JPH09197628A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the cemented carbide performance, and to provide the excellent quick processing performance and stability, and to reduce a load to be applied to the environment with the developing liquid at a low pH by processing the halogenated silver photosensitive material, which includes a first developing accelerator, with the developing liquid, which is mainly composed of ascorbic acid or the like and which includes a second developing accelerator. SOLUTION: The halogenated silver photosensitive material, which includes the hydrazine derivative and a first developing accelerator in an emulsion layer or other hydrophilic colloid layer, is processed with the developing liquid at 9.0-10.5 pH, which includes a second developing accelerator expressed with a formula. In the formula, Z<1> means a metal atomic group to be required for cooperating with N and X<1> so as to form a nitride included hetero ring formed of five or six members, and X<1> means N or CR<12> . R<1> means alkyl group, R<11> and R<12> mean hydrogen atom and halogen atom or the like. m<1> means the numeric 0 or the maximum numeric, which can be substituted for a ring, or less. Y<1> means a pair of ions for charge balance, and n<1> means a numeric to be required for charge balance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver salt photographic image forming method for photoengraving.

[0002]

2. Description of the Related Art A method of producing a high contrast image using a hydrazine derivative is well known and widely used for photolithography. However, since a high pH is generally required, the developer is easily oxidized by air and is unstable.

Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. JP-A-1-17993
No. 9 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorbing group for silver halide emulsion grains and a nucleating agent also having an adsorbing group was used to obtain a pH of 11.0. The processing method of developing with the following developing solution is described. U.S. Pat. Nos. 4,998,604 and 4,994,365 disclose hydrazine compounds having a repeating unit of ethylene oxide and hydrazine compounds having a pyridinium group. However, as is clear from these examples, the high contrast is not sufficient, and the high contrast and the required D
Getting max is difficult.

Further, the pH of the developing solution is increased by the concentration of the developing agent due to air oxidation and evaporation of water, or is lowered by the absorption of CO ₂ gas in the air and the development processing of the exposed photosensitive material. It is not always kept constant. If the pH of the developer changes, the photographic performance also changes, and especially the contrast adjustment performance changes, so it was necessary to add a large amount of replenisher.

As described above, there has been a demand for an image forming method in which the development pH is further lowered and the change in photographic performance due to the pH change is small, but the conventional technique cannot satisfy the demand.

On the other hand, in order to reduce the influence on the environment, attempts have been made to replace hydroquinone, which has been conventionally used universally, with ascorbic acid. Special table flat 6
-505574 (corresponding WO Patent 93/11456),
US 5,236,816 and US 5,264,3
No. 23 discloses an image forming method in which a silver halide light-sensitive material containing a hydrazine derivative and a developing solution containing ascorbic acid are used for processing. According to the description, a high-contrast image cannot be obtained unless a 3-pyrazolidone derivative is used as a super-additive auxiliary developing agent together with an ascorbic acid developing agent and the pH of the developing solution is relatively high. In fact, as a result of our additional test, the ultra-high contrast performance could not be obtained unless the pH was high such as pH ≧ 11.0. It has also been found that, as a serious drawback of this system, when the developer is air-oxidized or fatigued during film processing, the pH is remarkably lowered and the ultra-high contrast performance is extremely impaired.

Further, EP 573,700 discloses a development processing method in which a developing solution in which ascorbic acid and a 3-pyrazolidone derivative are used in combination uses a replenishing solution having a higher pH and substantially the same components. There is. However, EP 573,700 does not describe a super-high contrast sensitive material using a hydrazine derivative. Further, as described above, in the developer using ascorbic acid and the 3-pyrazolidone derivative, the developer pH is 9.0 to 10.
In the range of 5, the ultrahigh contrast performance of the hydrazine ultrahigh contrast sensitive material cannot be obtained. When the alkalinity is high such that pH ≧ 11.0, ultra-high contrast performance can be obtained, but the pH drop due to the air oxidation of the developer becomes severe, and the tendency becomes even stronger when a replenisher having a higher pH is used, and the development during running processing is promoted. It becomes almost impossible to keep the liquid pH constant.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to adjust pH
Relates to a development processing method of a silver halide photographic light-sensitive material for plate-making which achieves super-high contrast performance, is excellent in rapid processing property, is stable, and has little environmental load by using a developer having a low pH of 10.5 or less. It is a thing.

[0009]

The above object of the present invention is to provide at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative and The silver halide light-sensitive material containing the development accelerator of (1) contains a second development accelerator represented by the general formula (NI), (N-II) or (PI), containing ascorbic acid as a developing agent. It was solved by an image forming method characterized by processing with a developing solution containing pH 9.0 to 10.5. General formula (NI)

[0010]

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[0011] In the formula, Z ¹ is N, represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic ring of 5 or 6 membered jointly with X ^1, X ¹ represents N or CR ^12. Here, R ¹² has the same meaning as R ¹¹ . R ¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ¹¹ represents a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. m ¹ is 0 or an integer equal to or less than the maximum substitutable number in the ring. When m ¹ is 2 or more, each R ¹¹ may be the same or different, and each R ¹¹ may be bonded to form a ring. Further, two kinds of radicals having one arbitrary hydrogen atom taken out from the general formula (N-I) may be bonded to each other to form a bis type structure. Y ¹ is a counter ion for charge balance, and n ¹ is a number required for charge balance.

General formula (N-II)

[0013]

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In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group and may be the same or different. R ²² , R ²³ and R ²⁴ may combine to form a monocyclo or bicyclo 5- to 7-membered nitrogen-containing heterocycle. Further, from the general formula (N-II), an arbitrary hydrogen atom 1
Two dissociated radicals may combine to form a bis type structure. Y ² is a counter ion for charge balance, and n ² is a number required for charge balance.

General formula (P-I)

[0016]

[Chemical 6]

In the formula, R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, which may be the same or different. From the general formula (P-I), any one hydrogen atom or 2
The dissociated radicals may combine with each other to form a bis-type structure or a tris-type structure. Y ⁷ is a counter ion for charge balance, and n ⁷ is a number required for charge balance.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below. The present invention is characterized in that two kinds of development accelerators are used in combination. The first development accelerator is a nucleation accelerator and is used by being added to a photosensitive silver halide emulsion layer or other hydrophilic colloid. To be It is a compound that is diffusion resistant so that it is not dissolved in the developing solution during the development process so that the working efficiency is not lowered, or that it is adsorbable to silver halide. The second development accelerator is used by being added to the developing solution and accelerates normal development and nucleation development. It is water-soluble or alkali-soluble. Next, general formulas (N-I) and (N-II) will be described in detail. Z ¹ is N, represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic ring of 5 or 6 membered jointly with X ^1, X ¹ represents N or CR ^12. Where R ¹² is R
Synonymous with ¹¹ . The 5-membered nitrogen-containing heterocycle formed by Z ¹ , N and X ¹ is, for example, pyrazole, imidazole, oxazole, thiazole, triazole or tetrazole. Examples of R ¹¹ or R ¹² bonded to each other to form a condensed heterocycle include indazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole and benzisoxazole. Z ¹
As the 5-membered nitrogen-containing heterocycle completed by (4), pyrazole, imidazole, oxazole, benzimidazole and benzothiazole are preferable, imidazole, oxazole and benzothiazole are more preferable, and imidazole is most preferable. 6 formed by Z ¹ , N and X ¹
The membered nitrogen-containing heterocycle is, for example, pyridine, pyrazine, pyrimidine, pyridazine or triazine. R ¹¹
Or as R ^{12 which} is bonded to form a condensed ring,
For example, quinoline, isoquinoline, naphthyridine, phthalazine, quinoxaline, kyrizoline, synonine, pteridine, purine, acridine, phenanthridine, phenazine, phenanthroline. The 6-membered nitrogen-containing heterocycle completed by Z ¹ is preferably pyridine, quinoline, isoquinoline or phenanthridine, more preferably pyridine, quinoline or isoquinoline, most preferably pyridine.

R ¹ and R ²¹ , R ²² , R ²³ and R ²⁴ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. These include those each having a substituent. As the substituent, an alkyl group, an alkenyl group,
Alkynyl group, hydroxyl group, mercapto group, nitro group, carboxyl group, cyano group, halogen atom, aryl group, heterocyclic group, mercapto-substituted heterocyclic group, alkoxy group, aryloxy group, acylamino group, thioamide group, alkylamino group , Anilino group, ureido group, thioureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, thiocarbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group , Heterocyclic thio groups, sulfinyl groups, phosphonyl groups, phosphoryl groups, seleno groups, aryloxycarbonyl groups, acyl groups, thiocarbonyl groups and combinations thereof.

More specifically, R ¹ and R ²¹ , R ²² , R ²³ ,
An example of R ²⁴ is shown. The alkyl group has 1 to 10 carbon atoms,
Preferably, it is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, allyl, propargyl, octyl, decyl, 2-butenyl, 2-hydroxyethyl, benzyl,
It is 4-methylbenzyl, 2-methoxyethyl, butoxycarbonylmethyl, phenylcarbamoylmethyl, 2-methanesulfonamidoethyl, 2-methanesulfonylethyl, methylthioethyl.

The alkenyl group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and examples thereof include ethynyl and phenylethynyl.

The aryl group is an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, such as phenyl.
Naphthyl and p-methoxyphenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the number of kinds of elements may be one or more, for example,
2-furyl, 2-thienyl and 4-pyridyl.

R ¹ is preferably an alkyl group, an alkenyl group or an alkynyl group, more preferably an alkyl group or an alkenyl group, and most preferably an alkyl group. R ²¹ , R ²² , R ²³ , and R ²⁴ are preferably an alkyl group and a case where R ²² , R ²³ and R ²⁴ are bonded to form a monocyclo or bicyclo 5- to 7-membered nitrogen-containing heterocycle.

R ¹¹ and R ¹² represent a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. As the group bonded at the carbon atom of R ¹¹ and R ¹² , an alkyl group, an alkenyl group,
An alkynyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carboxyl group, a cyano group, and a heterocyclic group are bonded with an oxygen atom as a hydroxy group, an alkoxy group, an aryloxy group, Heterocyclic oxy group, acyloxy group, carbamoyloxy group, sulfonyloxy group,
Examples of a compound bonded by a nitrogen atom include an acylamino group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, and a sulfonamide group. , An imide group, a heterocyclic group is bonded with a sulfur atom, an alkylthio group,
Arylthio group, heterocyclic thio group, sulfamoyl group,
Examples thereof include an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfonyl group, a sulfo group, and a sulfinyl group. These may be further substituted with the groups described as the substituents for R ¹ .

R ¹¹ and R ¹² will be described in more detail. The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group has 1 to 1 carbon atoms.
0, preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, 1-butylpentyl, benzyl, 3
-Hexanoyloxypropyl, methoxyethyl, methylthioethyl. The alkenyl group has 2 to 2 carbon atoms.
Examples thereof include vinyl, 1-propenyl, 1-hexenyl, styryl and the like. The alkynyl group has 2 to 10 carbon atoms, and examples thereof include ethynyl, 1-butynyl, phenylethynyl and the like. The aryl group is an aryl group having a carbon number of 6 to 12, and examples thereof include phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 10 carbon atoms, and examples thereof include carbamoyl, N-ethylcarbamoyl, N, N-diethylcarbamoyl, N-octylcarbamoyl and N-phenylcarbamoyl.

The alkoxycarbonyl group has 2 carbon atoms.
10 to, for example, methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 13 carbon atoms and is, for example, phenoxycarbonyl. The acyl group has 1 to 10 carbon atoms, and examples thereof include acetyl and benzoyl. The heterocyclic group linked by a carbon atom on the ring is a 5- or 6-membered saturated or unsaturated heterocyclic ring having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms. The number of heteroatoms constituting the ring and the types of elements may be one or more, for example, 2-furyl, 2-thienyl,
2-pyridyl and 2-imidazolyl.

The alkoxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxy and 2-
Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 12 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m-.
(3-hydroxypropionamide) phenoxy. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or more, and examples thereof include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy,
2-pyridyloxy. The acyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy, and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-hexylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has 1 to 10 carbon atoms.
And examples thereof include methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 10 carbon atoms,
Preferably, those having 1 to 6 carbon atoms such as acetamide,
Hexanoamide, phenoxyacetamide, p-chlorobenzoylamino. The alkylamino group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylamino and N- (2-hydroxyethyl) amino. The arylamino group has 6 to 12 carbon atoms and is, for example, anilino or N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. Number of atoms and type of element is 1
One or more may be used, and examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino, and 4-pyridylamino.

The ureido group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, 3-phenoxypropylureido, N, N-diethylureido and 2-methanesulfonamidoethylureido. is there.

The sulfamoylamino group has 0 carbon atoms.
-10, preferably those having 0-6 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and is, for example, methoxycarbonylamino. The aryloxycarbonylamino group has 7 to 13 carbon atoms, and examples thereof include phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino.

The sulfonamide group has 1 to 1 carbon atoms.
0, preferably those having 1 to 6 carbon atoms, such as methanesulfonamide and p-toluenesulfonamide.

The imide group has 4 to 10 carbon atoms, and examples thereof include N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocyclic ring composed of a nitrogen atom and at least one of a carbon atom, an oxygen atom or a sulfur atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 1 carbon atoms.
0, preferably those having 1 to 6 carbon atoms, such as methylthio, 2-phenoxyethylthio, and 2-propionyloxyethylthio. Arylthio group has 6 carbon atoms
To 12 such as phenylthio and 2-carboxyphenylthio. Heterocyclic thio group has 1 carbon
5 to 5 membered saturated or unsaturated heterocyclic thio groups containing at least one oxygen atom, nitrogen atom, or sulfur atom, the number of heteroatoms constituting the ring and the kind of element are 1 There may be one or more, for example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms
0, preferably those having 0 to 6 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl. Alkoxysulfonyl group has 1 to 1 carbon atoms
0, preferably having 1 to 6 carbon atoms, for example, methoxysulfonyl. The aryloxysulfonyl group has 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.

R ¹¹ and R ¹² are preferably an alkyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyano group, an alkoxy group, an aryloxy group, a carbamoyloxy group, an acylamino group, Ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, sulfamoyl group, sulfonyl group, alkylthio group, and more preferably alkyl group, aryl group, carbamoyl group, acylamino group, ureido group, sulfonamide group. , A sulfamoyl group, most preferably an alkyl group, an aryl group, a carbamoyl group, and a sulfamoyl group.

Y ¹ and Y ² are counterions for charge balance, and are anions or cations when two or more anionic groups are present in the molecule. Examples of the anion include chlorine ion, bromine ion, iodine ion, p-toluenesulfonate ion, sulfate ion, perchlorate ion, trifluoromethanesulfonate ion, boron tetrafluoride ion, phosphorus hexafluoride ion and the like. Examples of the cation include sodium ion, potassium ion, lithium ion, calcium ion, ammonium ion, tetrabutylammonium ion, and triethylammonium ion. n ¹ and n ² are numbers necessary for charge balance, and are 0 when forming an intramolecular salt.

When two R ¹¹ 's combine to form a ring when m ¹ is 2 or more, there may be mentioned 5- to 7-membered aromatic and non-aromatic carbocycles and heterocycles.

The compounds represented by (N-I) and (N-II) of the present invention may have a group for promoting adsorption to silver halide. As the adsorption promoting group to silver halide, a part thereof is already shown as a substituent of R ¹ , but preferably thioamides (eg thiourethane, thioureido, thioamide), mercaptos (eg 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2
-Mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole, etc. heterocyclic mercapto, alkylmercapto, arylmercapto), a sulfide group and a 5- or 6-membered member that produces iminosilver It is a nitrogen-containing heterocycle (for example, benzotriazole).

From the formula (N-I), two radicals free of any one hydrogen atom are combined to form a bis type structure, preferably the following general formulas (N-III) and (N-).
IV). General formula (N-III)

[0041]

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In the formula, Z ³¹ and Z ³² are Z in formula (N-I).
¹ , X ³¹ and X ³² are X ¹ , R ³¹ and R ³² are R ¹¹ , and Y ³
Is synonymous with Y ¹ , m ³¹ , m ³² is m ¹ , and n ³ is synonymous with n ¹ . R ³ is a divalent linking group (an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group and a —O— or —S group in which a hydrogen atom is removed from R ^1.
-, - NH -, - CO -, - it is the concatenation alone or in comprising a combination groups such) - SO _2. These preferable ones are also the same as those in the formula (NI).

The alkylene group for R ³ is, for example, ethylene, trimethylene, pentamethylene, octamethylene, propylene, 2-butene-1,4-yl, 2-butyn-1,4-yl or p-xylylene. The alkenylene group is, for example, ethene-1,2-yl. The alkynylene group is ethyn-1,2-yl. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. R ³ is preferably an alkylene group, an alkenylene group, or a group in which they are combined with —O— or —S—, and more preferably an alkylene group or a group in which an alkylene group is combined with —O— or —S—.

General formula (N-IV)

[0045]

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In the formula, Z ⁴¹ and Z ⁴² are Z in formula (NI).
¹ , X ⁴¹ and X ⁴² are X ¹ , R ^4a and R ^4b are R ¹ ,
R ⁴¹ and R ⁴² are R ¹¹ , Y ⁴ is Y ¹ , and m ⁴¹ and m ⁴² are m ^1.
And n ⁴ is synonymous with n ¹ . R ⁴³ is a divalent linking group having a hydrogen atom removed from R ¹¹ . These preferable ones are also the same as those in the formula (NI).

From the general formula (N-II), two radicals free of one arbitrary hydrogen atom are combined to form a bis type structure, preferably those represented by the following general formula (NV). is there. General formula (N-V)

[0048]

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In the formula, (R ^52a , R ^53a , R ^54a ) and (R ^52b , R ^53b , R ^54b ) have the same ^meanings as (R ²² , R ²³ , R ²⁴ ) in formula (N-II). Y ⁵ is Y ² and n
⁵ has the same meaning as n ² . R ⁵¹ is a divalent linking group having a hydrogen atom removed from R ²¹ . These preferred ones also have the formula (N
-The same as II). Among the general formulas (N-I) to (N-V), those represented by the following general formula (N-VI) are more preferable. General formula (N-VI)

[0050]

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In the formula, Z ⁶¹ is a group shown below.

[0052]

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Z ⁶² is a group represented by Z ⁶¹ or a hydrogen atom. L ⁶¹ , L ⁶² , and L ^{63 each} have 2 or 3 carbon atoms in the main chain.
Is an alkylene group of, for example, ethylene, propylene, trimethylene. X ⁶¹ and X ⁶² are -S- or-
O-, Y ⁶ has the same meaning as Y ^{1 in} formula (NI), and n ⁶ has the same meaning as n ^{1 in} formula (NI). As Z ⁶¹ and Z ⁶² , pyridinium, trialkylammonium and N-methylpiperidinium are more preferable. Next, specific examples of the compounds represented by the general formulas (NI) and (N-II) in the present invention are shown, but the invention is not limited thereto.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

[Chemical 21]

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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The general formulas (NI) and (NI) of the present invention are
The compounds represented by I) are known compounds described in JP-A-5-53231, JP-A-6-161009, U.S. Pat. No. 5,474,879 and the like, among which the solubility in a developing solution is high. At room temperature, 1 × 10 ⁻⁶ mol / liter or more, preferably 1 × 10 ⁻⁵ mol / liter or more.

When the compound represented by the general formula (N-I) of the present invention is added to the developing solution, it varies depending on the kind of the compound used, but it is 1 × 10 ^-6 mol to 1 × 10 ^-1 per liter of the developing solution. A molar range is suitable, a range of 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol is preferred, and a range of 5 × 10 ⁻⁵ to 5 × 10 ⁻³ mol is particularly preferred.

Next, the compound represented by formula (PI) will be described in detail. General formula (PI)

[0075]

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In the formula, R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group (these include those having a substituent) and any hydrogen Radicals having one or two atoms may be bonded to each other to form a bis type structure or a tris type structure. Y ⁷ is a counter ion for charge balance, and n ⁷ is a number required for charge balance.

As R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ , those mentioned for R ¹ in formula (NI) can be mentioned. R ⁷¹ , R
^The substituent which ⁷² , R ⁷³ and R ⁷⁴ have is represented by the general formula (N-
Examples are the substituents of R ¹ in I) or those mentioned for R ¹¹ . Examples of Y ⁷ and n ⁷ include those described for Y ¹ and n ¹ in the general formula (NI). As R ⁷¹ , R ⁷² , R ⁷³ , and R ⁷⁴ , an aryl group and an alkyl group are preferable, and R ⁷¹ ,
It is more preferable that R ⁷² and R ⁷³ are an aryl group or an alkyl group, and R ⁷⁴ is an alkyl group. In addition, the general formula (P-
In I), it is preferable that two radicals having a hydrogen atom removed from R ⁷⁴ be bonded to form a bis type structure represented by the general formula (P-II).

General formula (P-II)

[0079]

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In the formula, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R
⁸⁶ has the same meaning as R ^{71 in} formula (P-I), and Y ⁸ and n ⁸
Is synonymous with Y ⁷ and n ^{7 in} formula (P-I). L is a divalent group in which one hydrogen atom is taken from R ⁷⁴ of the general formula (P-I), preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, when group (R ⁸⁷ is the hydrogen or R ⁸¹ group having the same meaning, a plurality of R ⁸⁷ are present in the molecule, - further these groups and -CO- group, -O- group, -NR ⁸⁷ These may be the same or different, and may be bonded to each other), a divalent group formed by combining a —S— group, a —SO— group, and a —SO ₂ — group. Is. It is particularly preferable that L is a divalent group having a total carbon number of 6 or less, which is bonded to the P atom by its carbon atom. Among the general formula (P-II), the general formula (P-
The compound represented by III) is more preferable. General formula (P-III)

[0081]

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Here, R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ ,
R ⁹⁶ is an aryl group or an alkyl group, and L ⁹¹ , L
⁹² and L ⁹³ are alkylene groups having 2 or 3 carbon atoms in the main chain, for example, ethylene, propylene and trimethylene. X ⁹¹ and X ⁹² are —O— or —S—, Y ⁹ and
n ⁹ has the same meaning as Y ⁷ and n ^{7 in} formula (P-I), respectively. The compound represented by (P-I) of the present invention may have an adsorption promoting group for silver halide. The adsorption promoting group to silver halide is preferably thioamides (eg thiourethane, thioureido, thioamide), mercaptos (eg 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-).
1,3,4-thiadiazole, 2-mercapto-1,
Heterocyclic mercapto such as 3,4-oxadiazole, alkylmercapto, arylmercapto, a 5- or 6-membered nitrogen-containing heterocycle (for example, benzotriazole) which forms a sulfide group and imino silver.

Many of the compounds represented by formula (P-I) of the present invention are known and some of them are available as reagents. Among them, the solubility in a developing solution at room temperature is 1
× 10 ^-6 mol / liter, preferably 1 × 10 ^-5 mol / liter
More than liter is selected. As a general synthesis method, there is a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. Specific examples of the compound represented by formula (P-I) are shown below. However, the present invention is not limited to the following compounds.

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[0085]

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[0090]

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[0092]

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[0093]

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[0094]

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[0095]

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The addition amount of the compound of the general formula (P-I) of the present invention is not particularly limited, but it is preferably 1 × 10 ^-6 to 1 × 10 ^-2 mol per liter of the developing solution. Especially, the preferable addition amount is in the range of 1 × 10 ⁻⁵ to 2 × 10 ⁻³ mol. The developer (development starter and developer replenisher) of the present invention contains at least one ascorbic acid or derivative thereof as a developing agent. Preferred ascorbic acid or its derivative is a compound represented by the general formula (II).

[0097]

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In the general formula (II), R ₁ and R ₂ are each a hydroxy group or an amino group (having 1 carbon as a substituent).
To 10 alkyl groups such as methyl group, ethyl group, n-
Includes those having a butyl group, a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-
A toluenesulfonylamino group, an alkoxycarbonylamino group (a methoxycarbonylamino group, etc.), a mercapto group, and an alkylthio group (a methylthio group, an ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group, or P and Q are bonded to each other, together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y; It represents an atomic group necessary for forming a 7-membered ring. Specific examples of the ring structure, -O -, - C (R 4) (R 5) -, -
_{C (R 6) =, -} C (= O) -, - N (R 7) -, - N =,
Are configured in combination. However, R ₄ , R ₅ , R ₆ ,
R ₇ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group or a sulfo group can be mentioned as the substituent), a hydroxy group or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. And preferred examples of the 5- to 7-membered ring are:
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
A uracil ring can be mentioned.

Y is a group composed of ＯO or ＮN—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), a carboxy group. Represents an alkyl group (for example, carboxymethyl, carboxyethyl). Specific examples of the compound represented by formula (II) are shown below, but the present invention is not limited thereto.

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[0103]

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Of these, ascorbic acid and erythorbic acid (diastereomers of ascorbic acid) are preferred. The amount of ascorbic acid used is generally in the range of 5 × 10 ⁻³ mol to 1 mol, and particularly preferably 10 ⁻² mol to 0.5 mol, per liter of the developing solution.

Aminophenols are used as auxiliary developing agents. As aminophenols, 4-aminophenol, 4-amino-3-methylphenol, 4- (N-
Methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N-
(2'-hydroxyethyl) -2-aminophenol,
2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, N-β -Hydroxyethyl-4-aminophenol, N- (4'-hydroxyphenyl) pyrrolidine, N- [gamma] -hydroxypropyl-4-aminophenol, 6-hydroxyl-
Examples include 1,2,3,4-tetrahydroquinoline, N, N-dimethyl-4-aminophenol, N, N-diethylaminophenol, and hydrochlorides and sulfates of these compounds.

The amount of aminophenol used is generally in the range of 5 × 10 ⁻⁴ to 0.5 mol, preferably 10 ⁻³ to 0.1 mol, per liter of the developing solution.

The addition ratio of the developing agent and the auxiliary developing agent can be arbitrarily selected as long as they are within the ranges of the above respective addition amounts.

The developer of the present invention further comprises hydroquinone or its derivative (hydroquinone monosulfonic acid, hydroquinone disulfonic acid, methylhydroquinone, chlorohydroquinone, etc.), or 3-pyrazolidone or its derivative (eg, 1-phenyl-3-pyrazolidone). , 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-Phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, etc.) may be additionally included. 1x addition amount
10 ⁻³ to 0.8 mol / liter, preferably 1 × 10
^-2 to 0.4 mol / l.

The developer of the present invention preferably contains a preservative and an alkali in addition to the above-mentioned essential components. Sulfite can be used as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The larger the amount of preservative added, the better the preservative properties of the developer, but on the other hand, the amount of silver ions dissolving out of the photosensitive material into the developer increases, so that silver sludge gradually accumulates in the developer. Have negative effects. Since the developer of the present invention has high stability, sufficient preservation can be obtained with a small amount of sulfite added. Therefore, the amount of sulfite added is preferably 0.5 mol or less per liter of developer. More preferably, 0.0
2 to 0.4 mol / liter is preferred. Particularly preferably, it is 0.
02 to 0.3 mol / liter is preferable.

Additives other than those mentioned above include
Development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or its derivatives; mercapto Compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds may be included as antifoggants or black pepper inhibitors. 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-thiadiazole-
Examples thereof include sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.05 to 2 mmol, per liter of developer. In order to suppress the accumulation of silver sludge in the developing solution, known silver sludge inhibitors can be used.

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

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

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
Hydroxyalkylidene-diphosphonic acid described in No. 227639 and the like, and Research Disclosure (Research Disclosure)
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

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

Further, if necessary, a toning agent, a surfactant,
It may contain an antifoaming agent, a hardening agent and the like.

The developing solution used in the present invention contains carbonate, boric acid and borate (eg boric acid, pH buffering agent).
Borax, sodium metaborate, potassium borate) Sugars (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphate described in JP-A-60-93433 (Eg, sodium salt, potassium salt), aluminate (eg, sodium salt) and the like, and preferably carbonate and borate. The pH buffer is 0.1-1.
The amount used is 5 mol / liter, preferably 0.2 to 1.2 mol / liter. More preferably, it is used in an amount of 0.3 to 1.0 mol / liter. The development temperature and time are interrelated and are determined in relation to the total processing time, but generally the development temperature is about 20 ° C to about 50 ° C, preferably 25 ° C.
At 45 ° C, the development time is 5 seconds to 2 minutes, preferably 7 seconds to 6
0 seconds.

The pH of the development initiating solution of the present invention is 9.0-1.
It is 0.5. As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate) can be used.

The composition of the development replenisher is basically the same as that of the development starter except for pH. The pH of the development replenisher is set higher than the pH of the development starter. Preferably, the pH of the development replenisher is 0.2 to
It is set to 1.5 units, particularly preferably 0.3 to 1.0 unit higher. However, if the pH of the replenisher is too high, the replenisher itself is likely to be oxidized by air.
The upper limit of H is preferably about 11.2. By performing the running process while replenishing the developing replenisher as described above, it is possible to almost eliminate the fluctuation of the pH value of the developer which is actually processing the photosensitive material, and to set the p value set at the start of development.
The photosensitive material is processed at a pH value almost the same as H (that is, the pH value of the development starter solution). The pH of the development starter solution and the development replenisher solution may be adjusted by adding the above-mentioned alkaline agent to the development starter solution to prepare a development replenisher solution. Alternatively, based on the development replenisher solution, acetic acid, glacial acetic acid, or sulfamic acid may be added. Alternatively, an acid such as sulfuric acid may be added to lower the pH to obtain a developing starter solution.
Alternatively, the development initiating solution and the development replenishing solution may be separately prepared to have compositions optimized within the above-mentioned addition amounts.

In the present invention, the processing is carried out while replenishing the development replenisher according to the processing amount of the silver halide light-sensitive material. The replenishment amount of the developing replenisher is usually 500 ml or less per square meter of the light-sensitive material, but can be made smaller than usual by the present invention, and low replenishment of 200 ml or less per square meter of the light-sensitive material, and further 150 ml or less. However, stable processing is possible.

The developed light-sensitive material is usually fixed, washed (stabilized), and dried. The fixing solution used in the fixing step is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid,
It is an aqueous solution containing Tylon, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid and their 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, 0.2 to 1.5 mol /
Liters. The fixing solution may optionally contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), and a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing promoters. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and 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. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
No. 58-122536, alcohols having a triple bond in the molecule, U.S. Pat.
A thioether compound described in JP-A-126449;
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid; and inorganic acids such as boric acid, phosphate, and sulfite. Buffers can be used. Acetic acid, tartaric acid, and sulfite are preferably used. The pH buffer agent is used for the purpose of preventing the pH of the fixing agent from rising due to the carry-in of the developing solution, and is 0.01 to 1.0.
Mol / l, more preferably about 0.02 to 0.6 mol / l. The pH of the fixing solution is preferably from 4.0 to 6.5, particularly preferably from 4.5 to 6.0. Further, as a dye elution accelerator, JP-A-64-473 is used.
The compound described in No. 9 can also be used.

The hardening agent in the fixing solution includes 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 preferred addition amount is
0.01 mol to 0.2 mol / liter, more preferably 0.03
~ 0.08 mol / l. The fixing temperature is about 20 ° C
At about 50 ° C, preferably 25-45 ° C, the fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds. The replenishing amount of the fixing solution is 500 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.

Silver salts accumulate in the fixing solution as the process proceeds. The fatigued fixing solution can be recycled for removing silver salts by a known silver recovery means. It is possible to use a method of removing silver ions into metallic silver by electrolytic reduction and then filtering and removing with a filter, a method of removing silver ions by adsorbing it on a strongly adsorbing compound, and a method of protruding the silver ions on the surface of a metal filament to remove them. These silver recovery devices may be installed in the fixing solution circulation line or may be processed offline.

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

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer. The treatment liquid used in the present invention may be in the form of a powder and solidified. As the method, a known method can be used.
259921, JP-A-4-85533, JP-A-4-
It is preferable to use the method described in 16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Regarding the roller transport type automatic developing machine, US Pat. Nos. 3,025,779 and 35,
No. 45971, etc., and is herein simply referred to as a roller transport type processor. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Four steps of a stabilization step may be used instead of the washing step.

Next, the silver halide photographic light-sensitive material to which the development processing method of the present invention is applied will be described. Although any of the hydrazine derivatives used in the present invention can be used, compounds represented by the following general formula (I) are preferable. General formula (I)

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In the formula (I), R ₁ is an aliphatic group, an aromatic group,
Alternatively, it represents a heterocyclic group, and R ₂ is a hydrogen atom or a blocking group. G ₁ is a —CO— group, a —SO ₂ — group, a —S
O- group, -CO-CO- group, a thiocarbonyl group, an iminomethylene group or _{-P (O) (R 3)} - represents a group, R ₃
It is selected from the same range as the groups defined in R _2, may be different from R _2.

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 (I), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, particularly 1 to 3 carbon atoms.
20 straight, branched or cyclic alkyl groups. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent. In the general formula (I), the aromatic 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.

Particularly preferred as R ₁ is an aryl group. The aliphatic group, aromatic group or heterocyclic group represented by R ₁ may be substituted. Representative examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring, and a pyridinium. Group, hydroxy group,
Groups having an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or arylsulfonyloxy group, an amino group, a carbonamide group, a sulfonamide group, a ureido group, a thioureido group, a semicarbazide group, a thiosemicarbazide group, a urethane group, and a hydrazide structure; A group having a quaternary ammonium structure, an alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, carboxyl group, sulfo group,
Acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, phosphoric amide group, diacylamino group, imide group, group having an acylurea structure, group containing selenium atom or tellurium atom, 3 Groups having a quaternary sulfonium structure or a quaternary sulfonium structure, and preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably having an alkyl moiety). A monocyclic or bicyclic one having 1 to 3 carbon atoms, an alkoxy group (preferably 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms) ), An acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 carbon atom) Those with 30), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably those having 1 to 30 carbon atoms).

The blocking group for R ₂ is an alkyl group,
There are an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group, and a hydrazino group.

In formula (I), 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,
5- and 6-membered compounds containing oxygen and sulfur atoms, for example, imidazolyl, pyrazolyl, triazolyl,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic one, an unsubstituted amino group as the amino group, and an alkylamino group having 1 to 10 carbon atoms. A group and an arylamino group are preferred. R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ .

Preferred among the groups represented by R ₂ are alkyl groups (eg, methyl group, trifluoromethyl group, 2-carboxy-tetrafluoroethyl group, 3 and 3 when G ₁ is —CO— group. -Hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, methyl group substituted with pyridinium group, etc.), aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-
Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), especially a hydrogen atom,
A trifluoromethyl group is preferred. Also, G ₁ is -SO ₂
In the case of a group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, dimethylamino group). Etc.) are preferred.

When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and a substituted or unsubstituted amino group are preferred. In the general formula (I), G represents a -CO- group, -CO
A CO- group is preferred, and a -CO- group is most preferred. or,
R ₂ splits the G ₁ -R ₂ moiety from the residual molecule,
₁ -R ₂ moiety of atoms may be such as to rise to cyclization reaction to form a cyclic structure containing, examples, include those described in, for example, JP-A-63-29751 Can be

The substituents of R ₁ and R ₂ in formula (I) may be further substituted, and preferable examples thereof include those exemplified as the substituents of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, 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-1-100530.

R ₁ or R ₂ of the general formula (I) may be a porcelain having a group which enhances adsorption on the surface of the silver halide grain incorporated therein. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
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 group described in 3-234246 is mentioned.

Particularly preferred hydrazine derivative in the present invention is that R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure, or a phenyl group having an alkylthio group, G is -CO- group or -COCO- group, hydroxymethyl R ₂ is the electron withdrawing group or 2-position as a substituent alkyl group or a substituted aryl group (substituent Group), or a hydrazine derivative which is a substituted or unsubstituted amino group. It should be noted that any combination of the above-mentioned options of R ₁ and R ₂ is possible and preferable.

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

[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
No. 4,459,347 and 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
No. 4,994,365, No. 5,041,355
No. 5,104,769, British Patent 2,011,
391B, EP 217,310, EP 301,310,
No. 799, No. 356, 898, JP-A-60-1797.
No. 34, No. 61-170733, No. 61-27074
No. 4, 62-178246, 62-270948
Nos. 63-29751, 63-32538, 63-110407, 63-121838, and 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
No. 234246, No. 63-294552, No. 63-3
Nos. 06438 and 64-10233, JP-A-1-90
No. 439, No. 1-100530, No. 1-1095941
No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2
No. 83549, No. 1-285940, No. 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-
No. 285343, No. 2-289843, No. 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3-54549, No. 3-125134, No. 3
Nos. -184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, 3-282536, 4-51143, 4-56842, 4-84134, 2-230
No. 233, No. 4-96053, No. 4-216544
Nos. 5-45761, 5-45762, 5-
No. 45763, No. 5-45764, No. 5-45765
And Japanese Patent Application No. 5-94925 can also be used.

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, particularly 1 × 1.
The range of 0 ^-5 mol to 2 × 10 ^-2 mol is a preferable addition amount. The hydrazine derivative in the present invention is contained in the emulsion layer and / or another hydrophilic colloid layer. Here, examples of the other hydrophilic colloid layer include a protective layer, a layer provided between the emulsion layer and the support, and an intermediate layer.

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 Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared 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 silver halide photographic light-sensitive material of the present invention comprises an amine derivative, an onium salt, a disulfide derivative as a first development accelerator in at least one layer of a silver halide emulsion layer or another hydrophilic colloid layer. And a nucleation accelerator selected from hydroxymethyl derivatives. These nucleation accelerators may be used alone or in combination of two or more. As the amine derivative, for example, JP-A-Sho 6
0-140,340, 62-50,829, 6
2-222, 241, 62-250, 439, 62-280, 733, 63-124, 045,
The compounds described in 63-133,145, 63-286,840 and the like can be mentioned. The amine derivative is more preferably JP-A-63-124,045.
63, 133-145, 63-286, 84.
Compounds having a group capable of adsorbing to silver halide described in No. 0, etc., or compounds having a carbon number sum of 20 or more described in JP-A No. 62-222,241.
The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A Nos. 62-250,439 and 62-280.
The compound described in No. 733 etc. can be mentioned. Examples of preferable phosphonium salts include the compounds described in JP-A Nos. 61-167,939 and 62-280,733. Examples of the disulfide derivative include, for example, JP-A-61-1981,1.
No. 47 can be mentioned. As the hydroxymethyl derivative, for example, US Pat. No. 4,693,
Nos. 956, 4,777,118, EP 231,85
No. 0, JP-A-62-50,829 and the like can be mentioned, more preferably a diarylmethanol derivative.

Specific examples of the nucleation accelerator are shown below. However, the present invention is not limited to the following compounds.

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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The optimum addition amount of these compounds varies depending on the kind thereof, but is 1.0 × 1 per mol of the hydrazine compound.
0 ^-2 mol to 1.0 × 10 ² mol, preferably 1.0 × 10 ² mol
It is desirable to use it in the range of 10 ⁻¹ mol to 1.0 × 10 mol. These compounds are dissolved in an appropriate solvent (H ₂ O) such as alcohols such as methanol and ethanol, acetone, dimethylformamide, and methylcellosolve, and added to the coating solution.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver chloride, silver bromide, and mixed silver halides such as silver chlorobromide, silver iodobromide and salts. Silver iodobromide or the like can be used. Silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferred. The silver iodide content is preferably 3 mol% or less, more preferably 0.5 mol or less. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but a cubic is preferred. The average grain size of the silver halide is preferably 0.01 μm to 0.7 μm, more preferably 0.05 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100. It is preferable that the expressed coefficient of variation is 15% or less, more preferably 10% or less, with a narrow particle size distribution. The silver halide grains may have a uniform inner or surface layer or different layers. The photographic emulsion used in the present invention is C. by P. Glafkides.
himie et Physique Photographique (Paul Montel, 1967), Photographic Emulsi by GFDufin
on Chemistry (The Focal Press, 1966), V.
Making and Coating Photographi by L. Zelikman et al
c It can be prepared by a method described in Emulsion (The Focal Press, 1964).

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 0 and No. 52-16364,
A method in which the addition rate of silver nitrate or alkali halide is changed according to the grain growth rate, and a method disclosed in British Patent No. 4,242,4
No. 45 and Japanese Patent Application Laid-Open No. 55-158124, it is preferable to use a method of changing the concentration of the aqueous solution and to grow the solution quickly within a range not exceeding the critical saturation.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, usually, an unstable type and / or an unstable type selenium compound is added, and the emulsion is stirred at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1.
3489, JP-A-4-25832, and 4-1092.
No. 40, No. 4-324855, etc. can be used. It is particularly preferable to use the compounds represented by formulas (VIII) and (IX) in JP-A-4-324855.

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 silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 4-129787, J. Chem. Soc. Chem. Commu
n., 635 (1980), 1102 (1979), 645 (1979), J. Chem. Soc. Perkin. Trans., 1,
2191 (1980), edited by S. Patai, The Chemistry of
OrganicSerenium and Tellurium Compounds, Vol1
(1986) and the compound described in Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but 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 45 ° C. 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide, and about 10 ^-7 to 10 ^-2 mol per mol of silver halide. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt and the like may coexist in the process of formation of silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in EP 293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

The silver halide photographic light-sensitive material of the present invention preferably contains a rhodium compound in order to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, rhodium (III) halide compounds or rhodium complex salts having halogens, amines, oxalates and the like as ligands, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium ( III) complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg, KCl, NaCl: KBr, Na
A method of adding Br or the like) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The total addition amount of the rhodium compound is 1 × 10 ^{-8 to} 5 × 1 per mol of the finally formed silver halide.
0 ^-6 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
0 ^-6 mol. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion. Particularly, they can be added at the time of emulsion formation and incorporated into silver halide grains. preferable.

The silver halide photographic light-sensitive material of the present invention preferably contains an iridium compound in order to achieve high sensitivity and high contrast. Various compounds can be used as the iridium compound used in the present invention,
For example, hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like can be mentioned. These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.). Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total amount of the iridium compound added is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ^-6 mol is suitable, preferably 5 × 10 ^-8 to 1 ×.
It is 10 ^-6 mol. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. The amount of the metal is preferably 1 × 10 ^-9 to 1 × 10 ^-4 mol per mol of silver halide. Further, in order to incorporate the metal, a metal salt in the form of a single salt, a double salt, or a complex salt can be added at the time of preparing particles.

A contact film or contact paper that can be handled in a bright room is generally called a bright-room return sensitive material, and a silver chloride emulsion is preferable for such a sensitive material.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item This section 1) Silver halide emulsion JP-A-2-97937, page 20, lower right column, line 12 and its manufacturing method, see page 21, left lower column, line 14, JP-A-2-12236. The selenium sensitization method described on page 7, upper right column, line 19 to page 8, lower left column, line 12 and Japanese Patent Application No. 2-189532. 2) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17 The lower left column, line 20, and further, the spectroscopy described in JP-A Nos. 1-112235, 2-124560, 3-79928, Japanese Patent Application Nos. 3-189532, 3-411064 and 6-103272. Sensitizing dye. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 to page 4, right Lower column, line 18, Japanese Patent Application No. 5-204325. 4) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; and JP-A-1-237538 The thiosulfinic acid compounds described in Japanese Patent Publication No. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 7) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 9) Hardener JP-A-2-103536, page 18, right upper column, 5th line to 17th line. 9) Dyes: Dyes in the lower right column, lines 1 to 18 of page 17 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 12) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 13) Dihydroxy compounds described in JP-A-3-39948, page 11, upper left column to first benzenes, page 2, lower left column, and EP452772A.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0185]

【Example】

Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] An aqueous solution of silver nitrate, potassium bromide, sodium chloride and K corresponding to 3.5 × 10 ^-7 mol per mol of silver.
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ⁻⁷ mol
A halogen salt aqueous solution containing (H ₂ O) Cl ₅ , sodium chloride, and a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinthione were added by stirring by a double jet method to give an average particle size of 0.25 μm. Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

After that, the product was washed by a flocculation method in a conventional manner, 40 g of gelatin was added per 1 mol of silver, 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver, and the pH was adjusted to 6.0. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was further added as a preservative. Each of the obtained particles has an average particle size of 0.25 μm.
m, silver chlorobromide cubic grains having a silver chloride content of 70 mol%. (Coefficient of variation 10%)

Preparation of Coating Sample On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, from the support side,
Samples were prepared by applying the layers sequentially to form a UL layer, an EM layer, a PC layer, and an OC layer. The preparation method and application amount of each layer are shown below.

(UL Layer) A dispersion of 30% by weight of polyethyl acrylate in gelatin was added to an aqueous gelatin solution and coated so that the amount of gelatin was 0.5 g / m ² .

[0189] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver Triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ⁻⁴ mol of the following compound (p), and 4 × 10 ⁻⁴ mol of the following compound (A) as a nucleation accelerator. Was added. Further, 100 mg of hydroquinone and 30 mg / m ^{2 of} N-oleyl-N-methyltaurine sodium salt were added.
Added as applied. Then hydrazine derivative (Compound No. 17) a ^{1 × 10 -5 mol / m 2} , the water-soluble latex 200 mg / m ² indicated by (d), the dispersion of 200 mg / m ² of polyethyl acrylate, methyl acrylate Latex copolymer of 2-acrylamide-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5:
7) 200 mg / m ^2, an average particle diameter of the colloidal silica 200 mg / m ² of 0.02 [mu] m, sodium dodecylbenzenesulfonate 30 mg / m ^2, 1,3-vinylsulfonyl-2-propanol further as a hardener 20
0 mg / m ² was added. The pH of the solution was adjusted using acetic acid.
Prepared to 65. They were coated so that the coated silver amount was 3.5 g / m ² .

(PC layer) A dispersion of 50 wt% ethyl acrylate in gelatin aqueous solution, and
The following surfactant (w) was added at 5 mg / m ² , and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² , and gelatin was applied at 0.5 g / m ² . .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 4 having an average particle size of about 3.5 μm 4
0 mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² and silicone oil 2
0 mg / m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (e) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate were coated.

[0192]

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

[0194]

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SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² Dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0196]

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

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment As a developing solution, the following developing solution A was used as a comparative developing solution and Table 1 was used.
The developing solution containing the second development accelerator of the present invention shown in (1) was added at 1.0 × 10 ⁻³ mol / liter. 4 above sample
Through an interference filter having a peak at 88 nm, it was exposed to xenon flash light having an emission time of 10 ⁻⁵ sec through a step wedge, developed at 35 ° C. for 20 seconds, and then fixed, washed with water and dried. Developer A Potassium hydroxide 25.0 g Diethylenetriaminepentaacetic acid 2.0 Potassium carbonate 30.0 Sodium sulfite 10.0 Potassium bromide 2.0 5-Methylbenzotriazole 1.0 N-Methyl-p-aminophenol 7.5 Sodium erythorbate 30.0 Boric acid 12.0 Dimercaptothiadiazole 0.08 Add water to make 1.0 liter. (PH adjusted to 9.7)

[0199]

[Table 1]

The fixing solution used had the following formulation. (Formulation of fixing solution) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 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 3 liters by adding water

(2) Evaluation of Image Contrast and Sensitivity As an index (gamma) indicating the image contrast, from the point of fog + density 0.1 of the characteristic curve, fog + density 3.
Points of 0 were connected by a straight line, and the slope of this straight line was represented as a gamma value. That is, gamma = (3.0−0.1) / [l
og (exposure to give a density of 3.0)-(exposure to give a density of 0.1)], indicating that the larger the gamma value, the harder the photographic characteristics. As a graphic arts photosensitive material, gamma is preferably 10 or more, and more preferably 15 or more. Photosensitivity is the logarithmic value of the reciprocal of the exposure amount that gives a density of 1.5,
It was expressed as a relative value with respect to the developer A after 20-second processing. Dmax is the maximum blackening density. To evaluate development progress, 35 ℃ 3
The treatment was performed for 0 seconds. The smaller the difference in sensitivity between the 20-second processing and the 30-second processing and the Dmax difference, the faster the development progress. Sensitivity difference (ΔS) = (30 second processing sensitivity) − (20 second processing sensitivity) Dmax difference (ΔDmax) = (30 second processing Dmax) − (20 second processing Dmax) The above results are shown in Table 1. It was shown to. By using the compound of the present invention, high contrast and Dmax can be obtained even after 20 seconds of treatment. Also, even if the development time is extended to 30 seconds, the sensitivity and
It can be seen that the increase in Dmax is small and the current progress is extremely fast. In other words, it shows that stable performance can be obtained with a developing time as short as 20 seconds.

Example 2 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. [Emulsion B] Emulsion except that 1 mg of selenium sensitizer of the following structural formula per mole of silver, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid were added and chemically sensitized at 60 ° C. to obtain an optimum sensitivity. A was adjusted in the same manner as in A.

[0203]

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Preparation of coating sample In place of the sensitizing dye in the EM layer of Example 1, the following compound (S-3) was added in an amount of 2.1 × 10 ⁻⁴ mol per mol of silver to prepare an emulsion for the EM layer. A sample was prepared in the same manner as in Example 1 except that Emulsion B was used.

[0205]

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<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 633 nm and passed through a step wedge to emit light for 10 ⁻⁶ se.
The substrate was exposed to xenon flash light of c. The same treatment as in Example 1 was performed and the same results as in Example 1 were obtained. Example 3 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 1 except that the sensitizing dye in the EM layer of Example 1 was changed to the following compound (S-4).

[0207]

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<Evaluation of Photographic Performance> The above sample was tested for 780n.
Through an interference filter having a peak at m, it was exposed with a xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge. After developing with the developer A described in Example 1 for 30 seconds at 35 ° C., fixing (the same as in Example 1), washing with water, and drying were performed. Evaluation of various performances was performed in the same manner as in Example 1. <Results> By using the light-sensitive material of the present invention and the developer, a light-sensitive material for a semiconductor laser scanner having high image quality and good processing stability could be obtained.

Example 4 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 1 except that the sensitizing dye in the EM layer of Example 1 was changed to the following compound (S-5). Created.

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<Evaluation of Photographic Performance> The above sample was exposed to tungsten light at 3200 ° K through a step wedge. The developer A described in Example 1 was used for 30 at 35 ° C.
After developing for a second, fixing, washing with water and drying were performed. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) as the fixer
Was used. Evaluation of various performances was performed in the same manner as in Example 1.

<Results> As in Example 1, by using the light-sensitive material of the present invention and the developer, it was possible to obtain a light-sensitive material having high image quality and good processing stability.

Example 5 Based on the photosensitive material formulation of Example 5 of Japanese Patent Application No. 5-202547, a coating sample containing the hydrazine derivative of the present invention was prepared, and a development treatment was conducted in the same manner as in Examples 1 and 2. , Evaluated. As in Example 1 of the present specification, a good photographic light-sensitive material could be obtained.

Example 6 Developer No. 4 of Example 1 was prepared from a pack stored in the solid state. In the method for manufacturing the pack of the solid processing agent, the components of the developing solution are solidly laminated and packed in a bag made of an aluminum foil coated with a plastic material. The order of stacking is from the top, the first layer is sodium erythorbate, the second layer and other components, the third layer is sodium bisulfite, the fourth layer is potassium carbonate, the fifth layer is potassium hydroxide, and the mixture is evacuated in a conventional manner and the system is vacuumed. And sealed.

<Results> Even if a developing solution prepared from this solid processing agent was used in the development processing of Examples 1 to 5, Example 1 was used.
Similar results to ~ 5 were obtained.

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Claims (3)

[Claims] 1. A silver halide light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, and the emulsion layer or another hydrophilic colloid layer containing a hydrazine derivative and a first development accelerator. Containing ascorbic acid as a developing agent and a second development accelerator represented by the general formula (N-I), (N-II) or (P-I).
An image forming method, which comprises processing with a developer of 0 to 10.5. General formula (N-I): In the formula, Z ¹ represents a non-metal atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle in cooperation with N and X ¹ .
X ¹ represents N or CR ¹² . Here, R ¹² has the same meaning as R ¹¹ . R ¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ¹¹ is a hydrogen atom, a halogen atom, or a carbon atom, an oxygen atom,
It represents a substituent bonded to the ring by a nitrogen atom or a sulfur atom. m
¹ is 0 or an integer equal to or less than the maximum substitutable number in the ring.
When m ¹ is 2 or more, each R ¹¹ may be the same or different, and each R ¹¹ may be bonded to form a ring.
Further, two kinds of radicals having one arbitrary hydrogen atom taken out from the general formula (N-I) may be bonded to each other to form a bis type structure. Y ¹ is a counter ion for charge balance, and n ¹
Is the number required for charge balance. General formula (N-II) In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and may be the same or different.
R ²² , R ²³ and R ²⁴ may combine to form a monocyclo or bicyclo 5- to 7-membered nitrogen-containing heterocycle. Further, two kinds of radicals obtained by removing one arbitrary hydrogen atom from the general formula (N-II) may be bonded to each other to form a bis type structure. Y ² is a counter ion for charge balance, and n
² is the number required for charge balance. General formula (P-I) In the formula, R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and they may be the same or different. From the general formula (P-I), arbitrary radicals having one or two hydrogen atoms may be bonded to each other to form a bis type structure or a tris type structure. Y ⁷ is a counter ion for charge balance, and n ⁷ is a number required for charge balance. 2. The image forming method according to claim 1, wherein a developing solution containing aminophenols is used as an auxiliary developing agent. 3. A solution containing 0.4 mol / liter or less of sulfite, a developing starter solution having a pH of 9.0 to 10.0, and a solution having a higher pH than that used as a developing replenisher. The image forming method according to claim 1 or 2.