JP3422095B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the development of a silver halide black and white photographic light-sensitive material to form a silver image as a final image.
More specifically, it relates to a processing method , and more specifically, it can be handled in an environment that can be called a bright room and can form a negative tone silver image with high contrast. of silver halide black-and-white photographic light-sensitive material
The present invention relates to a development processing method .

[0002]

2. Description of the Related Art Among photoengraving processes in the field of print reproduction, particularly in the work processes of collecting and returning plates, the work efficiency and work environment are improved by working in a brighter environment. That is, there is provided a silver halide light-sensitive material for plate making that can be handled in an environment that can be called a bright room. As a method of making a light-sensitive material that can be handled in a bright room by lowering its sensitivity to visible light, a silver halide emulsion mainly containing silver chloride, a rhodium salt, an iridium salt,
A method using an emulsion to which inorganic and organic desensitizers such as pinacryptol yellow and phenosafranine are added is well known. 0.05 to 0.5 without chemical sensitization
A method of using a rhodium salt and / or an organic desensitizer in a fine grain silver chloride or fine grain silver chlorobromide emulsion having a size of μm is preferably used. Furthermore, in combination with these emulsions,
A method of incorporating a yellow dye or an ultraviolet absorbing dye into a light-sensitive material is used for the purpose of sensitivity adjustment and safelight safety.

On the other hand, the light-sensitive material used in the plate-collecting and reversing process has the following features:
There is a demand for what has a so-called ultra-high contrast photographic property, which has a high blackening density in which image areas and non-image areas are clearly distinguished. In particular, the halftone image and the line image original as the return original are overlapped and exposed (so-called character image formation is performed).
In this case, there is a demand for a light-sensitive material having good line drawing reproduction performance (extracted character quality).

As a method for imparting ultra-high contrast photographic characteristics to a light-sensitive material, a method of incorporating a vitrazine derivative or a tetrazolium compound into the light-sensitive material is known, and the above-mentioned inorganic and organic desensitizers and yellow. When a method of incorporating a dye or an ultraviolet-absorbing dye into the light-sensitive material is combined, problems may occur such that the contrast enhancement effect of the hydrazine derivative or tetrazolium compound is obstructed and good line drawing reproduction performance is lost. It was

As an image system capable of obtaining ultrahigh contrast photographic characteristics in a silver halide black and white photographic light-sensitive material for return,
JP-A-60-140338, JP-A-61-238049
No. 63-183438, No. 63-296034.
No. 61-198147, No. 61-198148.
No. 61-240235. However, the pH of the developer used in these inventions is 11 or more. A developer with a pH of 11 or more is easily oxidized by air and is unstable and cannot withstand long-term storage. Therefore, a silver halide photographic light-sensitive material containing a hydrazine derivative is developed with a developer having a lower pH to obtain a high contrast image. Is required.

However, when the pH of the developing solution is low, the effect of increasing the contrast of the hydrazine derivative is lowered, and a high contrast image cannot be obtained. Although attempts have been made to develop more active hydrazine derivatives and nucleation accelerators in order to promote higher contrast, the long-term storage stability of the light-sensitive material may be reduced in some cases.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a reversal silver halide photographic light-sensitive material which can be handled under bright safelight (substantially bright room) and has ultrahigh contrast photographic characteristics. Another object of the present invention is to provide a development processing method . A second object of the present invention is to provide a method for processing a light-sensitive material which can be handled under a bright safelight (substantially in a bright room) and has good line image reproduction performance (extracted character quality). To provide. A third object of the present invention, even when a stable pH to air oxidation is treated with 11 or lower pH developers have ultrahigh contrast photographic characteristics, development of the light-sensitive material outline characters quality is good To provide a method . A fourth object of the present invention is to provide a light-sensitive material having good long-term storage stability.

[0008]

These and other objects of the present invention are provided in a method for processing a silver halide photographic light-sensitive material for a bright room having at least one silver halide emulsion layer on a support. The emulsion layer contains at least 1 × 10 ⁻⁵ mol of a heavy metal ion selected from Ir, Ru, Rh, Re and Cr per mol of silver, and is chemically sensitized with at least one of a selenium sensitizer and a tellurium sensitizer. A hydrazine derivative represented by the general formula (VI) and a general formula (VII) in at least one of the emulsion layer and the other hydrophilic colloid layer, which contains a perceived silver chloride content of 95 mol% or more.
To (X), a bright-room silver halide photographic light-sensitive material containing at least one of nucleation accelerators having a pH of 9.0.
~ 11.0 developer processing characterized by processing
It was achieved by a logical method .

The present invention will be described in detail below. To the present invention
The silver halide emulsion used is Rh, Ir, Ru, R
At least one heavy metal selected from e and Cr is contained. Preferred as these heavy metals are metal coordination complexes, and hexacoordination complexes represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (In the formula, M is a heavy metal selected from Rh, Ir, Ru, Re, and Cr. L is a bridging ligand. Y is oxygen or sulfur. M = 0, 1, 2 and n = 0, -1,-.
2 and -3. ) Preferred examples of L are halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyan. Nate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands. Specific examples of the metal coordination complex are shown below. 1. [Rh (H ₂ O) Cl ₅ ] ^-2 2. [RuCl ₆ ] ^-3 3. [Ru (NO) Cl ₅ ] ^-2 4. [RhCl ₆ ] ^-3 5. [Ru (H ₂ 0) Cl ₅ ] ^-2 6. [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 7. [Re (NO) Cl ₅ ] ^-2 8. [Ir (NO) Cl ₅ ] ^-2 9. [Ir (H ₂ 0) Cl ₅ ] ^-2 10. [Re (H ₂ 0) Cl _5] ^-2 11. [RhBr _6] ^-3 12. [ReCl _6] ^-3 13. [IrCl _6] ^-3 14. _{[Re (NS) Cl 4 (SeCN} ) ] ^{- 2} 15. [Cr (CN) ₆ ] ^-3

The above metal complex can be added to the silver halide during grain preparation. To the present invention
The content of the heavy metal in the silver halide grains used is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol per mol of silver halide. It is preferably 10 ^{−5 to} 3 × 10 ⁻⁴ mol.
Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grain is not particularly limited, but it is preferable that the heavy metal is more present outside the grain.

[0011] The silver halide emulsion of the bright room for silver halide photographic light-sensitive material of the present invention is 95 mol% or more, particularly 99 mol% or more is made of silver chloride silver chlorobromide, silver chloroiodobromide or chloride It is silver. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
JP-A-4-25832 and JP-A-4-109240.
It is preferable to use the compounds described in Japanese Patent Application No. 3-82929 and Japanese Patent Application No. 3-82929. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropion, 2-
(Selenobutyric acid), selenoesters, diacylselenides, (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium and the like. The 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 play no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. The non-unstable selenium compound used in the present invention is Japanese Patent Publication No. 46-45.
No. 53, Japanese Patent Publication No. 52-34492 and Japanese Patent Publication No. 52-
The compound described in 34491 is used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (I) and (II) are preferable. General formula (I)

[0013]

[Chemical 9]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represents an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg vinyl group, propenyl group), aralkyl group (eg benzyl group, phenethyl group), aryl group (eg phenyl group, penta) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR ₁ (R ₂ ),-
Represent OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R
₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group ) May be sufficient. In formula (I), Z ₁ is preferably an alkyl group, an aryl group or —NR
₁ (R ₂ ) and Z ₂ represents -NR ₅ (R ₆ ). R ₁ ,
R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (I), more preferably N,
N-dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide. General formula (II)

[0015]

[Chemical 10]

In the formula, Z ₃ , Z ₄ and Z _{5, which} may be the same or different, each represents an aliphatic group, an aromatic group, a heterocyclic group,
-OR ₇ , -NR ₈ (R ₉ ), -SR ₁₀ , -SeR ₁₁ , X,
Represents a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ are aliphatic groups,
It represents an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom. In the general formula (II), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ ,
The aliphatic group represented by R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (eg, methyl group, ethyl group, n-group).
Propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, A propargyl group, a 3-pentynyl group, a benzyl group, a phenethyl group). In the general formula (II), Z ₃ , Z ₄ , Z ₅ , R
_The aromatic group represented by ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, a phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3
-Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (II), Z ₃ ,
The heterocyclic group represented by Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Unsaturated heterocyclic groups (eg, pyridyl group, thienyl group,
Furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (II), R ₇ ,
The cation represented by R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In formula (II), Z ₃ , Z ₄ or Z ₅ is preferably an aliphatic group, an aromatic group or -O.
Represents R _7, R ₇ represents an aliphatic group or an aromatic group. In formula (II), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate is more preferable. Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

[0020]

[Chemical 14]

[0021]

[Chemical 15]

[0022]

[Chemical 16]

[0023]

[Chemical 17]

[0024]

[Chemical 18]

Examples of the tellurium sensitizer used in the present invention include US Pat. Nos. 1,623,499, 3,320,069, 3,772,031 and British Patent 235. No. 211, No. 1,121,496
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 635 (1980), ibid 1102 (19
79), ibid 645 (1979), Journal of Chemicals
Society Perkin Transaction (J.Che
m.Soc.Perkin Trans.) 1, 2191 (1980), S. Patay (SP
atai), The Chemistry of Organic Selenium and Tellurium Companies (The Ch
emistry of Organic Selenium and Tellurium compound
s), Vol 1 (1986), and Vol 2 (1987). As a specific tellurium sensitizer,
For example, colloidal tellurium, telluroureas (eg, allyl tellurourea, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N′N′-dimethyltelurourea, N, N′-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), isotellocyanates (for example, allyl isotellurocyanate), telluroketones (for example, telluroacetophenone), telluroamides (for example, telluroacetamide,
N, N-dimethyl tellurobenzamide), tellurohydrazide (eg N, N ′, N′-tolumethylmethyl tellurobenzhydrazide), telluroester (eg t-butyl-t)
-Hexyl telluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, diethylcarbamoyltelluride, bis (ethoxycarbonyl) telluride), (di)
Tellurides, other tellurium compounds (eg British Patent No. 1,
Negatively charged telluride ion-containing gelatin described in No. 295,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyl tellurocyanate). Of these tellurium compounds, the following general formulas (III), (IV) and (V) are preferable. General formula (III)

[0026]

[Chemical 19]

In the formula, R ₁₁ , R ₁₂ and R ₁₃ are aliphatic groups,
Aromatic group, heterocyclic group, OR ₁₄ , NR ₁₅ (R ₁₆ ), S
It represents R ₁₇ , OSiR ₁₈ (R ₁₉ ) (R ₂₀ ), X or a hydrogen atom. R ₁₄ and R ₁₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₁₅ and R _17
16 represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, R ₁₈ , R ₁₉ and R ₂₀ represent an aliphatic group, and X represents a halogen atom. Next, the general formula (III) will be described in detail. In the general formula (III), R ₁₁ , R ₁₂ ,
R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀
The aliphatic group represented by is preferably one having 1 to 30 carbon atoms, and particularly a straight chain, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl, ethyl, n
-Propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl,
Examples thereof include cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl and phenethyl. In the general formula (III), R ₁₁ ,
The aromatic group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ preferably has 6 to 30 carbon atoms,
Particularly, it is a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. General formula (I
In II), the heterocyclic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ is a 3- to 10-membered compound containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a saturated or unsaturated heterocyclic group of the ring. These may be a single ring or may form a condensed ring with another aromatic ring or a heterocycle. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocycle, such as pyridyl,
Furyl, thienyl, thiazolyl, imidazolyl and benzimidazolyl can be mentioned. In the general formula (III), R
_The cations represented by ₁₄ and R ₁₇ are alkali metals and ammonium. In the general formula (III), the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom,
Represents a bromine atom and an iodine atom. Further, the aliphatic group, aromatic group and heterocyclic group may be substituted.
The following are mentioned as a substituent. Examples of typical substituents include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, acylamino groups, ureido groups, urethane groups, sulfonylamino groups, sulfamoyl groups, Carbamoyl group, sulfonyl group, sulfinyl group,
Alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, diacylamino group, imide group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group, carboxy group, hydroxy group, phosphono Group, nitro group, and heterocyclic group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₁₁ , R ₁₂ and R ₁₃ may combine with each other to form a ring together with a phosphorus atom, and R ₁₅ and R ₁₆
May combine with each other to form a nitrogen-containing heterocycle. General formula (II
In I), preferably R ₁₁ , R ₁₂ and R ₁₃ represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group. General formula (IV)

[0028]

[Chemical 20]

In the formula, R ₂₁ represents an aliphatic group, an aromatic group, a heterocyclic group or --NR ₂₃ (R ₂₄ ) and R ₂₂ represents --NR.
_{25 (R 26), - N} (R 27) N (R 28) R 29 or -OR
Represents ₃₀ . R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R
₂₉ and R ₃₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Where R ₂₁ and R ₂₅ , R ₂₁ and R ₂₇ , R ₂₁ and R ₂₈ , R ₂₁ and R ₃₀ , R ₂₃ and R ₂₅ , R ₂₃ and R
₂₇ , R ₂₃ and R _28, and R ₂₃ and R ₃₀ may combine to form a ring. Next, general formula (IV) will be described in detail.
In the general formula (IV), R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ have the same meanings as in formula (III). In the general formula (IV), R ₂₃ , R ₂₄ , R
_The acyl group represented by ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ is preferably one having 1 to 30 carbon atoms, and particularly preferably a straight chain or branched acyl group having 1 to 20 carbon atoms. Yes,
For example, acetyl, benzoyl, formyl, pivaloyl,
Decanoyl is given. Where R ₂₁ and R ₂₅ , R ₂₁ and R
_27, R ₂₁ and R _28, R ₂₁ and R _30, R ₂₃ and R _25, R ₂₃ and R _27, if R ₂₃ and R ₂₈ and R ₂₃ and R ₃₀ are combined to form a ring, for example an alkylene group , An arylene group, an aralkylene group or an alkenylene group. Also,
The aliphatic group, aromatic group, and heterocyclic group have the general formula (II
It may be substituted with the substituents mentioned in I). General formula (I
In V), preferably R ₂₁ is an aliphatic group, an aromatic group or-
NR ₂₃ (R ₂₄ ) is represented, and R ₂₂ is —NR ₂₅ (R ₂₆ ). R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ represent an aliphatic group or an aromatic group. In formula (IV), more preferably R ₂₁
Represents an aromatic group or —NR ₂₃ (R ₂₄ ), and R ₂₂ represents —
Represents NR ₂₅ (R ₂₆ ). R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆
Represents an alkyl group or an aromatic group. Here, R ₂₁ and R ₂₅ and R ₂₃ and R ₂₅ are an alkylene group, an arylene group,
It is more preferable to form a ring via an aralkylene group or an alkenylene group. General formula (V)

[0030]

[Chemical 21]

In the formula, R ₃₁ and R ₃₂ may be the same or different, and an aliphatic group, an aromatic group, a heterocyclic group,
It represents (C = Y ')-R ₃₃ . R ₃₃ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₃₄ (R ₃₅ ), OR ₃₆ or SR ₃₇ , and Y ′ represents an oxygen atom, a sulfur atom or N.
Represents R ₃₈ . R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group,
n represents 1 or 2. Next, the general formula (V) will be described in detail. In the general formula (V), R ₃₁ , R ₃₂ ,
The aliphatic group, aromatic group or heterocyclic group represented by R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ has the same meaning as in formula (III). In addition, R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ ,
The aliphatic group, aromatic group and heterocyclic group represented by R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ may be substituted with the substituents represented by formula (III). Where R ₃₁ and R ₃₂ and R ₃₄
And R ₃₅ may combine with each other to form a ring. General formula (V)
Among them, preferably R ₃₁ and R ₃₂ are a heterocyclic group or-(C
= Y ') - represent R _33. R ₃₃ represents NR ₃₄ (R ₃₅ ) or OR ₃₆ , and Y ′ represents an oxygen atom. R ₃₄ , R ₃₅
And R ₃₆ represents an aliphatic group, an aromatic group or a heterocyclic group. In formula (V), more preferably R ₃₁ and R ₃₂ represent — (C═Y ′) — R ₃₃ . R ₃₃ is NR ₃₄ (R ₃₅ )
And Y'represents an oxygen atom. R ₃₄ and R ₃₅ represent an aliphatic group, an aromatic group or a heterocyclic group. The following formula 2
Specific examples of the compounds represented by formulas (III), (IV) and (V) of the present invention are shown in 0 to 34, but the present invention is not limited thereto.

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23]

[0034]

[Chemical formula 24]

[0035]

[Chemical 25]

[0036]

[Chemical formula 26]

[0037]

[Chemical 27]

[0038]

[Chemical 28]

[0039]

[Chemical 29]

[0040]

[Chemical 30]

[0041]

[Chemical 31]

[0042]

[Chemical 32]

[0043]

[Chemical 33]

[0044]

[Chemical 34]

[0045]

[Chemical 35]

[0046]

[Chemical 36]

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide emulsion grain. The following tests can be conducted for the rate of silver telluride formation in a silver halide emulsion. When a large amount is added (for example, 1 × 10 ⁻³ mol / mol Ag), the formed silver telluride has absorption in the visible region. Therefore, regarding sulfur sensitizers, E. Moisar
Journal of Photographic Science, 14 volumes, 181 pages (1966) and 16 volumes, 102 pages (1968).
The method described in can be applied. The amount of silver sulfide produced in a silver halide emulsion was determined by the same method as that obtained from the infinite reflectivity of the emulsion in the visible range (520 nm) using the Kubelka-Munk equation. The silver telluride formation rate can be easily determined. Further, since this reaction is apparently close to the first-order reaction, the quasi-first-order reaction rate constant can also be obtained. For example, average particle size 0.5μm
Of silver bromide octahedron emulsion (containing 0.75 mol of AgBr and 80 g of gelatin in 1 kg of emulsion), pH = 6.3, pAg =
While keeping the temperature at 8.3, the temperature is kept at 50 ° C., and 1 × 10 ⁻³ mol / mol Ag of a tellurium compound dissolved in an organic solvent (such as methanol) is added. Place the emulsion in a 1 cm thick cell on a spectrophotometer with an integrating sphere, 520 with reference to the blank emulsion.
The reflectance (R) at nm is measured over time. The reflectance is substituted into the Kubelka-Munk equation (1-R) ² / 2R, and the pseudo first-order reaction rate constant k (min ^-1 ) is determined from the change in the value. Kubelka-Mu because R = 1 always unless silver telluride is produced
The value of nk remains the same as 0 without tellurium compound. A compound having an apparent first-order reaction rate constant k of 1 × 10 ⁻⁸ to 1 × 10 ⁰ min ⁻¹ under exactly the same conditions as in this test method is preferable. Further, in a smaller addition amount range where absorption in the visible region is difficult to detect, the produced silver telluride can be separated from the unreacted tellurium sensitizer and quantified. For example, after separation by immersion in an aqueous solution of a halogen salt or an aqueous solution of a water-soluble mercapto compound, a trace amount of Te is quantitatively analyzed by an atomic absorption method or the like. The reaction rate greatly varies within a range of several digits depending on the type of compound, the silver halide composition of the emulsion to be tested, the temperature to be tested, pAg, pH and the like. The tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride with respect to a specific silver halide emulsion having a halogen composition and a crystal habit to be used. Generally speaking, for a silver bromide emulsion, the temperature is 40 to 95 ° C. and the pH is 3
A compound capable of forming silver telluride in the range of 10 to 10 or pAg of 6 to 11 is preferably used in the present invention, and in this range, the pseudo first-order reaction rate constant k according to the above test method is 1 ×. A compound falling within the range of 10 ⁻⁷ to 1 × 10 ⁻¹ min ⁻¹ is more preferable as the tellurium sensitizer.

General formulas (III), (IV) and (V) of the present invention
The compound represented by can be synthesized according to a known method. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969, 292.
7; Journal of Organometallic Chemistry (J. Organomet. Chem.) 4, 320 (1965); ib
id, 1,200 (1963); ibid, 113, C35
(1976); Phosphor
us Sulfur) 15, 155 (1983); Chemist Ber. 109, 2996 (1976); Journal of Chemical Society Chemicals.
Communication (J.Chem.Soc.Chem.Commun.) 635
(1980); ibid, 1102 (1979); ibid, 6
45 (1979); ibid, 820 (1987); Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.) 1, 219.
1 (1980); edited by S. Patai, The Chemistry of Organo Selenium
and Tellurium Compounds) Volume 2 216-267 (1
987), Tetrahedron Letters
tters) 31, 3587 (1990), Journal of Chemical Research, Synopses (J. Chem. Res., S
ynopses) 2, 56 (1990), Brettan of the
Chemical Society of Japan (Bull.Chem.
Soc. Japan) 62, 2117 (1989), ibid, 60,
771 (1987), Journal of Organometallic Chem. 33.
8, 9 (1988), ibid, 306, C36 (198)
6), The Chemical Society of Japan, Volume 7, 1475 (1987), Zeitschrift Chem.
ie) 26, 179 (1986), Chemistry Letters 3, 475 (1987), Indian Journal of Chemistry (Indian J)
ournal of Chemistry, Section A) 25A, 57 (19
86), Angewandte Chemie 9
7, 1051 (1985), Spectrochimica Acta, Part A 38A, 185 (19)
82), Organic Preparation and Procedia International (Organic Preparatio
ns and Procedures International) 10, 289 (19
78), Organometallics 1,
470 (1982).

The amounts of these selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ^{−7 to} 5 × 10
^Use about ^-3 mol.

The conditions for the chemical sensitization in the present invention are:
Although not particularly limited, the pH is 5 to 8, 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 use a gold sensitizer, and specific examples thereof include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, etc., and 10 ⁻ per mol of silver halide. ^{About 7} to 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.

[0053] The silver halide emulsion of the bright room for silver halide photographic light-sensitive material of the present invention has an average particle size is less than 0.20 [mu] m. Especially 0.08 to 0.16 μm
Is preferred. If the particle size exceeds 0.2μ, γ decreases and Dmax of the practical skill decreases. In the present invention, the reaction temperature is 50 ° C. or lower, preferably 40 ° C. or lower as a mixing condition for adjusting the silver halide grains, and the silver potential is 70 mV under a condition of sufficiently high stirring speed for uniform mixing.
Above, preferably 300 mV ~ 500 mV, or
5,6-Cyclopentane-4-hydroxy-1,3,3
Good results can be obtained by adjusting at 80 mV to 120 mV in the presence of a stabilizer such as a, 7-tetrazaindene. The particle size distribution is basically not limited, but it is preferably monodisperse. The term "monodispersion" as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size, and more preferably within ± 20%. Used in the present invention
The silver halide grains are preferably grains having a regular crystal structure such as a cube or octahedron, and a cube is particularly preferable.

The hydrazine derivative used in the present invention is
It is a compound represented by the following general formula (VI). General formula (VI)

[0055]

[Chemical 37]

In the formula, R ₁ represents an aliphatic group or an aromatic group substituted with a sulfonamide group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group or an aryloxy group. Represents a group, an amino group or a hydrazino group. A ₁ and A ₂ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (VI), the aliphatic group substituted by the sulfonamide group represented by R ₁ is preferably one having 1 to 30 carbon atoms, particularly straight chain or branched one having 1 to 20 carbon atoms. Alternatively, it is a cyclic alkyl group. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. In the general formula (VI), the aromatic group substituted by the sulfonamide group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Of these, an aryl group is particularly preferable.

In formula (VI), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred.

R ₂ may be substituted, and preferable typical substituents are, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group, a hydroxy group, an alkoxy group and an aryloxy group. Groups, acyloxy groups, alkyl or aryl sulfonyloxy groups, amino groups, carbonamido groups, sulfonamide groups, ureido groups, thioureido groups, semicarbazide groups, thiosemicarbazide groups, urethane groups, hydrazide groups, quaternary ammonium structures Group having, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen Child, a cyano group, a phosphoric acid amide group,
Examples thereof include a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and preferable substituents are linear, branched or cyclic. An alkyl group (preferably having a carbon number of 1 to 20),
Aralkyl group (preferably 1 to 1 carbon atoms in the alkyl part)
3 monocyclic or bicyclic), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms),
Acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (Preferably having 1 to 3 carbon atoms
0) and so on.

Preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc. ), An aralkyl group (for example, an o-hydroxybenzyl group), an aryl group (for example, a phenyl group,
3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-
(E.g., a hydroxymethylphenyl group), and a hydrogen atom and a trifluoromethyl group are particularly preferable. Also, R ₂ is C
The portion of OR ₂ is split from the rest of the molecule, and -CO-R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group Can be mentioned)). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (VI) may be further substituted, and preferable examples thereof include those exemplified as the substituent of R ₂ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent ...
., And may be multiply substituted, and the preferable examples are also those exemplified as the substituent of R ₂ .

R ₁ or R _{2 in} the general formula (VI) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R _{2 in} the general formula (VI) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in U.S. Pat. Nos. 4,385,108 and 4,459,34.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

In the present invention, a particularly preferred hydrazine derivative is a group in which R ₁ is a ballast group or a group that promotes adsorption to the surface of a silver halide grain via a sulfonamide group,
It is a group having a quaternary ammonium structure or a phenyl group having an alkylthio group, and R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). ) Is a hydrazine derivative. Note that any combination of the above R ₁ and R ₂ options is possible and preferred. In particular a phenyl group having a group or an alkylthio group R ₁ promotes adsorption to silver halide grain surfaces through a sulfonamide group, a hydrazine derivative R ₂ is a substituted alkyl group are preferred.

Specific examples of the compound represented by the general formula (VI) are shown below. However, the present invention is not limited to the following compounds.

[0067]

[Chemical 38]

[0068]

[Chemical Formula 39]

[0069]

[Chemical 40]

[0070]

[Chemical 41]

[0071]

[Chemical 42]

[0072]

[Chemical 43]

[0073]

[Chemical 44]

[0074]

[Chemical formula 45]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016, 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 2-221953,
2-221954, 2-285342, 2-
285343, 2-289843, 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3, No. 3-54549, No. 3-125134, No. 3
-184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, No. 3-228536, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230.
No. 233, No. 4-96053, No. 4-216544.
No. 5, No. 5-45761, No. 5-45762, No. 5-
No. 45763, No. 5-45764, No. 5-45765.
And those described in Japanese Patent Application No. 5-94925 can be used in combination.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, and particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative 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 cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may 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 used in the present invention is a compound represented by the following general formulas (VII), (VIII), (IX) and (X).

[0079]

[Chemical formula 46]

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group bonded to the P atom by its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents May be linked to L.

[0081]

[Chemical 47]

In the formula, A represents an organic group for completing the heterocycle. B and D each represent a divalent group.
R ₁ and R ₂ each represent an alkyl group or an aryl group,
R ₃ and R ₄ represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt.

The general formula (VII) will be described in detail.

[0084]

[Chemical 48]

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group and a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have.

Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert group.
-A straight-chain or branched alkyl group such as a butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group; an aralkyl group such as a substituted or unsubstituted benzyl group; a cyclopropyl group, a cyclopen Cycloalkyl groups such as teal and cyclohexyl, aryl groups such as phenyl, naphthyl and phenanthryl; alkenyl groups such as allyl, vinyl and 5-hexenyl; cyclopentenyl, cyclohexenyl and other cyclo groups Alkenyl group; pyridyl group, quinolyl group,
Furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group,
Heterocyclic residues such as a morpholyl group, a pyrimidyl group and a pyrrolidyl group are mentioned. Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁ , R ₂ and R ₃ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1 2, a tertiary amino group, an alkyl or aryl ether group, an alkyl or aryl thioether group, a carbonamido group, a carbamoyl group,
Examples thereof include sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, cyano group and carbonyl group. Examples of the group represented by L include a group having the same meaning as R ₁ , R ₂ and R ₃ , as well as a trimethylene group, a tetramethylene group,
Polymethylene group such as hexamethylene group, pentamethylene group, octamethylene group and dodecamethylene group, divalent aromatic group such as phenylene group, biphenylene group and naphthylene group, polyvalent fat such as trimethylenemethyl group and tetramethylenemethyl group Examples thereof include polyvalent aromatic groups such as group groups, phenylene-1,3,5-toluyl group, and phenylene-1,2,4,5-tetrayl group.

Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion, carboxylate ion such as benzoate ion and p-toluenesulfonate. , Methane sulfonate, butane sulfonate, benzene sulfonate and other sulfonate ions, sulfate ions, perchlorate ions,
Examples thereof include carbonate ion and nitrate ion.

In the general formula (VII), R ₁ , R ₂ , R ₃
Is preferably a group having 20 or less carbon atoms, and an aryl group having 15 or less carbon atoms is particularly preferable. m is preferably 1 or 2, and when m is 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, and further, these groups and a -CO- group. , -O- group, -N
R ₄ — group (provided that R ₄ is a hydrogen atom or R ₁ , R ₂ , R
₃ represents a group having the same meaning as _3, and when a plurality of R _4's are present in the molecule, they may be the same or different and may be bonded to each other), —S— group, — SO-
It is a divalent group formed by combining a group and a —SO ₂ — group. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m represents an integer of 2 or more, R ₁ in the molecule,
R _2, R ₃ are each plurality of, the plurality of R _1, R _2, R ₃ may be different even in the same, respectively. n is preferably 1 or 2 and m is 1 or 2
Is preferred. X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt.

In order to add to a specific layer of the silver halide light-sensitive material as a part of the substituents of R ₁ , R ₂ and R ₃ , promotion of adsorption to a ballast group or silver halide for reducing diffusibility. It is preferable to have a group. The ballast group has a total number of carbon atoms of 15 or more and is preferably used in a silver halide photographic coupler. The adsorption promoting group for silver halide is preferably thioamides (eg thiourethane, thioureido, thioamide), mercaptos (eg 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-
Heterocycles such as mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole, etc., and 5- to 6-membered nitrogen-containing heterocycles that form iminosilver. (For example, benzotriazole).

Many of the compounds represented by the general formula (VII) of the present invention are known and commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method.

Specific examples of the compound represented by formula (VII) are shown below. However, the present invention is not limited to the following compounds.

[0092]

[Chemical 49]

[0093]

[Chemical 50]

[0094]

[Chemical 51]

[0095]

[Chemical 52]

[0096]

[Chemical 53]

[0097]

[Chemical 54]

[0098]

[Chemical 55]

[0099]

[Chemical 56]

[0100]

[Chemical 57]

Next, the general formula (VIII), general formula (IX) and general formula (X) will be described in more detail.

[0102]

[Chemical 58]

In the formula, A represents an organic group for completing the heterocycle, which 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 more preferred examples are a pyridine ring, a quinoline ring and an isoquinoline ring. In addition, A may be substituted, and as a preferable substituent,
Halogen atom (eg chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg methyl group, hydroxyethyl group etc.), substituted or unsubstituted aralkyl group (eg bezyl group, p-methoxyphenethyl group etc.) A substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, furyl group,
Thienyl group, naphthyl group, etc.), 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) Group), 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. Examples of particularly preferable substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. 2 represented by B and D
The valent group is alkylene, arylene, alkenylene, -S
_{O 2 -, - SO -,} - O -, - S -, - N (R 6) - those constituted singly or in combination are preferred. However, R ₆ represents an alkyl group, an aryl group, or a hydrogen atom. As a particularly preferable example, B and D include alkylene, arylene, -O-, and -S-, which may be used alone or in combination. R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group). ,
Furyl group, thienyl group, naphthyl group, etc.), 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) Group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group,
It represents an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. In particular,
As a preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents 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 above-mentioned 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. R ₅ has 1 to 2 carbon atoms
An alkyl group of 0 is preferable, and whether it is linear or branched,
Further, it may be a cyclic alkyl group. The alkyl group may be substituted with 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 . X represents an anion group, but X is not necessary in the case of an inner salt. Examples of X are chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

Adsorption to a ballast group or silver halide for decreasing the diffusivity in order to add it to a specific layer of a silver halide light-sensitive material as a part of the substituents of R ₃ , R ₄ and R _5. It is preferable to have a accelerating group. The ballast group has a total number of carbon atoms of 15 or more and is preferably used in a silver halide photographic coupler.
The adsorption promoting group for silver halide is preferably thioamides (eg thiourethane, thioureido, thioamide), mercaptos (eg 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2
-Heterocyclic mercapto such as mercapto-1,3,4-thiadiazole and 2-mercapto-1,3,4-oxadiazole, alkylmercapto, arylmercapto)
And a 5- or 6-membered nitrogen-containing heterocycle (eg, benzotriazole) that produces iminosilver.

The compounds represented by the general formula (VIII), the general formula (IX) and the general formula (X) of the present invention can be synthesized by a generally well-known method (for example, Quart. Rev., 16, 163 (196).
It can be easily synthesized according to 2).

Specific examples of the compounds represented by the general formula (VIII), the general formula (IX) and the general formula (X) are shown below. However, the present invention is not limited to the following compounds.

[0108]

[Chemical 59]

[0109]

[Chemical 60]

[0110]

[Chemical formula 61]

[0111]

[Chemical formula 62]

[0112]

[Chemical formula 63]

[0113]

[Chemical 64]

[0114]

[Chemical 65]

[0115]

[Chemical formula 66]

[0116]

[Chemical formula 67]

The addition amount of the compounds of the general formula (VII), general formula (VIII), general formula (IX) and general formula (X) of the present invention is as follows.
There is no particular limitation, but 1 × 10 per mol of silver halide
^-5 to 2 × 10 ^-2 mol is preferable, and a particularly preferable range is 2 × 10 ^-5 to 1 × 10 ^-2 mol. The nucleation accelerator used particularly preferably in the present invention is a compound represented by the general formula (IX).

Further, the general formula (VII) and the general formula (VII
When the compound of the formula (I), the general formula (IX) or the general formula (X) is contained in the photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and alcohols (for example, methanol or ethanol) when it is water-insoluble. It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as esters (eg ethyl acetate) and ketones (eg acetone). 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. It is also possible to create and use things. Alternatively, it can be used as a fine dispersion by a method known as a solid dispersion method.

In order to obtain a photographic property having a superhigh contrast and safe light safety that can withstand use in a bright room using the silver halide light-sensitive material for a bright room used in the present invention, a conventional infectious developer or US patent is used. PH 1 described in 2,419,975
It is not necessary to use a highly alkaline developer close to 3, and a stable developer can be used. That is, it is used in the present invention .
The light- sensitive silver halide light-sensitive material for bright room contains 0.15 mol / liter or more of sulfite ion as a preservative and has a pH of 9.5.
A sufficiently high-contrast image can be obtained with a developing solution of about 11.0.

There is no particular limitation on the development and fixing in the present invention, but it is preferable to use a dihydroxybenzene compound or reductone as a developing agent as a developing solution. Among these, a preferable developing solution in the case of using a dihydroxybenzene type developing agent has the following composition.
(1) 0.2 to 0.75 mol / liter of dihydroxybenzene type developing agent, (2) 0.001 to 0.06 mol / liter of 1-phenyl-3-pyrazolidone type or p-type
Aminophenol-based auxiliary developing agent, (3) 0.15-
It contains 1.2 mol / liter of free sulfite ion, (4) the compound represented by the general formula [XI], and the concentration ratio of the compound represented by the general formula [XI] and the dihydroxybenzene-based developing agent is 0.03. .About.0.12 and the pH is 9.0-11.
The developer is 0, and particularly preferably 9.5 to 10.7. General formula (XI)

[0121]

[Chemical 68]

In the formula, R ₁ and R ₂ each represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are It represents an atomic group which is bonded to each other to form a 5- to 8-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Y represents = 0 or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group.

Detailed description of the general formula [XI] and specific compounds are described in Japanese Patent Application No. 5-282101.
Of these, ascorbic acid and erythorbic acid (stereoisomers) are preferable. The addition amount of the compound of the general formula [XI] is the concentration ratio of (the compound represented by the general formula [XI] / hydroquinone type developing agent) (the concentration of the compound represented by the general formula [XI] is the same as that of the dihydroxybenzene type developing agent). The value divided by the concentration) is in the range of 0.03 to 0.12. A preferable concentration ratio is 0.03 to 0.10. A particularly preferable concentration ratio is 0.05 to 0.09.

Examples of the dihydroxybenzene type developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, but hydroquinone is particularly preferable. preferable. The concentration of the hydroquinone derivative in the developer is 0.2 to 0.75 mol / liter, preferably 0.2 to 0.5 mol / liter, particularly preferably 0.2 to 0.4 mol / liter. is there.

As the 1-phenyl-3-pyrazolidone derivative developing agent used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Trilyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like are preferable, and 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone are preferable.

As the p-aminophenol type developing agent used in the present invention, N-methyl-p-aminophenol, p
-Aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol, N- (4-hydroxyphenyl) glycine and the like, and among them, N-methyl-p-aminophenol is preferable. When the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
Mol / liter to 0.5 mol / liter, the latter of 0.0
It is preferably used in an amount of 6 mol / liter or less.

When the reductone is used as the developing agent, the compound of the above-mentioned general formula (XI) is preferably used as the reductone, and ascorbic acid or erythorbic acid (stereoisomer) is particularly preferable. In this case, as the auxiliary developing agent, the same ones as the dihydroxybenzene type developing agent can be used, and the p-aminofer type and / or 1-phenyl-3-pyrazolidone type auxiliary developing agent is preferable. When the compound of the general formula (XI) is used as a developing agent, the amount used is generally in the range of 5 × 10 ⁻³ mol to 1 mol, and particularly preferably 10 ⁻² mol to 0.5, per liter of the developing solution. It is a mole.

The preservative used in the developing solution preferred in the present invention is a free sulfite ion, and sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and the like can be added to the developing solution. The free sulfite ion concentration is 0.15 to 1.2 mol / liter,
It is preferably 0.3 to 1.0 mol / liter, and particularly preferably 0.3 to 0.8 mol / liter. The pH of the developer used in the developing treatment of the present invention is in the range of 9.0 to 11.0, preferably 9.5 to 10.7. Sodium hydroxide is used as the alkaline agent to set the pH.
It contains pH adjusters such as sodium carbonate, sodium triphosphate, potassium hydroxide, potassium carbonate, boric acid and the like.

In the developer used in the method of the present invention, a dialdehyde hardener or a bisulfite adduct thereof may be used. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α. Examples include -n-butoxyglutaraldehyde, α, α-diethylsuccindialdehyde, butylmaleindialdehyde, and bisulfite adducts thereof. Of these, glutaraldehyde or its bisulfite adduct is most commonly used. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time is not significantly prolonged. Specifically, it is 1 to 50 g, preferably 3 to 10 g per liter of the developing solution.

An antifoggant is used in the developer used in the method of the present invention, and examples thereof include indazole type, benzimidazole type and benztriazole type. 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-thiadiazol-2-yl) thio] butane Sodium sulfonate, 5-amino-1,
3,4-thiadiazole-2-thiol and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution. In addition to these organic antifoggants, for example, halides such as potassium bromide and sodium bromide can be used.

Further, various organic and inorganic chelating agents can be used in combination in the developing solution used in 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.
As the organic carboxylic acid, acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, acieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid , Itaconic acid, malic acid, citric acid,
Examples include tartar and the like, but the invention is not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitriloacetic acid, nitrilopropionic acid, ethylenediaminomonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriamine. Pentaacetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamino tetraacetic acid, etc. JP-A-52-25632, 55-67
No. 747, No. 57-102624, and Japanese Patent Publication No. 53-53
The compounds described in the specification of No. 40900 and the like can be mentioned.

As the organic phosphonic acid, US Pat.
4454, 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 issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminotetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition to 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.

Organic phosphonocarboxylic acids include those disclosed in JP-A Nos. 52-102726, 53-42730 and 54.
-112127, 55-4024, 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 alkali metal salts or ammonium salts. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 ×, per 1 liter of the developing solution.
It is 10 ⁻³ to 1 × 10 ⁻² mol.

In addition to the above composition, the developer used in the method of the present invention may optionally contain a buffering agent (eg, carbonate, alkanolamine), an alkaline agent (eg, hydroxide, carbonate), a solubilizing agent. (For example, polyethylene glycols,
These esters), pH adjusters (eg organic acids such as acetic acid), development accelerators (eg US Pat. No. 2,648,604).
No. 4, Japanese Patent Publication No. 4-9503, US Pat. No. 3,171,247.
Various pyridinium compounds and other cationic compounds described in No. 5, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9304, US Pat.
31832, 2950970, and 2577127.
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in JP-B-44-9
509, Belgian Patent 682862, organic solvents described in U.S. Pat. No. 3,012,242, thioether compounds, etc., especially thioether compounds are preferable), and surfactants may be contained.

The development processing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the processing temperature is about 20 ° C. to about 50 ° C. and the processing time is 10 seconds to 2 minutes. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 400 ml or less, preferably 200 ml or less.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH.
Modifiers (eg ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
Examples thereof include amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added.
Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator,
For example, Japanese Examined Patent Publication Nos. 45-35754 and 58-12253.
5, thiourea derivatives described in JP-A Nos. 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat.
Examples include mesoionic compounds described in JP-A-229860, and compounds described in JP-A-2-44355 may be used. The pH of the fixer is preferably 4.0 to 6.5,
Particularly preferably, it is in the range of 4.5 to 6.0. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 ° C.
~ 45 ° C, fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is 600 ml / m ² or less, and particularly preferably 300 ml / m ² or less with respect to the processing amount of the light-sensitive material.

The light-sensitive material that has been developed and fixed is then washed with water or stabilized. The washing or stabilizing treatment can be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. That is, not only is it possible to save water,
The piping for installing the automatic processor can be eliminated. When the washing with water is carried out with a small amount of water, JP-A-63-18350,
It is more preferable to provide a squeeze roller septic tank described in JP-A No. 62-287252. In addition, various oxidants may be added or filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with anti-vibration means according to the process by the method of the present invention is disclosed in Japanese Patent Laid-Open No.
No. 0-235133, it can also be used for a processing solution having a fixing ability, which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when a small amount of water is used and / or to prevent the treatment agent component attached to the squeeze roller from being transferred to the treated film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-1
The dye adsorbent described in No. 63456 may be installed in the washing tank.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and an example thereof is JP-A-2-201357.
The baths containing the compounds described in JP-A No. 2-132435, JP-A No. 1-125255, and JP-A No. 46-44446 may be used as the final bath of the light-sensitive material. In this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH buffers, hardeners, bactericides, fungicides, alkanolamines and surface active agents. As the water used for the agent, tap water, deionized water and halogen, ultraviolet germicidal lamps and various oxidizers (ozone,
It is preferable to use water sterilized by hydrogen peroxide, chlorate, etc.).

The treatment liquid preferably used in the present invention is preferably stored in the packaging material having low oxygen permeability described in JP-A-61-73147. On the other hand, in the case of reducing the replenishment amount, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area with the air in the processing tank. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and the roller-conveying type automatic developing machine comprises four steps of development, fixing, washing and drying. Can be preferably used. Further, the above treatment liquid may be used as a solid treatment agent. The solid processing agent preferably used in the present invention is in the form of powder, tablets, granules, powder, lumps or pastes, and the preferred form is JP-A-61-25.
The form or tablet described in 9921. The method for producing tablets is described in, for example, JP-A-51-61837 and JP-A-54-1.
55038, 52-88025, British Patents 1, 2
It can be produced by a general method described in JP-A No. 13,808.
No. 2-109043, No. 3-39735, No. 3-39739, and the like. Furthermore, the powder treating agent is disclosed in, for example, JP-A-54-13.
3332, British Patents 725,892 and 729,8
62 and German Patent 3,733,861 and the like, but can be produced by a general method.

The bulk density of the solid processing agent preferably used in the present invention is preferably 0.5 to 6.0 g / cm ³ , particularly from the viewpoint of its solubility and the effect of the object of the present invention. It is preferably 1.0 to 5.0 g / cm ³ .

There are no particular restrictions on the various additives and the like used in the light-sensitive material used in the present invention , and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and spectral enhancement described in JP-A Nos. 1-112235, 2-124560, 3-79928, 5-11389, and Japanese Patent Application No. 3-411064. Sensitive dye. 2) Surfactants, antistatic From JP-A-2-12236, page 9, upper right column, line 7 or the same, from antistatic agent, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column, line 18. 3) Antifoggant, Stability JP-A-2-103536, page 17, lower right column 19, agent line to page 18, upper right column, line 4 and lower right column, line 1 to line 5. Further, thiosulfinic acid compounds described in JP-A-1-237538. 4) Compound having an acid group From JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A 2-55349, page 8, lower right column, line 13 Page 11, upper left column, line 8. 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 7) Dye JP-A-2-103536, page 17, lower right column, line 1 to line 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 Dyes described in Kaihei 2-294638 and JP-A-63-296039. Further, solids described in WO88 / 04794, European Patent No. 456148, JP-A-5-11382, Japanese Patent Application No. 5-224717, Japanese Patent Application No. 6-117454, and the like. Disperse dye. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Redox compounds Compounds represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and general compounds described in pages 3 to 20 of JP-A 3-174143. Formulas (R-1), (R-2), (R-3), Compound Examples 1 to 75, compounds described in Japanese Patent Application No. 3-69466 and JP-A No. 4-278939. 11) Monomethine compound A compound of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to items, page 12, lower left column, and European Patent No. 452,772A. 13) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. Further, in Japanese Patent Publication No. 46-22507, Japanese Patent Publication No. 50-73625, US Pat. Nos. 34 88708, 3939130, 392 9482, and Japanese Patent Application No. 5-300182, or in the specification. Polymer latices having active methylene groups as described. 14) Organic desensitizers Compounds described in Japanese Patent Publication No. 3-76450, Japanese Patent Application Laid-Open No. 63-64039, Japanese Patent Application No. 6-117454, or the like or the description thereof. 15) Amino group, Ammoni JP-A-63-133145, page 8, line 5 to um group, and nitrogen-containing, page 40, line 5. Compounds containing elementary heterocycles

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[0145]

【Example】

Example 1 <Emulsion preparation> Emulsion A: in a 1.5% gelatin aqueous solution of pH = 2.0 containing sodium chloride and 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per mol of silver kept at 40 ° C. Aqueous silver nitrate solution and 3.5 × 10 ^-5 mol of (NH ₄ ) ₂ per mol of silver
An aqueous sodium chloride solution containing Rh (H ₂ O) Cl ₅ was simultaneously added by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds to half the amount of silver of the final particles to prepare 0.12 μm of particles for the core. Then, a silver nitrate aqueous solution and 10.
An aqueous sodium chloride solution containing 5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added in the same manner as above for 7 minutes to prepare silver chloride cubic particles having an average particle size of 0.15 μm. . (Coefficient of variation: 12%) After that, washing with water by a flocculation method well known in the art to remove soluble salts, gelatin was added,
Compound-A and phenoxyethanol were used as preservatives without chemical ripening, 50 mg each per 1 mol of silver, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as stabilizer was 10 ⁻ per 1 mol of silver. ³ mol was added. (As final particles, pH = 5.7, pAg = 7.5, Rh = 7 × 1
It became 0 ^-5 mol / Ag mol. )

Emulsion B: Just like Emulsion A, grain formation, washing with water, addition of gelatin, adjustment of pH 5.7 and pAg 7.5, and addition of 1.6 × 10 ^-5 mol of sodium thiosulfate per mol of silver, 0.4 × 10 ^-5 mol of the selenium sensitizer of the present invention (II-41) and 4 × 10 ^-5 mol of chloroauric acid were added, and 6
After heating at 0 ° C. for 60 minutes for chemical sensitization, a stabilizer and a preservative were added in the same manner as in Emulsion A.

Emulsion C: Doped in grain formation (N
The emulsion is exactly the same as Emulsion B except that the amount of H ₄ ) ₂ Rh (H ₂ O) Cl ₅ is 10 ⁻⁶ mol / Ag mol.

Emulsion D: Doped in grain formation (N
The emulsion is exactly the same as Emulsion B except that the amount of H ₄ ) ₂ Rh (H ₂ O) Cl ₅ is 5 × 10 ⁻⁶ mol / Ag mol.

Emulsion E: Doped in grain formation (N
The emulsion is exactly the same as Emulsion B except that the amount of H ₄ ) ₂ Rh (H ₂ O) Cl ₅ is 6 × 10 ^-5 mol / Ag mol.

Emulsion F: Just like Emulsion A, grain formation, washing with water, addition of gelatin, adjustment of pH 5.7 and pAg 7.5, and further sensitization of the tellurium of the present invention by 2 × 10 ^-5 mol per mol of silver The agent (V-70) and 4 × 10 ⁻⁵ mol of chloroauric acid were added, the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization, and then, like the emulsion A, a stabilizer and a preservative were added.

Emulsion G: The metal species doped in grain formation is K ₂ Ru (NO) Cl ₅ , and the doping amount is 6 × 10 ^-5.
The emulsion is exactly the same as Emulsion A except that it is mol / Ag mol.

Emulsion H: The metal species doped in grain formation is K ₂ Ru (NO) Cl ₅ , and the doping amount is 6 × 10 ^−5.
The emulsion is exactly the same as Emulsion B except that it is mol / Ag mol.

Emulsion I: K ₂ doped in grain formation
The emulsion is exactly the same as Emulsion H except that the amount of Ru (NO) Cl ₅ is 5 × 10 ⁻⁶ mol / Ag mol.

<Preparation of Coating Solution for Emulsion Layer and Coating Thereof> The following compounds were added to the emulsions shown in Table 1 and the coating amount of gelatin was 1.1 g / m ² on the following support including the undercoat layer, coated silver. The silver halide emulsion layer was coated so as to have an amount of 2.5 g / m ^{2 in} the constitution of one layer or two layers. (The coating amount of the compound is the total coating amount of the emulsion layer) 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 10 mg / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² Compound-B 10 mg / m ² Compound-C 20 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 900 mg / m ² Compound-D (hardener) 150 mg / m ² Further, the nucleation accelerator and the hydrazine derivative of the present invention were added so as to be coated as shown in Table 1.

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer.

<Preparation and Coating of Emulsion Protecting Lower Layer Coating Liquid>
The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 0.7 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.7 g / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² compound-A 5 mg / m ² compound-E 10 mg / m ² compound-F 20 mg / m ²

<Preparation and Coating of Emulsion Protecting Upper Layer Coating Liquid>
The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin was 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.8g / m ² amorphous silica matting agent 40 mg / m ² (average particle size 3.5 [mu], pore diameter 25 Å, surface area 700m ² / g) amorphous silica matting agent 10mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycinpottadium 5 mg / m ² sodium dodecylbenzenesulfonate 30 mg / m ² compound-A 5 mg / M ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

<Preparation of Coating Liquid for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 77.
It was applied so as to be mg / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ² Gelatin (Ca ⁺⁺ content 3000 ppm) 77 〃 Sodium dodecylbenzene sulfonate 10 〃 Sodium dihexyl-α-sulfosuccinate 40 〃 Polystyrene Sodium sulfonate 9〃 Compound-A 7〃

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 2.92 g / m ² . Gelatin (Ca ⁺⁺ content 30 ppm) 2.92 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 54 mg / m ² Compound-H 140 〃 Compound-I 140 〃 Compound-J 40 〃 Dodecylbenzenesulfonic acid Sodium 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound-K 5 〃 N-perfluorooctanesulfonyl-N-propyl glycine potassium 5 〃 Sodium sulfate 50 〃 Sodium acetate 85 〃

(Support, Undercoat Layer) A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated on both sides with the first and second undercoat layers having the following composition. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25〃 polystyrene fine particles (average particle size 3µ) 0.05〃 compound-L 0.20 〃 Colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 〃 Water added 100 〃 Further, 10 wt% KOH was added to dry the coating solution adjusted to pH = 6. When the temperature is 180 ° C. for 2 minutes, the dry film thickness is 0.1.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 Methylcellulose 0.05 〃 Compound-M 0.02 〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 〃 Compound-A 3.5 × 10 ^-3 〃 acetic acid 0.2 〃 water was added 100 〃 This coating solution was applied at a drying temperature of 170 ° C for 2 minutes so that the dry film thickness was 0.1 µ.

[0163]

[Chemical 69]

[0164]

[Chemical 70]

[0165]

[Chemical 71]

<Evaluation Method> Photographic Properties The sample thus obtained was exposed through an optical wedge with a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and was developed by Fuji Photo Film Co., Ltd. automatic developing machine FG-680AG and a developing solution. The sample was treated with No. 1 at 38 ° C. for 20 seconds, fixed, washed with water and dried. The fixer used was fixer 1. The following items were evaluated for these samples. 1) Sensitivity (S _1.5 ); Logarithmic value of the exposure amount giving a density of 1.5 (the smaller the value, the higher the sensitivity.) 2) γ; (1.5-0.1) / {log (exposure amount giving a density of 1.5) -log ( Exposure dose giving a density of 0.1)}

Extracted Character Image Quality To evaluate the extracted character image quality, Japanese Patent Publication No. 2-28,85
No. 6 of the document shown in FIG. 1 "Transparent embedding base / film having line image positive image formed (line image original) / transparent embedding base / film having dot image formed (mesh) Point original), and the emulsion surface of each sample are brought into close contact with each other.
Image development was performed by a 627FM printer, and development processing was performed. (Same processing as above) The exposure time of each sample is as follows:
It was determined to be imaged on each sample as a halftone dot area 50% halftone dot. Here, the first character image quality is the same as the first character quality 5.
When an appropriate exposure is performed using a document as shown in the figure such that 50% halftone dot area is 50% halftone dot area on the return photosensitive material.
It is the image quality with which characters with a width of μm can be reproduced, and it is a very good extracted image quality. On the other hand, the extracted character image quality 1 is an unexplained extracted character quality, which is an image quality that can reproduce only a character having a width of 150 μm or more when the same appropriate exposure is given, and is between 4 and 2 in the sensory evaluation between 5 and 1. Rank is set. A level of 3 or more is a practical level.

Practical technique Dmax The maximum blackening density when a 50% halftone original document described in the evaluation of character image quality without a dot is exposed to a 50% halftone dot area on a film sample.

Storability ΔS _{1.5 The} sample was left under the condition of 70 ° C. at 50 ° C. for 3 days, and then the processing described in the evaluation of photographic characteristics was performed to change the sensitivity immediately after coating (S _1.5 immediately after coating−S _1.5 50 ° C.). 70% 3d: The larger the numerical value, the more sensitized there is.)

[0170] <Developer 1>   Potassium hydroxide 35.0 g   Diethylenetriamine-pentaacetic acid 2.0 g   Potassium carbonate 12.0 g   Sodium metabisulfite 40.0 g   Potassium bromide 3.0 g   Hydroquinone 25.0 g   5-methylbenzotriazole 0.08 g   4-hydroxymethyl-4-methyl-1-phenyl-3-     Pyrazolidone 0.45g   2,3,5,6,7,8-hexahydro-2-thioxo-     4- (1H) -quinazolinone 0.04 g   2-Mercaptobenzimidazole-5-sulfonic acid     Sodium 0.15g   Sodium erythorbate 3.0 g   Add potassium hydroxide and add water to 1 liter     Adjust the pH to 10.5. 1 liter

<Fixer 1> Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Add water to 1 liter Add 2 liters of water to 1 liter of the above fixing solution Used.

As is clear from Table 1, the samples of the present invention (Nos. 7 to 13 and 18) show photographic characteristics of high gradation of γ10 or more, excellent image quality of extracted characters and high practical Dmax of 5.0 or more. Furthermore, it has good storage stability and can maintain these high qualities for a long period of time.

[0173]

[Table 1]

The heavy metal species of Emulsion B was changed to K ₃ CrCN ₆ , K ₃ ReCl ₆ , K ₂
When three kinds of emulsions prepared by changing to Ir (NO) Cl ₅ were evaluated in the same manner as Emulsion B in Table 1, it was confirmed that they had high contrast, high Dmax, high image quality and good storability.

Example 2 The sample of Example 1 (Nos. 1, 4 to 8) was made 3 times with the developer 2.
Evaluation was performed in the same manner as in Example 1 except that the treatment was performed at 8 ° C. for 20 seconds CFG-680AG).

[0176] <Developer 2>   Metol 7.5g   Sodium ascorbate 30.0g   Sodium metaborate 70.0g   Potassium bromide 1.0g   5-methylbenzotriazole 10.0 mg   Sodium hydrogen sulfite 22.0 g   1 liter with water     pH = 9.8

The evaluation result shows that the contrast becomes even harder than in Example 1,
The samples of the present invention (Nos. 7 to 8) were excellent in the image quality of extracted characters, and the practical skill Dmax was as high as 5.0 or more.

[0178]

EFFECT OF THE INVENTION Halogenation containing a heavy metal ion selected from Ir, Ru, Rh, Re and Cr and chemically sensitized with at least one of selenium and tellurium sensitizers and having a silver chloride content of 95 mol% or more. It is possible to achieve high contrast and high image quality in a low pH developing solution, which has been impossible in the past, by the development processing method of a bright room silver halide photographic light-sensitive material containing silver and a hydrazine derivative and a nucleation accelerator. It was
Further, the storage stability of the light-sensitive silver halide photographic light-sensitive material was improved.

Continuation of front page (56) Reference JP-A-1-167746 (JP, A) JP-A-6-19035 (JP, A) JP-A-6-75322 (JP, A) JP-A-5-273710 (JP , A) JP-A-6-230497 (JP, A) JP-A-6-250322 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/06 501 G03C 1/035 G03C 1/09 G03C 1/295

Claims (3)

(57) [Claims] 1. A current bright room for silver halide photographic light-sensitive material having a silver halide emulsion layer at least one layer on a support
In the image processing method , Ir, Ru, Rh,
At least one compound represented by the following general formulas (I) to (V), containing at least 1 × 10 ⁻⁵ mol of a heavy metal ion selected from Re and Cr per mol of silver halide.
Containing at least one hydrazine derivative represented by the following general formula (VI) in at least one of the emulsion layer and other hydrophilic colloid layers. A silver halide photographic light-sensitive material for a bright room containing one kind and at least one kind of nucleation accelerators represented by the following general formulas (VII) to (X),
Characterized by processing with a developer of H 9.0 to 11.0
A method for developing a silver halide photographic light-sensitive material for a bright room. General formula (I) In the formula, Z ₁ and Z ₂ may be the same or different and each is an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, —NR ₁ (R ₂ ), —OR ₃ or —.
Represents SR ₄ . R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R ₁ and R ₂
May be a hydrogen atom or an acyl group. General formula (II) In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group or -OR.
_{7, -NR 8 (R 9)} , - SR 10, represented -SeR _11, X, a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈
And R ₉ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom. General formula (III): In the formula, R ₁₁ , R ₁₂ and R ₁₃ are an aliphatic group, an aromatic group, a heterocyclic group, OR ₁₄ , NR ₁₅ (R ₁₆ ), SR ₁₇ and OSiR ₁₈
(R ₁₉ ) (R ₂₀ ), X or a hydrogen atom. R ₁₄ and R ₁₇ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₁₅ and R ₁₆ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and R ₁₈ , R ₁₉
And R ₂₀ represents an aliphatic group, and X represents a halogen atom. General formula (IV): In the formula, R ₂₁ is an aliphatic group, an aromatic group, a heterocyclic group or -N
Represents R ₂₃ (R ₂₄ ), R ₂₂ represents —NR ₂₅ (R ₂₆ ), −
N (R ₂₇ ) N (R ₂₈ ) R ₂₉ or —OR ₃₀ is represented. R
₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ and R ₃₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Where R ₂₁ and R ₂₅ , R ₂₁ and R ₂₇ , R ₂₁ and R
₂₈ , R ₂₁ and R ₃₀ , R ₂₃ and R ₂₅ , R ₂₃ and R ₂₇ , R ₂₃ and R ₂₈
And R ₂₃ and R ₃₀ may combine to form a ring. General formula (V) In the formula, R ₃₁ and R ₃₂ may be the same or different, and an aliphatic group, an aromatic group, a heterocyclic group,-(C = Y ')
Represents R ₃₃ . R ₃₃ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, NR ₃₄ (R ₃₅ ), OR ₃₆ or SR ₃₇ , and Y ′ represents an oxygen atom, a sulfur atom or NR ₃₈ . R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and n represents 1 or 2. General formula (VI) In the formula, R ₁ represents an aliphatic group or an aromatic group substituted with a sulfonamide group, R ₂ represents a hydrogen atom, an alkyl group,
It represents an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. A
₁ and A _{2 each} represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. [Chemical 7] In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic residue, which may further have a substituent. m is an integer of 1 to 4, L is P
Represents an m-valent organic group that is bonded to an atom and its carbon atom,
n represents an integer of 1 to 3, X represents an n-valent anion, and X may be linked to L. [Chemical 8] In the formula, A represents an organic group for completing the heterocycle.
B and D each represent a divalent group. R ₁ and R ₂ each represent an alkyl group or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X
Represents an anion group, but X is not necessary in the case of an inner salt. 2. The hydrazine derivative represented by the general formula (VI) is characterized in that R ₁ is a group which promotes adsorption to the surface of the silver halide grain through a sulfonamide group or a phenyl group having an alkylthio group. The method for developing a silver halide photographic light-sensitive material for a bright room according to claim 1. 3. The nucleation accelerator is a compound represented by the general formula (IX), according to claim 1 or 2.
Development method of silver halide photographic light-sensitive material for bright room .