spectral sensitivity is suitable mainly for semiconductor lasers. The compounds represented by these general formulas are superior to other sensitizing dyes in terms of sensitivity and residual color, but it cannot be said that the spectral sensitization efficiency is sufficiently high, and further the intrinsic desensitization is caused by the addition amount. It may happen. As a method for increasing the efficiency of spectral sensitization, for example, for He-Ne laser light source applications,
JP-B-49-25500, and JP-A-59-19032 and 59-192242 for use in semiconductor lasers.
No., etc., but there is a case where deterioration of UV transmittance in the post-exposure returning step, residual color and the like become a problem. Further, in recent years, there has been a strong demand in the printing industry for work efficiency and speedup.

In order to meet the needs of these printing fields,
For exposure machines (scanners, plotters), it is desired to increase scanning speed, increase the number of lines and narrow the beam for higher image quality, and for silver halide photographic light-sensitive materials, high sensitivity and process stability. It is desired that the development is excellent and that development processing can be performed quickly. The high silver chloride silver halide emulsion to be used in this method is generally known to have low sensitivity, and it has been a challenge to overcome these points in order to put it into practical use.

In order to improve the sensitivity and Dmax of high silver chloride grains, a photographic light-sensitive material containing tabular grains whose main plane is the (1,0,0,) plane is disclosed in JP-A-7-110554. Although disclosed, there is a problem in that fogging occurs due to stability over time after the production of the light-sensitive material or the pressure during transport of the film.

[0006]

Therefore, the first object of the present invention is to have an appropriate spectral sensitivity to a laser light source used for exposure, and to provide high sensitivity and high sensitivity in short exposure with high illuminance.
An object of the present invention is to provide a silver halide photographic light-sensitive material having a Dmax and a small performance variation even when stored for a long time, and having improved pressure resistance. A second object of the present invention is to provide an ultra-high-contrast silver halide photographic light-sensitive material and a method of processing the same, which has little fluctuation in photographic properties in long-term operation even when the amount of replenishment of the developing solution in the automatic processor is reduced. It is in.

[0007]

For the first object of the present invention, in a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the halogenation is carried out. The silver emulsion is a tabular grain having a silver chloride content of 80 mol% or more, the main plane is the (100) plane, the average aspect ratio is 2 or more and less than 5, and the average grain size is 0.5 μm.
In the silver halide photographic light-sensitive material, the emulsion layer or other hydrophilic colloid layer is represented by the general formula (1), (2), (3), (4), (5) )
And a silver halide photographic light-sensitive material characterized by containing at least one of the compounds represented by (6) and (6). General formula (1)

[0008]

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In the formula, Z represents N or C—X (X represents an alkyl group or an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl group or an aryl group having a hydrophilic group. General formula (2)

[0010]

[Chemical 12]

In the formula, R ¹ and R ² may be the same or different and each is a hydroxy group, a hydroxyalkyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an alkoxy group, a phenoxy group or an alkyl group. ,
It represents an aryl group, an alkylthio group or a phenylthio group. General formula (3)

[0012]

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In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a 1,2,3 secondary amino group. , Carbonamide group, sulfonamide group, alkyl group, aryl group, at least 1
5- or 6-membered heterocycle containing N, O, S atoms,
It represents a formyl group, keto group, sulfonic acid group, carboxylic acid group, alkylsulfonyl group or arylsulfonyl group. General formula (4)

[0014]

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In the formula, Z represents an alkyl group, an aryl group or a heterocyclic group, and M represents a metal atom or an organic cation. General formula (5)

[0016]

[Chemical 15]

In the formula, Y represents a group of atoms necessary for forming an aromatic ring or a hetero ring. General formula (6)

[0018]

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In the formula, Y represents a group of atoms necessary for forming an aromatic ring or a hetero ring, and n represents an integer of 2 to 10. For the first object of the present invention, on the support,
In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer, the silver halide emulsion is tabular grains having a silver chloride content of 50 mol% or more, the main plane being a (100) plane, A silver halide photographic light-sensitive material characterized by having an average aspect ratio of 2 or more and less than 5 and an average grain size of less than 0.5 μm and having a film surface pH on the emulsion layer side of 4.5 or more and less than 6.0. It can also be achieved by a silver halide photographic light-sensitive material characterized by being present. Further, for the second object of the present invention, in the method of developing the above silver halide photographic light-sensitive material after image exposure while replenishing the developing solution, the development initiation solution and the development replenishing solution are dihydroxybenzene-based. Liquid 1 containing a developing agent and an auxiliary developing agent exhibiting superadditivity therewith
A solution having a property that the pH rise when 0.1 mol of sodium hydroxide is added to liter is 0.25 or less, and the pH of the development starter solution is 9.5 or more and less than 11.0. Therefore, a method of developing and processing a silver halide photographic light-sensitive material is preferable, which is characterized in that the replenishing amount of the developing solution is 225 ml / m ² or less.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail.

In the present invention, tabular silver halide grains having a (1,0,0) plane as a main plane and having a silver chloride content of 50% or more are described in European Patent No. 534,395A1 at page 7, line 53. From page 19, line 35 or JP-A-6-5
Paragraph numbers (0006) to (0024) of 9360 Publication
It can be prepared by the method described in. The silver halide grains of the present invention are preferably tabular silver halide grains in which 35% or more of the total projected area of all silver halide grains has a (1,0,0) plane as a main plane. It is more preferably 60% or more, still more preferably 80% or more. The aspect ratio of the tabular silver halide grains is 2 to
5 is preferred. The average projected grain size of the tabular silver halide grains is preferably 10 μm or less, more preferably 0.2 to 5 μm. Here, the aspect ratio refers to (diameter / thickness) of the tabular grain, and the diameter refers to the diameter of a circle having an area equal to the projected area of the grain when the grain is observed with an electron microscope. The thickness means the distance between the main planes of tabular grains. The average aspect ratio means the average value of the aspect ratios of all the tabular grains. The average projected grain size refers to the arithmetic mean value of the diameters of all the tabular grains. The principal plane refers to two parallel maximum outer surfaces in one tabular grain. The particle size distribution of the tabular grains is preferably monodisperse, and the coefficient of variation is preferably 40% or less, more preferably 20% or less. As the silver halide emulsion used in the present invention, it is necessary to use an emulsion composed of silver chloride, silver chlorobromide or silver chloroiodobromide and having an average silver chloride content of 50 mol% or more. The above is more preferable. Here, the silver iodide content is preferably 1 mol% or less, more preferably 0.2 mol% or less. In the present invention, the average silver chloride content is 5
If it is less than 0 mol%, the rapid processability tends to be poor.

The halogen composition of the emulsion may be different or the same between the grains, but it is preferable to use an emulsion having the same halogen composition between the grains because it is easy to make the properties of each grain uniform.

In the present invention, it is necessary that the bromine ions are localized on the particle surface, and the bromine ion content on the particle surface is at least twice the average bromine ion content on the entire particle. It is preferable that it is 3 times or more and 200 times or less, and it is particularly preferable that it is 5 times or more and 100 times or less. The surface defined in the present invention means a surface in a range measured by the XPS (X-ray Photoerectron Spectroscopy) method. This measuring method is specifically described by Someno and Yasumorii "Surface Analysis" Kodansha (19
Published in 1977).

The high silver chloride emulsion grains preferably have a structure in which the silver bromide localized phase is layered or non-layered on the surface of the silver halide grain. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%.
These localized phases can be present on the edges, corners or planes of the grain surface, and one preferable example is a grain epitaxially grown on the corner portion of the grain. The high bromine ion concentration on the surface of the grain means that a sparingly soluble bromide such as silver bromide or a water-soluble bromide such as potassium bromide, or US Pat. This is accomplished by adding a bromide ion donating compound, such as a bromide ion sustained release agent as described in No. 615.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. It is preferably less than 5μ, and the lower limit is about 0.02μ. Further, the particle size distribution thereof is preferably a so-called monodispersed coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% by weight of all grains as a projected area is also preferably used. You can The silver chlorobromide emulsion used in the present invention is a Chimie et Phisi by P. Glafkides.
que Photographique (Published by Paul Montel, 1967
), GF Duffin PhotographicEmulsion Chemi
stry (Focal Press, 1966), VL Zelikman
et al Making and Coating Photographic Emulsi
on (Focal Press, Inc., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt with a soluble halogen salt may be any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide grains of the present invention can be doped with iridium or rhodium using an iridium compound or rhodium compound. As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, iridium (III) halide compounds, iridium (IV) halide compounds, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III)
Alternatively, (IV) complex salt, hexaammineiridium (III) or (IV) complex salt, trioxalatoiridium (III) or (IV) complex salt and the like can be mentioned. In the present invention, among these compounds, a trivalent compound and a tetravalent compound can be arbitrarily combined and used. These iridium compounds are used by dissolving them in water or a suitable solvent,
A commonly used method for stabilizing an iridium compound solution, that is, a method of adding an aqueous hydrogen halide solution (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, NaBr, etc.) Can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide grain. The total addition amount of the iridium compound according to the present invention is 10 ^-9 mol or more, particularly 5 × 10 ^-9 to 1 × 1 per 1 mol of finally formed silver halide.
0 ^-4 mol is suitable, preferably 1 x 10 ^-8 to 1 x 1
It is 0 ^-5 mol, most preferably 5 × 10 ^{-8 to} 5 × 10 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion and at each stage before coating the emulsion, but in particular, it can be added at the time of grain formation and incorporated into the silver halide grains. preferable. Further, a compound containing a Group VIII atom other than the iridium compound may be used in combination with the iridium compound.

Among these metal ions, it is preferable to use them in the form of complex ions, and the ligand is cyano,
Groups and molecules such as isocyano, thiocyano, nitrosyl, thionitrosyl, amine and hydroxyl are preferably used.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a halogenated rhodium (III) compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaammine rhodium ( III) complex salts, trioxalatrodium (III) complex salts and the like. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of rhodium compounds, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide grain. The total addition amount of the rhodium compound according to the present invention is suitably 10 ^-9 mol or more, particularly 1 × 10 ^-9 to 1 × 10 ^-6 mol, and preferably 1 × 10 ^-9 to 1 × 10 ^-6 mol, per 1 mol of the finally formed silver halide. It is 5 × 10 ⁻⁹ to 1 × 10 ⁻⁶ mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add them at the time of grain formation and to incorporate them into the silver halide grains. .

In the present invention, a divalent or trivalent iron ion-containing compound can be used in combination with an iridium compound or a rhodium compound, and a water-soluble iron salt or iron complex salt is preferably used. Specific compounds are shown below. Ferrous nitrate ammonium basic ferric acetate ferric albumin ferric ammonium acetate ferric bromide ferric chloride ferric chloride ferric citrate ferric fluoride ferric formate Glycero ・ ferric phosphate, ferric hydroxide, ferric acid phosphate, ferric nitrate, ferric phosphate, ferric pyrophosphate, ferric pyrophosphate, sodium thiocyanate, ferric sulfate, ferric sulfate Iron Ammonium Ferrous arsenate Ferrous bromide Ferrous carbonate Ferrous chloride Ferrous ferrous citrate Ferrous ferrous formate Ferrous gluconate Ferrous ferrous hydroxide Ferrous iron ferrous iodide Ferrous lactate ferrous oxalate ferrous phosphate ferrous succinate ferrous sulfate ferrous thiocyanate ferrous nitrate ferric nitrate guanidine ferric ammonium citrate hexane cyanoferrate (II) acid Potassium bentacyanoammine ferrous potassium ethylenedinit (B) Sodium ferric tetraacetate Potassium hexacyanoferrate (III) Tris (dipyridyl) ferric chloride Ferric bentacyanonitrosyl ferric potassium Hexarea ferric chloride Especially hexacyanoferrate (II) and hexacyanoferrate (III) Ferrous thiocyanate and ferric thiocyanate show remarkable effects.

The present invention includes rhenium, ruthenium and osmium compounds such as European Published Patent (EP) 03.
No. 36689A, No. 0336427A1, No. 0336
The hexadentate coordination complexes described in Nos. 425A1 and 0336426A1, especially those containing at least 4 or more cyanide ligands can be used in combination. In a preferred embodiment, these compounds can be represented by the formula: [M (CN) ₆ -y Ly] ⁿ where M is rhenium, ruthenium, osmium, L is a bridging ligand, y is an integer 0, 1 or 2, and n is -2, -3 or -4.

The following can be mentioned as specific examples. [Re (CN) ₅ ] ^-4 [Ru (CN) ₅ ] ^-4 [Os (CN) ₅ ] ^-4 [ReF (CN) ₅ ] ^-4 [RuF (CN) ₅ ] ^-4 [OsF (CN) ₅ ] ^-4 [ReCl (CN) ₅ ] ^-4 [RuCl (CN) ₅ ] ^-4 [OsCl (CN) ₅ ] ^-4 [ReBr (CN) ₅ ] ^-4 [RuBr (CN) ₅ ] ^-4 [ OsBr (CN) ₅ ] ^-4 [ReI (CN) ₅ ] ^-4 [RuI (CN) ₅ ] ^-4 [OsI (CN) ₅ ] ^-4 [ReF ₂ (CN) ₄ ] ^-4 [RuF ₂ (CN ) _5] ^-4 [OSF ₂ (CN) _5] ^-4 [ReCl ₂ (CN) _4] ^-4 [RuCl ₂ (CN) _4] ^-4 [OsCl ₂ (CN) _4] ^-4 [RuBr ₂ (CN ) ₄ ] ^-4 [OsBr ₂ (CN) ₄ ] ^-4 [ReBr ₂ (CN) ₄ ] ^-4 [RuI ₂ (CN) ₄ ] ^-4 [OsI ₂ (CN) ₄ ] ^-4 [Ru (CN) ₅ (OCN)] ^-4 [Os (CN) ₅ (OCN) ^-4 [Ru (CN) ₅ (SCN)] ^-4 [Os (CN) ₅ (SCN)] ^-4 _{[Ru (CN) 5 (N 3} ) ] ^-4 _{[Os (CN) 5 (N 3} ) ] ^-4 [Ru (CN) ₅ (H ₂ O)] ^-3 [Os (CN) ₅ (H ₂ O)] ^-3

The above iron, rhenium, ruthenium and osmium compounds are preferably added during the formation of silver halide grains. The addition position may be evenly distributed in the particles, or may be localized in the early, middle, and late stages of particle formation.
It is preferred to add after 0%, more preferably 80% is formed. The addition amount is 10 ^-3 mol or less per 1 mol of silver, and preferably 10 ^-6 to 10 ^-4 mol. In the present invention, other metals contained in Group VIII, that is, cobalt, nickel, palladium, platinum and the like may be used in combination.

The grain formation of the silver halide emulsion of the present invention comprises
It is preferably carried out in the presence of a silver halide solvent such as a tetra-substituted thiourea or an organic thioether compound. Preferred tetra-substituted thiourea silver halide solvents used in the present invention are
It is described in JP-A Nos. 53-82408 and 55-77737.

The emulsion of the present invention is preferably selenium-sensitized. Here, the selenium sensitization is performed by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is preferably carried out by stirring the emulsion at 40 ° C. or higher for a certain period of time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides,
There are selenocarboxylic acids and esters, selenophosphates. Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compound (selenium atom is double-bonded to carbon atom of organic compound by covalent bond) a isoselenocyanate, for example, aliphatic isoselenocyanate such as allyl isoselenocyanate b selenourea (enol type For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N-dimethyl, diethyl, dimethyl, etc. An aromatic selenourea having one or more aromatic groups such as phenyl and tolyl; a heterocyclic selenoureas having a heterocyclic group such as pyridyl and benzothiazolyl c selenoketones, for example, selenacetone, Selenoacetophenone, selenoketo having an alkyl group bonded to> C = Se , Selenobenzophenone, etc. d selenoamides, for example, selenoacetamides e, selenocarboxylic acids and esters, for example, 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate, etc. III. Other a selenides, for example, diethylselena Id, diethyl diselenide,
Triphenylphosphine selenide, etc. b Selenophosphates, for example, tri-p-tolylselenophosphate, tri-n-butylselenophosphate, etc.

Preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used. Japanese Examined Sho 46-
4553, JP-B-52-34492 and JP-B-5
Selenium sensitization using the non-labile selenium sensitizer described in JP-A-2-34491 can also be used. Examples of the non-unstable selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenides, diaryl diselenides, 2-thioceretezolidinediones, and 2-selenooxo. Lysine thione and derivatives thereof are included. Japanese Examined Japanese Patent Publication Sho 52-38408
The non-labile selenium sensitizers and thioselenazolidinedione compounds described in JP-A No. 1994-1999 are also effective.

These selenium sensitizers are added at the time of chemical sensitization by dissolving them in water or an organic solvent such as methanol and ethanol alone or in a mixed solvent. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and preferably 1 mol of silver halide. Per 1 x 10 ^-8
It is more than a mole. More preferably 1 × 10 ⁻⁷ mol or more 1
× 10 ⁻⁵ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

In the present invention, tellurium sensitization can also be preferably used. As tellurium sensitizers, U.S. Pat.
623, 499, 3,320,069, 3,7
72,031, British Patent No. 235,211 and 1,
121,496, 1,295,462, 1,3
96,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemicals.
Communication (J.Chem.Soc.Chem.Commun.) 635 (1
980), ibid 1102 (1979), ibid 645 (1979), Journal of Chemical Society Perkin Trans (J. Chem. Soc. Perkin Trans.) 1, 2191 (1985)
It is preferable to use the compounds described in the above.

Specific tellurium sensitizers include colloidal tellurium and telluroureas (eg, allyl tellurourea,
N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ', N'-dimethyl tellurourea, N, N'-dimethylethylene tellurourea, N,
N'-diphenylethylene tellurourea), isotellocyanates (for example, allyl isotellurocyanate), telluroketones (for example, telluroacetone, telluroacetophenone), telluroamides (for example, telluroacetamide, N, N-dimethyl tellurobenzamide), tellurohydrazide. (For example, N, N ′, N′-trimethyltelurobenzhydrazide), telluroester (for example, t-butyl-t-hexyltelluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropyl). Phosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) and other tellurium compounds (eg negatively charged tellurium described in British Patent 1,295,462). Doion containing gelatin, Potassium nitrosium telluride, Potassium nitrosium tellurocyanate diisocyanate, tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate)
Etc.

The amount of these tellurium sensitizers used in the present invention varies depending on the silver halide grains used, the chemical ripening conditions, etc., but is generally from 10 ⁻⁸ to 1 mol per mol of silver halide.
10 ⁻² mol, preferably about 10 ^{−7 to} 5 × 10 ⁻³ mol is used.

Chemical sensitization is more effective when carried out in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include US Pat.
Nos. 271,157, 3,531,289, 3,574,628, JP-A-54-1019, and 5
(A) Organic thioethers described in JP-A-4-158917, JP-A-53-82408 and JP-A-55-7773.
No. 7, 55-2982 and the like (b) thiourea derivatives, and (c) the thiocarbonyl group described in JP-A No. 53-144319, sandwiched between an oxygen or sulfur atom and a nitrogen atom. Silver halide solvent having
(D) imidazoles described in No. 100717,
(E) Sulfite, (f) thiocyanate and the like. Particularly preferred solvents include thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide.

The silver halide photographic emulsion of the present invention has a higher sensitivity when combined with gold sensitization in chemical sensitization.
A low fog can be achieved. It is preferable to use sulfur sensitization together if necessary. Sulfur sensitization is usually carried out at a high temperature, preferably 40 ° C, by adding a sulfur sensitizer.
This is done by stirring the emulsion for a certain period of time.
The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For sulfur sensitization, known sulfur sensitizers can be used. For example thiosulfate,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like can be mentioned. Other US Patent No. 1,57
4,944, 2,410,689, 2,2
78, 947, 2, 728, 668, and 3,
501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-2
The sulfur sensitizers described in JP-A-4937, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but is not less than 1 × 10 ^-7 mol and not less than 5 × 10 ^-5 mol per mol of silver halide. The following are preferred.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide.

At the time of chemical ripening, there is no particular limitation on the timing and order of addition of the silver halide solvent and the gold sensitizer used in combination with the selenium sensitizer or tellurium sensitizer. The above compounds can be added at the same time (preferably) or during the chemical ripening, or at different addition points. In addition, the above compound may be added by dissolving the above compound in water or an organic solvent miscible with water, for example, a single solution or a mixed solution of methanol, ethanol, acetone or the like.

The method of reduction sensitization used in the present invention includes, as so-called reduction sensitizers, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, Reduction sensitization can be performed using a silane compound or a polyamine compound. Further, the pH of the emulsion was 7 or more or the pAg was 8.3.
It is possible to carry out reduction sensitization by keeping it below and aging. Further, reduction sensitization can be performed by introducing a single addition portion of silver ions during grain formation. However, it is preferable to carry out reduction sensitization using ascorbic acid and its derivative or thiourea dioxide in order to reduce the influence on grain formation and crystal growth and to carry out controlled reduction sensitization. The amount of the reduction sensitizer used depends on the type of the reducing agent, but varies from 10 ^-7 mol to 10 ^-2.
A mol / mol Ag amount is preferably used. Reduction sensitization is
It may be carried out at any point during grain formation, and may be carried out at any time after grain formation but before chemical sensitization.

The conditions for chemical sensitization are arbitrary, but the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. In particular, it is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide ^10-7 About 10 ^-2 mol can be used.

In the present invention, it is also preferable to use a sulfur sensitizer together. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylurea, allylthiourea), and rhodanines. 1 mol of silver halide About 10 ^-7 to 10 ^-2 mol can be used per unit.

Next, the mercaptoazoles represented by the general formula [1] used in the present invention will be explained. General formula [1]

[0051]

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In the formula, Z is N or C--X (X is an alkyl group,
Represents an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl group or an aryl group having a hydrophilic group. The alkyl group, aryl group and ammonium group represented by X, Y and M may further have a substituent. Preferred among the groups represented by X are a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms, or a substituted or unsubstituted phenyl group having 10 to 30 carbon atoms. Alternatively, it is an unsubstituted naphthyl group. Among the groups represented by Y, the preferred one is a hydrophilic group having 1 carbon atom.
To a substituted or unsubstituted alkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, particularly preferably a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms, or a carbon atom number It is a substituted or unsubstituted naphthyl group of 10 to 30. Preferred hydrophilic _groups, -SO 3 _M, -SO ₂ NH
^{_{R 1, -NHSO 2 R 1,}} -CO 2 NHR 1, -PO 3
M, PO (OR ¹ ) ₂ , PO (NHR ¹ ) ₂ , -COOM,
Alternatively, OH or the like is preferable. More preferably, -SO ₃
M, -COOM, -OH. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium. Specific examples of the compound represented by the general formula [1] used in the present invention are shown below, but the scope of the present invention is not limited to this compound example.

[0053]

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[0054]

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[0055]

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[0056]

[Chemical 21]

[0057]

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The compound represented by the general formula [1] can be easily synthesized by a method using isothiocyanate as a starting material, as is well known. The patents and literature examples in which the synthetic method is described as reference are shown below. U.S. Pat. No. 2,585,388,
2,541,924, JP-B No. 42-21842,
JP-A-53-50169; British Patent Nos. 1,27
5,701; D. A. Berges et all, “Journa
l of Heterocyclic Chemistry "15, 981 (1
978); “The Chemistry of Heterocyclic Chemis
try "Imidazole and Derivatives part I. 336-3
Page 39 Chemical Abstract 58,7921 (196
3) 394; E. Hoggarth “Journal of ChemicalS
ociety "1949, pp. 1160-1167 and S.M.
R. Sandler, W.M. Karo, “Organic Functional Gro
up Preparations ", Academic Press, 1968, 312-315.

These compounds are used as an aqueous solution, a hydrochloric acid aqueous solution, or a methanol solution as a photographic emulsion or a constituent layer other than the emulsion layer (for example, an overcoat layer, a filter layer, an intermediate layer, etc., but a layer adjacent to the emulsion layer is preferable. ) Is added to the hydrophilic colloid solution to make The timing of addition is not particularly limited, but when it is added to the photographic emulsion, it is convenient to add it after the second ripening and immediately before coating. The amount of these compounds added is usually in the range of 10 ⁻⁶ to 10 ⁻² mol, preferably 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol per mol of silver.

Next, the triazine compound represented by the general formula [2] used in the present invention will be explained. General formula [2]

[0061]

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In the formula, R ¹ and R ² may be the same or different from each other and each is a hydroxy group, a hydroxylamino group, an amino group or an alkylamino group (preferably having 1 carbon atom).
A mono- or di-substituted amino group of an alkyl group of 5 to 5), an aralkylamino group (preferably having a carbon number of 7 to 11), an arylamino group (preferably an amino group substituted by an aryl group having a carbon number of 6 to 10), Alkoxy group (preferably having 1 to 5 carbon atoms), phenoxy group, alkyl group (preferably having 1 to 5 carbon atoms), aryl group (preferably having 6 to 10 carbon atoms), alkylthio group (preferably C1-5) or a phenylthio group.
The alkyl moiety in each of the above groups is a hydroxy group, an alkoxy group (preferably having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms), an amino group, an alkylamino group (preferably having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms). It may have a substituent such as an alkyl group (mono- or di-substituted amino group). Further, in each of the groups represented by R ¹ and R ² , the aryl or phenyl moiety is a hydroxy group, an amino group, an alkylamino group (preferably a mono- or di-substituted amino group having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms). It may have a substituent such as an alkyl group (preferably having 1 to 4 carbon atoms, especially 1 to 2 carbon atoms), an alkoxy group (preferably having 1 to 4 carbon atoms, especially 1 to 2 carbon atoms). Examples of using the compound of the general formula [2] are described in JP-A-63-75737. The compounds of the general formula [2] preferably used in the present invention are exemplified below.

[0063]

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[0064]

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[0065]

[Chemical formula 26]

[0066]

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These compounds are available from Journal of the
Organic Chemistry, 27: 4054 (19)
62), Journal of the American Chemical Society, 73, 2981 (1951), and Japanese Patent Publication No. 49-10692. These compounds form a photographic emulsion or a constituent layer other than the emulsion layer (for example, an overcoat layer, a filter layer or an intermediate layer, but preferably adjacent to the emulsion layer) as an aqueous solution, a hydrochloric acid aqueous solution or a methanol solution. It is added to the hydrophilic colloid solution, but in the present invention, it is particularly preferably added to the photographic emulsion layer. The timing of addition is not particularly limited, but when it is added to the photographic emulsion, it is convenient to add it after the second ripening and immediately before coating. The addition amount of these compounds is usually 0.01 g to 10 per mol of silver.
g, particularly 0.1 g to 1 g.

Next, the dihydroxybenzenes represented by the general formula [3] of the present invention will be explained. General formula [3]

[0069]

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In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a primary, secondary, tertiary amino group. , Carbonamide group, sulfonamide group, alkyl group, aryl group, at least 1
Represents a 5- or 6-membered heterocyclic group containing N, O, S atoms, formyl group, keto group, sulfonic acid group, carboxylic acid group, alkylsulfonyl group, or arylsulfonyl group.

The compound of the general formula [3] will be described in more detail below. In the formula, R ¹ , R ² , R ³ and R ⁴ are hydrogen atom, hydroxy group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted Arylthio group, halogen atom, primary, secondary, tertiary amino group, substituted or unsubstituted carbonamido group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group A substituted or unsubstituted 5- or 6-membered heterocyclic group containing at least one N, O or S atom, a formyl group, a keto group, a sulfonic acid group, a carboxylic acid group, a substituted or unsubstituted alkylsulfonyl group A substituted or unsubstituted arylsulfonyl group.

As specific examples of these dihydroxybenzene derivatives, many examples are described in, for example, The Merck Index 10th edition, and US Pat. No. 2,728,
No. 659, No. 3,700,453, No. 3,227,5
52, JP-A-49-106329 and JP-A-50-15.
6,438, 56-109344, 57-22.
No. 237, No. 59-202465, No. 58-1743.
No. 1, Japanese Patent Publication No. 50-21249, No. 56-40818.
No. 59-37497, British Patent No. 752146,
No. 1086208, West German Patent Publication No. 2,149,789.
No. 5, Chemical Abstracts, Vol. 5, 6367h, JP-A-57-17949, and the like. Particularly preferred among these preferred dihydroxybenzenes are unsubstituted hydroquinones having a sum of Hammett sigma values of the substituents other than the two hydroxyl groups of -1.2 to +.
1.2, particularly preferably in the range of -1.0 to +0.5. Specific examples of these dihydroxybenzenes are shown below, but the present invention is not limited thereto.

[0073]

[Chemical 29]

[0074]

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[0075]

[Chemical 31]

[0076]

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[0077]

[Chemical 33]

The compound represented by the general formula [3] is preferably contained in an amount of 1 × 10 ^-6 to 5 × 10 ^-1 mol, and particularly 1 × 10 ^-5 to 8 mol per mol of silver halide.
The preferable addition amount is in the range of ^{x10 -2} mol.

When the compound of the general formula [3] is contained in the photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and alcohols (eg methanol, ethanol) esters (eg ethyl acetate) when it is water-insoluble. ),
It may be added to the silver halide emulsion solution or the hydrophilic colloid solution as a solution of a water-miscible organic solvent such as ketones (eg acetone). When it is added to the silver halide emulsion solution, it can be added at any time from the start of chemical ripening to the coating, but it is preferable to add it after the chemical ripening, especially the coating prepared for coating. It is preferably added to the liquid.

Next, the general formula [4] used in the present invention,
The thiosulfonic acid compound represented by [5] and [6] will be described.

[0081]

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However, Z: alkyl group (having 1 to 1 carbon atoms)
8), an aryl group (having 6 to 18 carbon atoms), or a heterocyclic group, Y: an atom necessary for forming an aromatic ring (having 6 to 18 carbon atoms), or a hetero ring, M: a metal atom, or an organic cation n: Represents an integer from 2 to 10. The alkyl group, aryl group, heterocyclic group, aromatic ring and heterocycle represented by Z and Y in the general formulas [4], [5] and [6] may be substituted. Examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group and a carboxyl group. be able to. Examples of the heterocycle represented by Z and Y include a thiazole, benzthiazole, imidazole, benzimidazole and oxazole ring. The metal atom represented by M is preferably an alkali metal atom such as sodium ion or potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group. A preferred group as Z is an alkyl group having 1 to 12 carbon atoms. The following can be mentioned as specific examples of the compounds represented by the general formulas [4], [5], and [6].

[0083]

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[0084]

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[0085]

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The compounds represented by the general formulas [4], [5] and [6] can be generally synthesized by a well-known method. For example, it can be synthesized by a method of reacting a corresponding sulfonyl chloride and sodium sulfide, or a method of reacting a corresponding sodium sulfinate and sulfur. On the other hand, these compounds can be easily obtained as commercial products. General formulas [4], [5], and
The addition amount of the compound represented by [6] is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol, and especially 5 × 10 ⁻⁵ to 1 mol of silver halide.
1 × 10 ⁻³ mol is preferable. The addition place of these compounds is preferably an emulsion layer, and the addition time is at the time of grain formation, chemical ripening or immediately before coating. Particularly preferred is immediately before coating.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but is 4 × 10 ⁻⁶ to 1 mol per mol of silver halide.
Used in the 8 × 10 ⁻³ molno range. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−7 to} 3.5 × per 1 m ² of surface area of the silver halide grain.
The addition amount range of 10 ⁻⁶ mol is preferable, and 6.5 × 10 is particularly preferable.
The addition amount range of ^{−7 to} 2.0 × 10 ⁻⁶ mol is preferable.

As the sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoholer cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOS
URE Item 17643 IV-A (Dec. 1978, p. 23) and Item 1831X (Dec. 1978, p. 437) or cited therein. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, as for A) an argon laser light source, JP-A-60-1
No. 62247, JP-A-2-48653, US Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
Trinuclear cyanine dyes described in JP-A-102229, merocyanines described in Japanese Patent Application No. 6-103272, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398.
No. 18, JP-A-62-284343, JP-A-2-10
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
No. 32, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242 and JP-A-3-67242, and general formula (IIIa) and general formula (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978)
(Published monthly), page 23, IV, J.

Specifically, S1-1 to S1-13, S2-1 to S2-10, S described in Japanese Patent Application No. 7-191007.
3-1 to S3-8, S4-1 to S4-9, S5-1 to S
5-20, Compound I described in Japanese Patent Application No. 6-103272
-1-I-34 are mentioned.

In the present invention, it is preferable to add an acid in order to keep the film surface pH below 6.0. The acid for adjusting the film surface pH used in the present invention may be either an organic acid or an inorganic acid, but an acid such as citric acid, phthalic acid, citric acid ester, salicylic acid or phosphoric acid is preferred, and an undercoat layer, an emulsion It may be added to any layer such as a layer and a protective layer. The "film surface pH" in the present invention means that 0.05 cc of water is added on the measuring surface of a photographic light-sensitive material of 1 cm ² and 90%.
It is a value measured using a silver chloride flat type composite electrode after being left for 10 minutes in an atmosphere of RH or more. A specific example of the flat electrode is a pH meter manufactured by Toa Denpa Kogyo Co., Ltd. The film surface pH in the present invention is 4.5 or more and less than 6.0, and particularly preferably 4.5 to 5.8.

The hydrazine derivative used in the present invention will be described. In the present invention, the compound of the general formula (I) described in Japanese Patent Application No. 6-47961 is used. Specifically, compounds represented by I-1 to I-53 described in the same specification are used.

The following hydrazine derivatives are also preferably used. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, pages 8 to 1 of the publication
Compounds 1 to 38 on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4-1 to 4-10 described on page 26, Compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formula (1) and the general formula (2) described in JP-A-6-289520, specifically, from page 5 of the same publication.
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically compounds I-1 to I-38 described on pages 5 to 10 of the same; Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the publication. Compounds represented by formula (H) and formula (Ha) described in JP-A-7-104426, specifically compound H described on pages 8 to 15 of the same;
-1-H-44.

The hydrazine derivative particularly preferably used in the present invention has an anionic group or a nonionic group which forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group,
And a hydrazine derivative represented by the general formula (D). First, the former will be described in detail.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means an atom selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom between a nitrogen atom and an anionic group near the anionic group of hydrazine.
It means that a binding chain formed by the individual is interposed. More preferably, a bond chain formed by 2 to 5 atoms selected from at least one of a carbon atom and a nitrogen atom is present as the vicinity, and a bond chain formed by 2 to 3 carbon atoms is more preferable. It is the case of intervening. The nonionic group that forms an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and has at least an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following formulas (A), (B) and (C). General formula (A)

[0095]

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(Wherein R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine). Represents a nonionic group forming an intramolecular hydrogen bond.) General formula (B)

[0097]

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(In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (C)

[0099]

[Chemical 40]

(Wherein X ³ represents a group capable of substituting on a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (A), (B) and (C) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, Allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amide group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

[0104] alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Linear, branched or cyclic alkoxy group such as methoxy, isopropoxy and benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom.
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group, or an alkynyl group. n ³ =
In the case of 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group of R ³ has a Hammett σ _m value of 0.2 or more, preferably 0.3.
As described above, for example, a halogen atom (fluorine, chlorine, bromine), a cyano group, a sulfonyl group (methanesulfonyl, benzenesulfonyl), a sulfinyl group (methanesulfinyl), an acyl group (acetyl, benzoyl), an oxycarbonyl group (methoxycarbonyl) ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² each represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-butene-1,4-yl, 2
-Butyn-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

Examples of the electron-withdrawing group possessed by L ¹ include R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid, and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). As the nonionic group, an oxygen atom, a nitrogen atom, a group having at least one of a sulfur atom and a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Y ¹ to Y ³ are preferably anionic groups, and more preferably carboxylic acids and salts thereof.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable groups include those mentioned as the substituents contained in R ¹ of the general formula (A). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler, or may have an adsorption promoting group to silver halide. The diffusion-resistant group has 8 to 30 carbon atoms, and preferably has 12 to 25 carbon atoms. As the adsorption-promoting group for silver halide, thioamides (eg, thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,2
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
It is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorptive group is protected and the protective group is removed at the time of development to increase the adsorptivity to silver halide.

In the general formulas (A), (B) and (C),
The radicals from which the hydrogen atoms of the two compounds are removed may combine with each other to form a bis type. In the general formulas (A), (B), and (C), the general formulas (A) and (B) are preferable, and the general formula (A) is more preferable. Further, in the general formulas (A), (B) and (C), the following general formulas (D), (E) and (F) are more preferable, and the general formula (D) is most preferable. General formula (D)

[0112]

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(In the formula, R ⁴ , X ⁴ and m ⁴ are respectively synonymous with R ³ , X ³ and m ^{3 of the} general formula (C), and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ¹ of the general formula (A). ) General formula (E)

[0114]

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(In the formula, R ⁵ , X ⁵ and m ⁵ have the same meanings as R ³ , X ³ and m ^{3 in} formula (C), respectively, and L ⁵ , Y ^{5 and}
Is synonymous with L ² and Y ^{2 in} the general formula (B). ) General formula (F)

[0116]

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(Wherein R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y is R ³ , R ³ , X ³ , m ³ , n ³ or Y in the general formula (C).
Synonymous with ³ . )

Specific examples of the nucleating agent used in the present invention are shown below, but the present invention is not limited thereto.

[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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Next, the hydrazine derivative represented by the general formula (D) will be described in detail. General formula (D)

[0126]

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In the formula, R ₀ represents a difluoromethyl group or a monofluoromethyl group, and A ₀ represents an aromatic group.
However, at least one of the substituents possessed by A ₀ is a diffusion resistant group, a silver halide adsorption promoting group, an alkylthio group, an arylthio group, a heterocyclic thio group, a quaternary ammonium group,
A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a saturated heterocyclic group containing a sulfide bond or a disulfide bond, or at least one of these groups It is a substituent containing.

Among the compounds represented by the general formula (D), preferred compounds are represented by the following general formula (1-a). General formula (1-a)

[0129]

[Chemical 51]

In the formula, R1 represents a difluoromethyl group or a monofluoromethyl group, A1 represents a divalent aromatic group, R2 and R3 represent a divalent aliphatic group or an aromatic group, and L1 and L2 are It represents a divalent linking group, and m2 and m3 each independently represent 0 or 1. X1 is a diffusion-resistant group, a group promoting adsorption to silver halide, an alkylthio group, an arylthio group, a heterocyclic thio group, a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom,
It represents an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a saturated heterocyclic group containing a sulfide bond or a disulfide bond.

Among the compounds represented by the general formula (1-a), preferred compounds are represented by the following general formula (1-b). General formula (1-b)

[0132]

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In the formula, X11, R11, R21, R31, L21, m21
And m31 are each X1 in the general formula (1-a).
, R1, R2, R3, L2, m2 and m3 have the same meanings, Y represents a substituent and n represents an integer of 0 to 4. Next, the compound represented by formula (D) will be described in detail. The aromatic group represented by A ₀ in the general formula (D) is a monocyclic or bicyclic aryl group and an aromatic heterocyclic group. Specific examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrrole ring, a furan ring, a thiophene ring, a thiazole ring and an indole ring. A ₀ preferably contains a benzene ring, and particularly preferably a benzene ring. A ₀ may be substituted with a substituent. Examples of the substituent include an alkyl group, an aralkyl group, an aryl group,
Alkoxy, aryloxy, hydroxy, acyloxy, acyl, oxycarbonyl, carbamoyl, N-sulfonylcarbamoyl, carboxyl, substituted amino, acylamino, sulfonamide, ureido, urethane, sulfonyl Ureido group,
Alkylthio, arylthio, sulfonyl, sulfamoyl, acylsulfamoyl, carbamoylsulfamoyl, sulfo, cyano, halogen, phosphinyloxy, phosphinylamino, sulfamoylamino And an oxamoylamino group. These groups may be further substituted. Among these, a sulfonamide group, a ureido group, an acylamino group, a carbamoyl group, an alkoxy group, a substituted amino group, an alkyl group, and an oxycarbonyl group are preferred, and a sulfonamide group and a ureido group are particularly preferred. Next, the specific group which the substituent of A ₀ should have is described in detail.
The diffusion resistant group means a diffusion resistant group in a photographic coupler or the like, a so-called ballast group, which is used when the compound of the present invention is added to a specific silver halide emulsion layer. Is a group that can easily prevent diffusion to other layers, or a group that can be prevented from being easily eluted in a developing solution during development. Specifically, it is a group having 8 or more total carbon atoms, preferably 8 to 16 total carbon atoms. As the ballast group, preferably, an alkyl group, an aryl group, an alkoxy group, an aryl group having 8 or more total carbon atoms is used. Examples include an oxy group, an oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a carbonyloxy group, a ureido group, a sulfamoyl group, and a combination thereof. When A ₀ has a ballast group, the total number of carbon atoms of A ₀ including the ballast group is 14 or more.

The adsorption promoting group to silver halide is preferably a thioamide group, a mercapto group, a group having a disulfide bond or a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption promoting group is a divalent group represented by -CS-amino- and may be a part of the ring structure or may be an acyclic thioamide group.
Useful thioamide adsorption promoting groups are described, for example, in US Pat.
30,925, 4,031,127, 4,08
Nos. 0,207, 4,245,037, 4,25
Nos. 5,511, 4,266,013 and 4,2
76, 364, and "Research Disclosure," Vol. 151, No. 1.
5162 (November 1976), and Vol. 176, N
o. 17626 (December 1978).

Specific examples of the acyclic thioamide group are, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group are, for example, 4-thiazoline-2-thione and 4-thiazoline-2-thione group. Imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3.
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione and the like can be mentioned. It may be substituted. As the mercapto group, an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the —SH group is bonded is a nitrogen atom next to it, a cyclic thioamide group having a tautomer relationship with Are synonymous, and specific examples of this group are the same as those listed above).

Examples of the 5- to 6-membered nitrogen-containing heterocyclic group include 5- to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like.
These may be further substituted with a suitable substituent.
Preferred as the adsorption promoting group is a cyclic thioamide group (that is, a mercapto-substituted nitrogen-containing heterocycle, for example, 2
-Mercaptothiadiazole group, 3-mercapto-1,
2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or a nitrogen-containing heterocyclic group forming iminosilver (for example, , A benzotriazole group, a benzimidazole group, an indazole group, etc.). In the present invention, the adsorption promoting group includes its precursor. The precursor is an adsorption promoting group with a precursor group, which is released by the developing solution for the first time during development, and reacts with hydroxide ion or sulfite ion in the developing solution or with a developing agent. It is disassembled as a scratch. Specifically, a carbamoyl group, a 1,3,3a, 7-tetrazainden-4-yl group, a uracil group, an alkoxycarbonyl group, or the 4-position is substituted with an ureido group, a sulfonamide group, or an amide group. 4-substituted-2,5-dihydroxyphenyl group and the like can be mentioned.

The alkylthio group is a substituted or unsubstituted, branched, cyclic or linear chain having 1 to 18 total carbon atoms.
The alkylthio group of is preferably a substituent thereof,
An aryl group, an alkoxy group (including an alkoxy group containing repeating ethyleneoxy or propyleneoxy units), a carboxyl group, a carbonyloxy group, an oxycarbonyl group, an acylamino group, a quaternary ammonium group,
Examples thereof include an alkylthio group, a heterocyclic group, a sulfonamide group, and a ureido group. Specific examples of the alkylthio group include the following groups.

[0138]

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The arylthio group is a substituted or unsubstituted arylthio group having a total of 6 to 18 carbon atoms, and as the substituent, the substituent which A ₀ of the general formula (D) may have is explained. The same thing as is mentioned. The arylthio group is preferably a substituted or unsubstituted phenylthio group, specifically, a phenylthio group and 4-τ.
-Butylphenylthio group, 4-dodecylphenylthio group and the like.

The heterocyclic thio group is a substituted or unsubstituted, saturated or unsaturated heterocyclic thio group having 1 to 18 carbon atoms and contains at least one oxygen atom, nitrogen atom, or sulfur atom. It is a 5- or 6-membered monocyclic heterocycle or a condensed heterocycle. Specifically, a benzothiazolylthio group, a 1-phenyl-5-tetrazolylthio group, 2
-Mercaptothiadiazolyl-4-thio group, pyridyl-
2-thio group and the like can be mentioned.

The quaternary ammonium group represents a quaternary aliphatic ammonium cation or a quaternary aromatic ammonium cation, and their counter anions. It may be a cyclic quaternary ammonium group, and the total carbon number of the quaternary ammonium cation is preferably 3 to 24. As the counter anion, specifically, chloro anion, bromo anion,
Examples thereof include iodo anion, sulfonate anion, and carboxylate anion. When the compound represented by the general formula (D) has a sulfo group, a carboxyl group, or the like, an inner salt may be formed.

When X represents a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, specific examples thereof include pyridinium group, quinolinium group, isoquinolinium group, phenanthrinium group, triazolinium group and imidazoli group. And a benzothiazolinium group. These groups may be further substituted with a substituent, but the substituent is preferably an alkyl group, an aryl group, an alkoxy group, an alkylcarbamoyl group, an amino group, an ammonium group or a heterocyclic group.

The alkoxy group containing an ethyleneoxy or propyleneoxy unit is specifically R ₄ -O- (CH ₂ CH ₂
O) _p- , R ₄ -O- ｛CH ₂ CH (CH ₃ ) O｝ _p- or R ₄ -O-
It is an alkoxy group represented by {CH ₂ CH (OH) CH ₂ O} _p − or the like. Here, p represents an integer of 1 or more, and R ₄
Represents an aliphatic group or an aromatic group. R ₄ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Specifically, CH ₃ O (CH ₂ CH ₂ O) ₃ −, C ₆ H ₁₃ O
(CH ₂ CH ₂ O) ₂ −, C ₄ H ₉ O− (CH ₂ CH ₂ CH ₂ O) ₂ −, C ₈ H ₁₇ OCH _{2
CH (OH) CH 2 O -} , C 12 H 25 O- {CH 2 CH (CH 3) O} 2 -, C 2 H
₅ O (CH ₂ CH ₂ O) _6- , and the like.

The saturated heterocyclic group containing a sulfide bond or a disulfide bond is specifically -S- or -S-.
It represents a 5- or 6-membered saturated heterocycle containing an S-bond and is preferably a group shown below.

[0145]

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Next, the compound represented by formula (1-a) will be described. In A ₁ is formula (1-a) represents a divalent aromatic group, which except where more limited Yu to be substituents of A ₀ In formula (1-a), general formula It is a group having substantially the same meaning as A _{0 in} (D), and its preferred range is also the same. That is, the divalent aromatic group represented by A ₁ in the general formula (1-a) is preferably
It is a monocyclic arylene group, more preferably a phenylene group. When A ₁ represents a phenylene group, this may have a substituent. Examples of the substituent of the phenylene group include those described for the substituent of A _{0 in} the general formula (D), and preferably an alkyl group, an alkoxy group, a hydroxy group, an amino group, an alkylamino group, an acylamino group. , Sulfonamide group, ureido group,
It is a halogen atom, a carboxyl group, a sulfo group, etc., and the total number of carbon atoms in these groups is 1 to 12, particularly preferably 1
~ 8. When A ₁ represents a phenylene group, particularly preferably when A ₁ represents an unsubstituted phenylene group.

In the general formula (1-a), R2 and R3 are 2
Represents a valent aliphatic group or aromatic group. The divalent aliphatic group is a substituted or unsubstituted, linear, branched or cyclic alkylene group, alkenylene group or alkynylene group, and the aromatic group is a monocyclic or bicyclic arylene group. R2 and R3 are preferably an alkylene group or an arylene group, and most preferably R2 represents a phenylene group and R3 represents a phenylene group or an alkylene group. These are A in the general formula (D).
_It may have the same substituent as described for the substituent of ₀ .

In the general formula (1-a), the divalent linking group represented by L1 and L2 means --O--, --S--, --N.
(R _N) - (R _N represents a hydrogen atom, an alkyl group or an aryl group,.), - CO -, - SO 2 -, group alone etc., or a group composed of a combination of these groups.
The group consisting of a combination here specifically means -CO.
_{N (R N) -, -} SO 2 N (R N) -, - COO -, -
_{N (R N) CON (R} N) -, - SO 2 N (R N) CO
_{-, - SO 2 N (R} N) CON (R N) -, - N
_{(R N) COCON (R N} ) -, - N (R N) SO 2 N
(R _N )-and the like. In the general formula (1-a), L
1 is preferably -SO ₂ NH -, - NHCONH-,
-O -, - S -, - N (R N) - a, and most preferably -SO ₂ NH -, - it is -NHCONH-. L2 is _{preferably, -CON (R N) -,} - SO 2 NH -, - N
_{HCONH -, - N (R N} ) CONH -, - is COO-. Here L ₂ is -CON (R _N) - or -N
When representing the (R _N) CONH-, as R _N is a substituted alkyl group, it may be a represent the -R ₃ -X groups in Formula (1-a).

In the general formula (1-a), X1 is a diffusion resistant group, an adsorption promoting group on silver halide, an alkylthio group,
It represents an arylthio group, a heterocyclic thio group, a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a heterocyclic group containing a disulfide bond. These are the same as those described above as the substituent of A ₀ of the general formula (D) or the group contained in the substituent. In the general formula (1-a), X1 is an alkylthio group,
When representing an arylthio group, a heterocyclic thio group, a quaternary ammonium group, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a heterocyclic group containing a disulfide bond, R3 is preferably an alkylene group,
m3 represents 1. When X1 in the formula (1-a) represents a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, the nitrogen-containing heterocyclic group is quaternized by the bond between the nitrogen atom and R3. In some cases, the nitrogen-containing heterocyclic group originally quaternized binds to L2 or L1 without via R3. In the former, m3 is 1 and R3 is preferably an alkylene group; in the latter, m3 represents 0.

Among the compounds represented by the general formula (1-a), more preferable ones are represented by the general formula (1-b). Wherein X11, R11, R21, R31, L21, m21 and m
31 is X1, R1 in the general formula (1-a),
R2, R3, L2, m2 and m3 are the same as defined above,
Y represents a substituent, and n represents an integer of 0 to 4. The substituent represented by Y has the same meaning as that described for the substituent that A1 may have in formula (1-a), and the preferred range is also the same. n is preferably 0 or 1, and more preferably n is 0.

In the compound represented by the general formula (1-b), when X11 represents an alkylthio group, more preferable ones are those represented by the following general formula (1-c). General formula (1-c)

[0152]

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In the formula, R ₁₂ is R ₁₁ in the general formula (1-b).
And R ₅ represents an alkylene group. L ₃₂
Represents an acylamino group, a carbamoyl group, a ureido group, an oxycarbonyl group or a sulfonamide group in connection with a benzene ring. When L ₃₂ represents an acylamino group, an oxycarbonyl group or a sulfonamide group, m ₄ represents 1, and when L ₃₂ represents a carbamoyl group or an ureido group, m ₄ represents 1 or 2. When m ₄ is 1,
R ₆ represents an unsubstituted alkyl group having a total carbon number of 7 or more, a substituted alkyl group having a total carbon number of 1 to 18, a cycloalkyl group having a total carbon number of 3 or more, and when m ₄ is 2, R ₆ is a total carbon number. Number 1
To 18 substituted or unsubstituted alkyl groups, 3 carbon atoms in total
It represents the above cycloalkyl group.

The compounds of the present invention are shown below, but the present invention is not limited thereto.

[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

[Chemical formula 61]

[0161]

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The hydrazine nucleating agent of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, It can be used by dissolving it in methyl cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine nucleating agent of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 × with ^respect to 1 mol of silver halide.
10 ⁻² mol is preferred, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferred, and 2 × 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferred.

Examples of the nucleation accelerator used in the present invention include:
The compounds described in JP-A No. 7-77783, page 48, lines 2 to 37 are mentioned, and specifically, the compounds A-1) to A-73) described on pages 49 to 58 of the same are used.

Nucleation accelerators preferably used in the present invention are onium salt compounds represented by the general formulas (I), (II), (III) and (IV), and amino compounds. This will be described in detail below.

First, the general formula (I) will be described in detail.

[0167]

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R in the formula₁, R₂, R_ThreeIs an alkyl group,
Alkyl group, aryl group, alkenyl group, cycloal
Represents a alkenyl group or heterocyclic residue, which are further substituted
It may have a group. m represents an integer, L is a P atom
And an m-valent organic group bonded at its carbon atom, n is
Represents an integer of 1 to 3 and X represents an n-valent anion.
However, X may be linked to L. R₁, R₂, R_Threeso
Examples of groups represented are methyl, ethyl,
Pill group, isopropyl group, butyl group, isobutyl group, s
ec-butyl group, tert-butyl group, octyl group, 2-d
Tylhexyl group, dodecyl group, hexadecyl group, octa
Linear or branched alkyl group such as decyl group, substituted or not
Aralkyl groups such as substituted benzyl groups; cyclopropyl
Groups such as radicals, cyclopentyl, cyclohexyl, etc.
Low alkyl group, phenyl group, naphthyl group, phenol
Aryl groups such as vinyl group; allyl group, vinyl group, 5-hexyl group
An alkenyl group such as a cenyl group; a cyclopentenyl group,
Cycloalkenyl groups such as cyclohexenyl group; pyridi
Group, quinolyl group, furyl group, imidazolyl group, thiazo
Ryl group, thiadiazolyl group, benzotriazolyl group,
Nzothiazolyl group, morpholyl group, pyrimidyl group, pyro
Heterocyclic residues such as lysyl groups are mentioned. These groups
Examples of the above substituted substituents include R₁, R₂, R_Threeso
In addition to the groups represented, fluorine atom, chlorine atom, bromine source
Child, halogen atom such as iodine atom, nitro group, 1,
A secondary or tertiary amino group, an alkyl or aryl ether group,
Alkyl or aryl thioether group, carbonamide
Group, carbamoyl group, sulfonamide group, sulfamoy
Group, hydroxyl group, sulfoxy group, sulfonyl group,
Carboxyl group, sulfonic acid group, cyano group or carbonic acid group
Group. Examples of the group represented by L include R
₁, R₂, R_ThreeIn addition to the groups synonymous with
Tramethylene group, hexamethylene group, pentamethylene
Group, octamethylene group, dodecamethylene group, etc.
Tylene group, phenylene group, biphenylene group, naphthylene
Divalent aromatic groups such as groups, trimethylenemethyl group, tetra
Polyvalent aliphatic groups such as methylenemethyl group, phenylene-
1,3,5-toluyl group, phenylene-1,2,4,5
-A polyvalent aromatic group such as a tetrayl group may be mentioned.
Examples of the anion represented by X include chlorine ion and odor.
Halide ions such as elementary ions and iodine ions, acete
Ion, oxalate ion, fumarate ion,
Carboxylate ion such as benzoate ion, p
-Toluene sulfonate, methane sulfonate, butane
Sulfonates such as sulfonate and benzene sulfonate
Toion, Sulfate ion, Perchlorate ion, Carbonate ion,
An example is nitrate ion. In the general formula (I),
R₁, R₂, R_ThreeIs preferably a group having 20 or less carbon atoms
In particular, an aryl group having 15 or less carbon atoms is particularly preferable. m is
1 or 2 is preferred, and when m represents 1, L is preferred
Is a group having 20 or less carbon atoms, and an
Particularly preferred is a alkyl group or an aryl group. m is 2
When forgoing, the divalent organic group represented by L is preferably an alkenyl group.
Xylene group, arylene group or a combination of these groups
Formed divalent group, and further, these groups and -CO- group,
-O- group, -NR_Four-Group (where R_FourIs a hydrogen atom or
R₁, R₂, R_ThreeRepresents a group synonymous with
R_FourAre present, they are the same or different
Or may be bonded to each other), -S
-Group, -SO- group, -SO₂-Formed by combining bases
Is a divalent group. When m represents 2, L is the carbon
A divalent group having 20 or less total carbon atoms bonded to a P atom.
Is particularly preferable. When m represents an integer of 2 or more,
R in the molecule₁, R₂, R_ThreeThere are multiple
The multiple R₁, R₂, R_ThreeEven though they are the same
It can be different. n is preferably 1 or 2 and m is
1 or 2 is preferable. X is R₁, R₂, R _ThreeOr
It may combine with L to form an inner salt. General of the invention
Many of the compounds of formula (I) are known
Are commercially available reagents. As a general synthetic method
Phosphinic acids, alkyl halides, sulfones
Method of reacting with alkylating agent such as acid ester: Yes
The counter anion of phosphonium salts is exchanged by a conventional method.
There is a way to do it. Specific examples of the compound represented by formula (I)
An example is shown below. However, the present invention is not limited to the following compounds
It is not something to be done.

[0169]

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[0170]

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[0171]

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[0172]

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General formulas (II) and (III) will be described in more detail.

[0174]

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In the formula, A represents an organic group for completing the heterocyclic ring, and may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A can be a 5- or 6-membered ring, and a more preferred example is a pyridine ring. B, 2 divalent group represented by C is an alkylene, arylene, alkenylene, -SO ₂ -, -
SO -, - O -, - S -, - N (R 5) - those constituted alone or in combination are preferred. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. As particularly preferred examples, B and C are alkylene, arylene, -O
-, -S- may be used alone or in combination. R ₁ and R ₂ are preferably an alkyl group having 1 to 20 carbon atoms, and may be the same or different. A substituent may be substituted on the alkyl group, and as the substituent,
Halogen atom (eg, chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl) Group), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), It represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group and an arylthio group. As a particularly preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. X represents an anion group, but in the case of an inner salt, X
Is not necessary. Examples of X include chlorine ion, bromine ion,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (1
962). )

Specific compounds of the general formulas (II) and (III) are shown below, but the invention is not limited thereto.

[0177]

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[0178]

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The general formula (IV) will be described in more detail.

[0180]

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The nitrogen-containing heteroaromatic ring represented by Z may contain a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom in addition to the nitrogen atom, and the benzene ring may be condensed. The heteroaromatic ring formed is preferably a 5- or 6-membered ring, more preferably a pyridine ring, a quinoline ring, or an isoquinoline ring. R ₅ is preferably an alkyl group having 1 to 20 carbon atoms, and may be a straight chain, branched chain, or cyclic alkyl group. More preferred is an alkyl group having 1 to 12 carbon atoms, and 1 to 8 carbon atoms
Is most preferred. X ⁻ represents an anion group, but in the case of an intramolecular salt, X ⁻ is not necessary. Examples of X ⁻ include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

The groups represented by Z and R ₅ may be substituted and preferred substituents include a halogen atom (eg chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg phenyl group, Tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (for example, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group,
Represents an alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino group, cyano group, nitro group, alkylthio group, arylthio group . Particularly preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. Other examples of the substituent of A include a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.) and a substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.). preferable. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (196
2). ) Specific compounds of the general formula (IV) are shown below, but the present invention is not limited thereto.

[0183]

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[0184]

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The following compounds are used as the amino compound. (Chemical formula 21) described in JP-A-7-84331,
Compounds represented by (Chemical Formula 22) and (Chemical Formula 23), specifically, compounds described on pages 6 to 8 of the same publication. JP-A-7-1
No. 04426, a compound represented by the general formula [Na], specifically Na-1 described on pages 16 to 20 of the same;
~ Na-22 compounds. General formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) and general formula (7) described in Japanese Patent Application No. 7-37817. ), Specifically, the compounds 1-1 to 1-19, the compounds 2-1 to 2-22, the compounds 3-1 to 3-36, and the compound 4- described in the same specification. 1 to 4-5 compounds, 5-1 to 5-41 compounds, 6-1 to 6-58 compounds and 7-1 to 7-38 compounds.

The nucleation accelerator of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl. It can be used by dissolving it in cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the powder of the nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The nucleation accelerator of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × 10 per mol of silver halide.
^-2 mol is preferable, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferable.

The developer used in the development processing of the light-sensitive material according to the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . Any known method can be used for the development processing of the present invention, and a known development processing solution can be used. The developing agent used in the developing solution used in the present invention is not particularly limited, but contains dihydroxybenzenes and auxiliary developing agents exhibiting superadditivity therewith. Furthermore, in terms of developing ability, it is 1 with dihydroxybenzenes.
A combination of -phenyl-3-pyrazolidones, a combination of dihydroxybenzenes and p-aminophenols is preferred.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
There are hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. Examples of the developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,
4-dimethyl-3-pyrazolidone, 1-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone and the like. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-
There are aminophenol, N- (4-hydroxyphenyl) glycine and the like, and among them, N-methyl-p-aminophenol is preferable. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably, it is in the range of 0.2 to 0.6 mol / liter. When the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.0
5 to 0.6 mol / liter, more preferably 0.2 to
0.5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter or less.

Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite.
The sulfite is used in an amount of 0.20 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably, 0.
It is 35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

The developer 1 used in the present invention.
The definition will be explained in detail because the pH increase when 0.1 mol of sodium hydroxide is added to liter is 0.25 or less. The developer has a p of the developer when 0.1 mol of sodium hydroxide is added to 1 liter of the developer having a pH of 10.5.
A developer having an H value of 10.75 or less. More preferably, the pH increase is 0.2 or less.

As the alkaline agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used. Additives other than those described above include development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine; A development accelerator such as imidazole or a derivative thereof; a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound as an antifoggant or black pep
per) may be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-
Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-
Sodium thiadiazol-2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-
Examples thereof include 2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. Examples of the organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730 and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, as a silver stain preventing agent in a developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, the compound described in JP-A-62-212651 can be used as the development unevenness preventing agent, and the compound described in JP-A-61-267759 can be used as the dissolution aid. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

In the developer used in the present invention, carbonate is used as a buffer, boric acid described in JP-A-62-186259, saccharides (for example, saccharose) and oximes described in JP-A-60-93433. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The pH of the developer is preferably 9.5 to 11.0, and particularly preferably 9.8 to 10.7. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7 seconds to 1 minute 30 seconds. When processing 1 square meter of the silver halide black and white photographic light-sensitive material, the replenisher amount of the developer is 225 ml or less, preferably 180 ml to 60 ml. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing agent for the fixing solution in the present invention is not particularly limited, but ammonium thiosulfate, ammonium thiosulfate, sodium thiosulfate, and mixtures thereof can be preferably used. The amount of the fixing agent used can be appropriately changed. The concentration in the working solution is generally 0.7 to about 2.0 mol / liter. The fixing treatment agent in the present invention contains a water-soluble aluminum salt which acts as a hardener, and examples thereof include ammonium sulfate, potassium alum, ammonium alum, zinc alum, aluminum nitrate, aluminum chloride, aluminum chlorate and the like. . These are preferably contained in an amount of 0.01 to 0.15 mol / liter as the aluminum ion concentration in the used liquid.

As the aluminum stabilizer in the present invention, 5-sulfosalicylic acid, iminodiacetic acid, sodium gluconate, sodium glucoheptanate, malic acid and tartaric acid are preferable.

Among them, gluconic acid, iminodiacetic acid, 5-
Sulfosalicylic acid, glucoheptanoic acid, their derivatives, or their salts are preferred. Here, gluconic acid may be an anhydride having a lactone ring. Among the above-mentioned compounds, gluconic acid, iminodiacetic acid and their alkali metal salts or ammonium salts are particularly preferable, and when these compounds dissolve the fixing agent of the present invention in water,
0.005-0.2 mol / liter, preferably 0.0
Used at a concentration of 05-0.1 mol / l. These compounds may be used alone or in combination of two or more. Furthermore, malic acid, tartaric acid, citric acid, succinic acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tyron, ascorbic acid, glutaric acid, organic acids such as adipic acid, aspartic acid, glycine, cysteine, etc. The combined use with aminopolycarboxylic acids such as amino acids, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid and nitrilotriacetic acid, and sugars is also preferable as an embodiment of the present invention.

If desired, the fixer may contain preservatives (eg, sulfite, bisulfite, etc.), pH buffers (eg, acetic acid, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, etc.), and pH adjusters (eg. For example, sodium hydroxide, ammonia, sulfuric acid, etc.), a chelating agent having the ability to soften water, a compound described in JP-A-62-78551, a surfactant, a wetting agent, a fixing accelerator and the like can be contained.
Examples of the surfactant include anionic surfactants such as sulfates and sulfin oxides, polyethylene-based surfactants and amphoteric surfactants described in JP-A-57-6840, and known defoaming agents are used. You can also do it. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof, and JP-B-45-35754 and JP-B-58-122.
Thiourea derivatives described in JP-A Nos. 535 and 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,126,459, JP-A-64-4739, JP-A-1-47939. No. 4739, 1-1
The mercapto compounds described in Nos. 59645 and 3-101728, the mesoionic compound described in No. 4-170539, and ammonium thiocyanate can be included. The fixing solid agent (powder, granule, granule, lump, paste) and tablet of the present invention may be composed of a plurality of layers such that adjacent layers do not have components that react with each other when they contact each other. Alternatively, a single and / or a blend of multiple components that do not react with each other may be coated with a water-soluble coating agent and / or a water-soluble film and packaged.

Any known method can be used for producing the fixing solid agent and the tablet in the present invention. For example, as a packaging method, there is JP-A-61-259921.
The methods described in JP-A-4-16841 and JP-A-4-78848 can be used. Further, as a method of solidification and tableting, there are disclosed in JP-A-4-85533 and JP-A-4-85533.
No. 85534, No. 4-85535, No. 5-13436.
No. 2, No. 5-197090, No. 5-204098,
No. 5-224361, No. 6-138604, No. 6-
The method described in 138605 or the like can be used.

As a method of dissolving and replenishing the treating agent of the present invention, a certain amount is dissolved with a dissolving device having a stirring function,
Method of replenishing, dissolving with a dissolving device having a dissolving portion and a portion for stocking the completed liquid, replenishing from the stock portion, adding a treating agent to the circulating system of the automatic developing machine according to the treatment to dissolve and replenish There are methods such as a method and a method of dissolving and replenishing with an automatic developing machine having a dissolving tank built therein, and any other known method can be used.

The pH of the fixing processing agent of the present invention when dissolved is 4.
It is 0 or more, preferably 4.6 to 5.5. The replenishing amount of the fixing solution is 600 ml / m ² or less with respect to the processing amount of light-sensitive material, preferably ^{500ml / m 2 ~60ml / m 2} .

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-287252. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 23
As described in JP-A No. 5133, it can be used for a processing solution having a fixing ability which is a preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferable.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. . Four steps of a stabilization step may be used instead of the washing step.

The solid processing agent used in the present invention is powder,
Tablets, granules, powders, lumps, or pastes are used, and the preferred form is the form or tablet described in JP-A-61-259921. The method for producing tablets is described in, for example, JP-A Nos. 51-61837 and 54-155038.
No. 52-88025, British Patent No. 1,213,808, and the like, and can be produced by a general method. Further, as a granule treating agent, for example, JP-A Nos. 2-109042 and 2-109.
It can be produced by a general method described in Nos. 043, 3-39735 and 3-39739. Further, the powder treating agent can be prepared by a general method as described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured.

The high density of the solid processing agent of the present invention means that its dissolution
From the viewpoint of sex and the effect of the object of the present invention, 0.5 to
6.0 g / cm^ThreeThose of 1.0 to 5.0 are particularly preferable.
g / cm ^ThreeAre preferred.

"Two types of particles having at least two mutually reactive particulate materials, separated by at least one intervening separation layer of a material inert to adjacent layers of reactive materials. In a solid processing agent characterized by placing a reactive substance of, a vacuum-packable bag as a packaging material, and evacuating and sealing the bag, the word "inert" means that when the substances are in physical contact with each other. It means that it does not react under normal conditions in the package, or that there is no reaction if there is any reaction. The inert substance, apart from being inert to the two mutually reactive substances, need only be inert in the intended use of the two reactive substances. Furthermore, an inert substance is a substance that is used simultaneously with two reactive substances. For example, since hydroquinone and sodium hydroxide react with each other in a developing solution when they come into direct contact, they can be stored in a package for a long period of time by using sodium sulfite or the like as a separation layer between hydroquinone and sodium hydroxide in vacuum packaging. Used as packaging materials for these vacuum packaging materials are bags made from a laminate of inert plastic film, plastic material and metal foil.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention and the development processing method. For example, those described in the following sections can be preferably used. Item Applicable place 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, right lower column, line 4, and JP-A 2-103536, page 16, lower right column, line 3 to the same Page 17, lower left column, line 20, and spectral sensitizing dyes described in JP-A Nos. 1-112235, 2-124560, 3-79928, Japanese Patent Application Nos. 3-189532 and 3-41, 1064. . 2) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to page 4, Lower right column, line 18. 3) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A-1-237538 The thiosulfinic acid compound described in the official gazette. 4) Polymer Latte JP-A-2-103536, page 18, lower left column, line 12 to line 20. 5) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to compound 19th line, upper left column, first line. 6) Mat agent / slip JP-A-2-103536, page 19, upper left column, line 15 From agent / plasticizer, page 19, upper right column, line 15 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 8) Dyes: Dyes from the lower right column, lines 1 to 18 of page 17, JP-A-2-103536, the solid dyes described in JP-A-2-294638 and JP-A-3-185773. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and Japanese Unexamined Patent Publication No. 1-131832 11) Redox compound Compounds represented by the general formula (I) in Japanese Unexamined Patent Publication No. 2-301743 (especially compound Examples 1 to 50), the general formulas (R -1), (R-2) and (R-3) described in JP-A 3-174 143, page 3 to page 20, compound examples 1 to 75, Further, the compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 12) Monomethine compound Compounds of general formula (II) described in JP-A-2-287532 (particularly compounds II-1 to II-26). 13) Dihydroxybe Compounds described in JP-A-3-39948, page 11, upper left column to twelfth genus, page lower left column, and EP452772A.

[0212]

【Example】

Example 1 <Preparation of emulsion> Preparation of emulsion A 1582 ml of gelatin aqueous solution (gelatin-1) was placed in a reaction vessel.
(Deionized calcari-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, HNO ₃ 1N liquid 7.
8 ml, pH 4.3), NaCl-1 solution (100 ml
13 ml of NaCl (containing 10 g of NaCl therein),
While maintaining the temperature at 0 ° C., the Ag-1 solution (AgNO
₃ containing 20 g) and X-1 solution (NaCl in 100 ml)
(Including 7.05 g) was simultaneously mixed and added at 62.4 ml / min in 15.6 ml portions. After stirring for 3 minutes, the Ag-2 solution (1
100 ml of AgNO _{3 in} 2 ml) and X-2 solution (100
(containing 4.2 g of KBr in 8 ml) at 80.6 ml / min.
8.2 ml was mixed simultaneously. After stirring for 3 minutes, Ag-
Solution 1 and solution X-1 were simultaneously mixed and added at a rate of 62.4 ml / min in 46.8 ml portions. After stirring for 2 minutes, aqueous gelatin solution 20
3 ml (gelatin-113 g, NaCl 1.3 g, pH
NaOH 1N solution was added to make it 6.0), and p
After setting Cl to 1.8, the temperature is raised to 75 ° C. and pCl
And then aged for 42 minutes. An AgCl fine grain emulsion (average grain diameter 0.1 μm) was added for 20 minutes at an addition rate of 2.68 × 10 ⁻² mol / min AgCl. 1 after addition
After aging for 0 minutes, a precipitating agent was added, the temperature was lowered to 35 ° C., and the precipitate was washed with water. Add an aqueous gelatin solution and p
H was adjusted to 6.0. The resulting emulsion was high silver chloride (100) tabular grains containing 1.3 mol% of AgBr based on silver. The shape characteristic values of the particles are shown in Table 1. Emulsions B to G as shown in Table 1 were prepared in the same manner by adjusting the amount of KBr added to solutions X-1 and X-2 and the temperature during grain preparation.

Preparation of Emulsion H 0.13 M silver nitrate aqueous solution and 1.5 × per mol of silver
^Contains 10 ^-7 moles of K ₂ Rh (H ₂ O) Cl ₅ and 2 × 10 ^-7 moles of K ₃ IrCl ₆ , containing 0.04 M potassium bromide and 0.09 M sodium chloride. The halogen salt aqueous solution was added to a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione by stirring with a double jet method at 38 ° C. for 12 minutes to obtain an average particle size of 0.13 μm and containing silver chloride. Nucleation was performed by obtaining silver chlorobromide grains having a rate of 70 mol%.
Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, a 0.26 M potassium bromide, and a halogen salt aqueous solution containing 0.65 M sodium chloride were added over 20 minutes by the double jet method.

Thereafter, 1 × 10 ⁻³ mol of KI solution was added to each emulsion for conversion, and the emulsion was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver, pH 6.5 and pAg 7.5. Then, the sensitizing dye of the present invention and the following comparative compound were added at 5 × 10 ⁻⁴ mol per mol of silver as shown in Table 1 at a temperature of 60 ° C. Furthermore, 7 mg of sodium benzenethiosulfonate and 2 m of benzenesulfinic acid per mol of silver
g, 8 mg of chloroauric acid, 200 mg of potassium thiocyanate and 5 mg of sodium thiosulfate were added and chemically sensitized by heating at 60 ° C. for 45 minutes, and then 4-hydroxy-6-methyl-1,3,3a as a stabilizer. , 7-Tetrazaindene 1
50mg was added, and proxel 100mg was added as a preservative.
Was added. The obtained particles each have an average particle size of 0.
The silver iodochlorobromide cubic grains had a size of 25 μm and a silver chloride content of 69.9 mol%. (Variation coefficient 10%) Table 1 shows characteristic values of Emulsions A to H.

[0215]

[Table 1]

After desalting these emulsions by a coagulation method,
62 g of gelatin and 1.75 g of phenoxyethanol were added to adjust to pH 6.5 and pAg 8.5 g.

<Chemical sensitization> Particle A prepared as described above
Chemical sensitization was performed while H was maintained at 60 ° C. with stirring. First, sodium benzenethiosulfonate was added in an amount of 10 ⁻⁴ mol per mol of silver halide, and then a diameter of 0.
10 μm AgBr fine particles 1.0 mol% based on the total silver amount
Then, AgI fine particles with a diameter of 0.01 μm were added in an amount of 0.1 mol% with respect to the total amount of silver, and thiourea dioxide was added in an amount of 1 × 10 ⁻⁶ mol / mol Ag, and the mixture was maintained for 22 minutes to reduce and increase I made a sense. Then 4-hydroxy-6
-Methyl-1,3,3a, 7-tetraazaindene to 3
× 10 ^-4 mol / mol Ag and sensitizing dyes D-1 and D-2 were added at 5 × 10 ^-4 mol / mol Ag, respectively. Further calcium chloride was added. Then sodium thiosulfate (6 × 10 ⁻⁶ mol / mol Ag) and selenium compound-I
(4 × 10 ⁻⁶ mol / mol Ag) was added. Further, 1 × 10 ⁻⁵ mol / mol Ag of chloroauric acid and 3.0 × 10 ⁻³ mol / mol Ag of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C.

[0218]

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<Preparation of Coated Sample> On a polyester terephthalate film support having a moisture-proof layer undercoat containing vinylidene chloride, an EM layer, a PC layer and a PC layer were sequentially formed from the support side.
A sample was prepared by coating so as to have a layer structure of the OC layer. The preparation method of each layer and the coating amount are shown below.

(EM) To the above emulsion, the compounds shown in Tables 2 and 3 were added, and further 5 mg of KBr per 1 mol of silver, 3 ×.
10 ⁻⁴ mol of a mercapto compound represented by the following (a),
2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline was added, 1 × 10 ⁻⁴ mol of the hydrazine derivative H-1 was added, and 4 × 10 ⁻⁴ mol of the following compound A-1 was used as a nucleation accelerator. , A-2 was added at 4 × 10 ⁻⁴ mol. Further, 20 mg / N-oleyl-N-methyltaurine sodium salt
m ² , dodecylbenzenesulfonic acid sodium salt 20 mg /
m ² and (d) compound 15 mg / m ² , average particle size 0.02 μ
200 mg / m ² of colloidal silica of m ² was added so that 100 mg of the water-soluble latex shown in (e) was added.
/ M ² , polyethyl acrylate dispersion 150 mg /
m ² , 150 mg / m ² of a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7), core-shell type latex (core Styrene / butadiene copolymer (weight ratio 37/63), shell; styrene / 2-acetoacetoxyethyl methacrylate (weight ratio 84/16), core /
(Shell ratio = 50/50) was added at 150 mg / m ² , and 1,3-divinylsulfonyl-2-propanol was added at 200 mg / m ² as a hardening agent. The pH of the solution was adjusted to 5.5 using acetic acid. Further, citric acid was added so that the pH on the film surface became the values shown in Tables 2 and 3. They were coated such that the coated silver amount was 2.8 g / m ² and gelatin was 1.3 g / m ² .

(PC) Gelatin 0.5 g / m ² , dispersion of polyethyl acrylate 250 mg / m ² , sodium ethylsulfonate 5 mg / m ² , 1,5-dihydroxy-2-
Benzaldoxime 10 mg / m ² , dye (a) 5 mg / m ²
m ^{2 was} applied. (OC) Gelatin 0.3 g / m ² , average particle size about 3.
An amorphous SiO ₂ matting agent 40 mg / m ² of 5 [mu] m, an average particle diameter of the colloidal silica 100 mg / m ² of 0.02 [mu] m, Methanol Silica 100 mg / m ^2, polyacrylamides 100
mg / m ² , silicone oil 20 mg / m ² and a compound represented by (f) 30 mg / m ^2, and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (g) as a coating aid and dodecylbenzene sulfone. 50 mg / m ² of sodium acid was applied.

[0222]

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These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ² Compound [a] 110 mg / m ²

[0224]

[Chemical 76]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [b], dye [c], dye [d], dye [e] Dye [b ] 120 mg / m ² dye [c] 50 mg / m ² dye [d] 30 mg / m ² dye [e] 30 mg / m ²

[0226]

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[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

<Exposure and development> Each sample prepared is 488 nm
Through an optical wedge for sensitometry through an interference filter having a peak at 1, and then exposed with xenon flash light with an emission time of 10 ^-5 sec, and a developing solution of the following composition
After developing at 30 ° C. for 30 seconds, fixing, washing with water, drying and processing were performed.
As the fixing solution, GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used. FG-6 manufactured by Fuji Photo Film Co., Ltd.
80AG was used.

<Developer formulation> Potassium hydroxide 40.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 3.0 g Hydroquinone 40.0 g 5-Methylbenzotriazole 0. 08 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 0.3 g sodium erythorbate 6.0 g potassium hydroxide is added, and water is added. To 1 liter and adjust the pH to 10.5. <Evaluation of Photographic Property> (Photographic Property-1) Performance obtained from a sample immediately after coating. (Photographic property-2) Performance obtained from a sample stored at a temperature of 50 ° C. and a humidity of 60% for 3 days.

<Photographic Evaluation Items> (Sensitivity) The sensitivity is shown by the relative value of the reciprocal of the exposure dose. (Γ) As an index showing the contrast of the image, a point of fog + density 0.3 to a point of fog + density 3.0 of the characteristic curve was connected by a straight line, and this straight line was expressed as a γ value. That is, γ = (3.0-0.3) / [log (exposure amount giving density 3.0) -log (exposure amount giving density 0.3)]
The larger the γ value, the harder the photographic characteristics are. (Dmax, fog) shows the maximum density and fog density, respectively.

<Evaluation of Pressure Property> Under the condition of 25 ° C. and 60% RH, the surface of the sample was rubbed with a sapphire needle having a diameter of 0.1 mm under a continuous load of 0 to 200 g, and then developed using the above developing solution. Then, the load at which fogging occurs was determined. Practically, it is preferable that fog does not occur under a load of less than 150 g.

The results are shown in Tables 2 and 3.

[0233]

[Table 2]

[0234]

[Table 3]

The sample of the present invention has little change in photographic performance with the passage of time and is less likely to cause pressure fog.

Example 2 <Preparation of Emulsion, Chemical Sensitization> Emulsions A to H of Example 1 were used to carry out chemical sensitization in the same manner as in Example 1. However, D-3 was used as the sensitizing dye.

[0237]

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<Preparation of Coating Sample> On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, a UL layer, an EM layer, and a support layer were sequentially formed from the support side.
A sample was prepared by coating so as to have a PC layer and an OC layer. The preparation method of each layer and the coating amount are shown below. (UL) as a UL layer, gelatin 0.5 g / m ^2, dispersion of 150 mg / m ² of polyethyl acrylate, following dye [a] 5 mg / m ^2, the compound (a) was 5 mg / m ² coating .

(EM) To the above emulsion, the compounds shown in Table 4 were added, and further, 5 mg of KBr per mol of silver, 3 × 10 ^-4.
Molar mercapto compound represented by the following (b), 2 × 1
0 ^-3 mol of 5-chloro-8-hydroxyquinoline was added, the hydrazine derivative H-2 was added 1 × 10 ^-4 mol,
4 × 10 ⁻⁴ mol of the following compound A-1 as a nucleation accelerator,
4 × 10 ⁻⁴ mol of A-2 was added. Further, N-oleyl-N-methyltaurine sodium salt 20 mg / m ² , dodecylbenzenesulfonic acid sodium salt 20 mg / m ² ,
The compound (e) was added in an amount of 15 mg / m ² , colloidal silica having an average particle size of 0.02 μm was added so as to be applied in an amount of 200 mg / m ² , and the water-soluble latex represented by (f) was added in an amount of 100 mg / m ^2.
m ² , 150 mg / m ^{2 of} polyethyl acrylate dispersion,
150 mg / m ² of a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7), core-shell type latex (core; styrene / Butadiene copolymer (weight ratio 37
/ 63), shell; styrene / 2-acetoacetoxyethylmethacrylate (weight ratio 84/16), core / shell ratio = 50/50) 150 mg / m ² , and 1,3-divinylsulfonyl-2 as a hardener. -2 propanol
00 mg / m ² was added. The pH of the solution was 5.5 using acetic acid.
Was prepared. Further, citric acid was added so that the pH on the film surface became the value shown in Table 3. The amount of silver coated on them is 3.5 g /
m ² and gelatin 1.5 g / m ² .

(PC) Gelatin 0.5 g / m ² , dispersion of polyethyl acrylate 250 mg / m ² , sodium ethylsulfonate 5 mg / m ² , 1,5-dihydroxy-2-
Benzaldoxime was applied at 10 mg / m ² . (OC) Gelatin 0.3 g / m ² , average particle size about 3.
An amorphous SiO ₂ matting agent 40 mg / m ² of 5 [mu] m, an average particle diameter of the colloidal silica 100 mg / m ² of 0.02 [mu] m, Methanol Silica 100 mg / m ^2, polyacrylamides 100
30 mg / m ^{2 of} a compound represented by mg / m ² , silicone oil 20 mg / m ² and (g) and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (h) as a coating aid and dodecylbenzene sulfone. 50 mg / m ² of sodium acid was applied.

[0241]

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These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ² Compound [a] 110 mg / m ²

[0243]

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SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [b], dye [c] and dye [d] dye [b] 40 mg / m ² Dye [c] 20 mg / m ² Dye [d] 90 mg / m ²

[0245]

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[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

<Exposure and development> Each sample prepared is 633 nm.
Through an interference filter having a peak at 1, a light was exposed with a xenon flash light having an emission time of 10 ⁻⁵ sec through an optical wedge for sensitometry, and the development process was performed in the same manner as in Example 1.

<Evaluation of Photographic Properties> The same procedure as in Example 1 was carried out. <Evaluation of pressure property> The same evaluation as in Example 1 was performed.

The results are shown in Table 4.

[0250]

[Table 4]

The samples of the present invention have little change in photographic performance with the passage of time and are less likely to cause pressure fog.

Example 3 Samples of the invention obtained in Example 1 (No. 4, 6,
8) and a comparative sample (No. 22) are shown in Table 5.
A running experiment was conducted with a developer to evaluate photographic characteristics. The running conditions are 80% blackening per day (10
Eight of the sheets were exposed to light, and the size of the whole paper (50.
40 times each film of 8 x 61.0 cm) is processed and running for 6 days and resting for 1 day
I went there. The replenishing amount is ^{250ml / m 2, 170ml / m} 2. The evaluation method is the same as the photo characteristics, and the replenishment amount is 2
Respect ^{50ml / m 2, 170ml / m} 2, and the photographic characteristics 3,4 respectively. The sensitivity was evaluated relative to the sensitivity of Experiment No. 1 as 100. The results are shown in Table 6. Experiment Nos. 2, 4, 6, 8, 10, 12 using the sample of the present invention and the preferred developing solution of the present invention showed good results.

[0253]

[Table 5]

[0254]

[Table 6]

Example 4 The sample of the present invention used in Example 2 (Sample No. 37)
~ 40) and comparative samples (Nos. 47 to 48), the same experiment as in Example 3 was carried out. As a result, the preferable constitutions of the present invention (Developers D-2 and D-4) had good running performance. showed that.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/34 G03C 1/34 5/29 501 5/29 501 5/30 5/30 5/31 5/31

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion has a silver chloride content of 80 mol%.
The tabular grains described above, the main plane of which is the (100) plane, the average aspect ratio is 2 or more and less than 5, and the average grain size is 0.
In the silver halide photographic light-sensitive material characterized by having a size of less than 5 μm, the emulsion layer or the other hydrophilic colloid layer has the general formula (1), (2), (3), (4),
A silver halide photographic light-sensitive material containing at least one of the compounds represented by (5) and (6). General formula (1) In the formula, Z represents N or C—X (X represents an alkyl group or an aryl group), M represents a hydrogen atom, a metal atom or ammonium, and Y represents an alkyl group or an aryl group having a hydrophilic group. General formula (2) In the formula, R ¹ and R ² may be the same or different and each is a hydroxy group, a hydroxyalkyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an alkoxy group, a phenoxy group, an alkyl group, an aryl group. ,
It represents an alkylthio group or a phenylthio group. General formula (3) In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, 1, 2, 3
Grade amino group, carbonamide group, sulfonamide group,
Alkyl group, aryl group, at least one N, O, S
It represents a 5- or 6-membered heterocycle containing atoms, a formyl group, a keto group, a sulfonic acid group, a carboxylic acid group, an alkylsulfonyl group or an arylsulfonyl group. General formula (4) In the formula, Z represents an alkyl group, an aryl group or a heterocyclic group, and M represents a metal atom or an organic cation. General formula (5) In the formula, Y represents an atomic group necessary for forming an aromatic ring or a hetero ring. General formula (6) In the formula, Y represents an atomic group necessary for forming an aromatic ring or a hetero ring, and n represents an integer of 2 to 10. 2. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide emulsion has a silver chloride content of 50 mol%.
The tabular grains described above, the main plane of which is the (100) plane, the average aspect ratio is 2 or more and less than 5, and the average grain size is 0.
A silver halide photographic light-sensitive material characterized by having a film surface pH on the emulsion layer side of 4.5 or more and less than 6.0 in the range of less than 5 μm. 3. The halogenated compound according to claim 1 or 2, wherein the silver halide emulsion layer and / or the other hydrophilic colloid layer contains a hydrazine derivative and a nucleation accelerator. Silver photographic light-sensitive material. 4. The nucleation accelerator is represented by the general formula (I), (II),
The silver halide photographic light-sensitive material according to claim 3, which is selected from compounds represented by (III) and (IV) and amino compounds. General formula (I) In the formula, R ₁ , R ₂ and R ₃ are an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group,
Represents a heterocycle residue. m is an integer, L is an n-valent organic group which is bonded to the P atom by its carbon atom, and n is an integer of 1 to 3. General formula (II): General formula (III): In the formula, A represents an organic group for completing the heterocycle.
B, and C is an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, - S -, - N
(R ₅ )-represents one or a combination of these. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. R ₁ and R ₂ each represent an alkyl group, and R ₃ and R 2
Each ₄ represents a substituent. X represents an anionic group, but X is not necessary in the case of an internal salt. General formula (IV): In the formula, Z represents an organic group for completing the heterocycle.
R ₅ represents an alkyl group. X represents an anionic group, but X is not necessary in the case of an internal salt. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion grains are chemically sensitized with at least one of a selenium compound and a tellurium compound. material. 6. A method of developing the silver halide photographic light-sensitive material according to claim 1, after imagewise exposure and replenishing with a developing solution, wherein the development initiation solution and the development replenishing solution are dihydroxy. It contains a benzene-based developing agent and an auxiliary developing agent that exhibits superadditivity with the benzene-based developing agent, and the pH rise is 0.25 or less when 0.1 mol of sodium hydroxide is added to 1 liter of the solution. A silver halide photographic light-sensitive material, which is a liquid having properties, wherein the pH of the development initiating liquid is 9.5 or more and less than 11.0, and the replenishing amount of the developing liquid is 225 ml / m ² or less. Development processing method.