JPH05323522A - Treatment of black and white silver halide photographic material - Google Patents

Abstract

PURPOSE:To provide images with little uneven development by using a fixing solution containing bromine ion and/or iodine ion or a developing solution containing a specified compound. CONSTITUTION:A photographic material is treated with a fixing solution containing 1X10<-2> mole of bromine-ion and/or 5X10<-4>-5X10<-2> mole of iodine ion per 1 litre. Or it is treated by a developing solution containing a compound having the formula wherein Y and Z may be same or different and stand for N or CR<2> (R<2> stands for substituted or unsubstituted alkyl or aryl); R<1> for alkyl or aryl or hetero cyclic group substituted with at least one of SO3M, -COOM, -OH, -NHSO2OR, SO2NR<3>R<4>, and NR<5>CONR<3>R<4> or alkyl or aryl; R<3>-R<5> for hydrogen atom, lower alkyl with l-4 carbon number; M for hydrogen atom, an alkali metal, and quaternary ammonium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a black and white silver halide photographic light-sensitive material comprising a silver halide emulsion containing 80 mol% or more of silver chloride and an iron compound using a roller-conveying type automatic processor.

[0002]

2. Description of the Related Art Silver chloride containing iron compounds is 80 mol%
The silver halide photographic light-sensitive material comprising silver chlorobromide, silver chloroiodide, silver chloroiodobromide, or pure silver chloride as described above can provide good photographic performance even if the developing time and fixing time are short. Further, it is excellent in that stable photographic performance can be obtained even if the developer replenishing amount and the fixing solution replenishing amount per unit processing area are reduced. However, the above silver halide photographic light-sensitive material has a drawback that uneven development is likely to occur when processed by a roller-conveying type automatic developing machine. As a method for solving such a problem, Japanese Patent Laid-Open No. Sho 6
The techniques described in Nos. 3-40154 and 62-212651 are known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image having less uneven development when a silver halide photographic light-sensitive material containing an iron compound having a silver chloride content of 80 mol% or more is processed by a roller-conveying type automatic processor. To provide.

[0004]

A high silver chloride grain containing 80 mol% or more of iron chloride, wherein the grain contains an iron compound in an amount of 10 ^-6 mol or more per mol of silver halide (silver mol). In the method of processing a black-and-white silver halide photographic light-sensitive material comprising a silver emulsion by using a roller-conveying type automatic developing machine, bromide ion is added at 1 × 10 ^-2 to 1 liter
1 mol and / or iodide ion of 5 × 10 ^{−4 to} 5 ×
A treatment method characterized by treatment with a fixing solution containing 10 ^-2 mol, or a high silver chloride grain containing 80 mol% or more of silver chloride, wherein the iron compound is in a silver halide mole (silver halide). In a method of processing a black-and-white silver halide photographic light-sensitive material comprising a silver halide emulsion containing 10 ^-6 mol or more per mol) using a roller-conveying type automatic processor, the compound represented by the following general formula (I) is contained. Processing method characterized by processing with a developing solution General formula (I)

[0005]

[Chemical 2]

In the formula, Y and Z may be the same or different and each is N or CR ² (R ² represents an alkyl group or an aryl group) and R ¹ is --SO ₃ M, --COOM or --O.
^{_{H, -NHSO 2 R 3, -SO}} 2 NR 3 R 4 , and -N
An alkyl group, an aryl group or a heterocyclic group or an alkyl group substituted with at least one selected from the group consisting of R ⁵ CONR ³ R ⁴ and a group in which the aryl group or the heterocyclic group is formed via a linking group; Represent. R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. M is a hydrogen atom,
Achieved by representing alkali metals, quaternary ammonium and quaternary phosphonium.

Bromide ion used in the fixing solution of the present invention
And iodide ion of water-soluble bromide salt or iodide salt
It is preferable to add the compound in the form of
Ammonium bromide, sodium bromide, potassium bromide
Aluminum, ammonium iodide, sodium iodide, potassium iodide
Alkali metal salt, ammonium salt, al
Potassium earth metal salts and the like can be mentioned. The bromide
ON concentration is 1 × 10 ^-2Between ~ 1 mol / l
And iodide ion concentration is 5 × 10^-Four~ 5 x 10 ^-2Mol /
Each liter has a favorable effect, but the odor is especially
1 x 10 for halide ions^-2~ 5 x 10^-1In moles
It is preferable that the iodide ion is 5 × 10.^-Four
~ 1 x 10^-2It is preferably molar. Where Io
If the number of inks exceeds the above range, fixing failure may occur, which is preferable.
Absent. If the amount is less than the above range, the desired effect cannot be obtained.
Yes.

The compound used in the developing solution of the present invention is represented by the general formula (I). General formula (I)

[0009]

[Chemical 3]

In the formula, Y and Z may be the same or different and each is N or CR ² (R ² represents a substituted or unsubstituted alkyl group or aryl group), R ¹ is --SO ₃ M, --COOM,
^{_{-OH, -NHSO 2 R 3, -SO}} 2 NR 3 R 4 and -NR ⁵ CONR ³ at least one substituted alkyl group selected from the group consisting of R ^4, an aryl group or a heterocyclic group or an alkyl group , Represents a group in which an aryl group or a heterocyclic group is formed via a linking group. R ³ , R
⁴ and R ^{5, which} may be the same or different, each represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. M represents a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium. Specific examples of the alkyl group represented by R ¹ include a linear or branched alkyl group having 1 to 20 carbon atoms (eg, methyl group, propyl group, hexyl group, dodecyl group, isopropyl group), 1 to 20 carbon atoms. Specific examples of the cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, etc.) and aryl group include 6 to 2 carbon atoms.
0 aryl group (for example, phenyl group, naphthyl group, etc.), specifically as a heterocyclic group, one or more nitrogen atoms,
5-membered, 6-membered or 7-membered heterocycles containing oxygen or sulfur atoms, etc., including those forming a condensed ring at an appropriate position (eg, pyridine ring, quinoline ring, pyrimidine ring) , Isoquinoline ring etc.). Further, the alkyl group (straight chain, branched alkyl group, cycloalkyl group), aryl group and heterocyclic group may be further substituted, and specifically, a halogen atom (F, Cl, Br, etc.), an alkyl group ( Methyl group, ethyl group), aryl group (phenyl group, p-chlorophenyl group, etc.), alkoxy group (methoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p- Toluenesulfonyl group, etc., carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), allyloxycarbonylamino group (phenoxy group, etc. Carbonylamino group, etc.), alkoxycarbonyl Group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, nitro group, amino group (unsubstituted amino group, dimethylamino group, etc.), alkylsulfinyl group (methoxysulfinyl group, etc.), aryl Examples thereof include a sulfinyl group (such as a phenylsulfinyl group), an alkylthio group (such as a methylthio group), and an arylthio group (such as a phenylthio group), and these substituents are 2
One or more may be substituted, and when two or more are substituted, they may be the same or different. Examples of the substituent of the alkyl group or aryl group represented by R ² include the same as the substituent of R ¹ . Further, as the above-mentioned linking group which may be contained in R ¹ , —S—, —O—, —NR ³ —, —CO—,
_{-SO -, - SO 2 -,} - SO 2 NR 3 -, - CONR
_{^{3, -COO -, - SO 2}} - is preferred. Here, the R ^3, the same meaning as R ^3, such as -NHSO ₂ R ³ described above. The following can be mentioned as specific examples of R ¹ having a linking group.

[0011]

[Chemical 4]

Among those represented by the general formula (I),
Particularly preferred are those represented by the general formula (II). General formula (II)

[0013]

[Chemical 5]

R ^{5 in the} general formula (II) is at least one-
_{COOM, -SO 3 M, -OH,} -NHSO 2 R 3, -
It represents a phenyl group substituted with SO ₂ NR ³ R ⁴ or —NR ³ CONR ³ R ⁴ , and this phenyl group may be further substituted with another substituent. The other substituents substituting the phenyl group are synonymous with the substituents of the alkyl group, aryl group and heterocyclic group represented by R ¹ in formula (I). Here -COOM, -SO ₃ M, -O
^{_{H, -NRSO 2 R 3, -SO}} 2 NR 3 R 4 , and -N
When there are two or more R ³ CONR ³ R ^4, they may be the same or different, and —COOM and —SO ₃ M are particularly preferable. M
Has the same meaning as that represented by the general formula (I). Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

Preferred compounds of general formula (I) in the developer.
High concentration range is 1 × 10^-Five~ 1 x 10 ^-2Mol / liter,
Particularly preferably 5 × 10^-Five~ 5 x 10^-3Mol / lit
The range is le.

The high silver chloride content in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is 80 mol% or more (average value).
Silver chloride, silver iodochloride, silver iodochlorobromide or silver chloride. It also includes pure silver chloride. The silver iodide content is preferably 1 mol% or less. Particularly preferred is silver chlorobromide or silver chloride containing 96 mol% or more (average value) of silver chloride. The high silver chloride emulsion used in the present invention preferably has a silver bromide localized layer in which the silver bromide content is relatively higher than that of the substrate in the silver halide grains.

A preferred example of such a localized structure is one having a localized phase on the surface of the silver halide grain or inside the grain close to the surface, and particularly in the edge portion or the corner portion of the crystal surface of the grain, or the crystal plane. Those having a localized phase in the form of protrusions are preferable. The halogen composition in the localized phase may have a silver bromide content of 10 mol% or more and 95 mol% or less.
It is preferable that the content is not less than mol% and not more than 90 mol%. Further, it is preferably 20 mol% or more and 60 mol% or less, and most preferably 30 mol% or more and 60 mol% or less. The remaining silver halide in the localized phase consists of silver chloride, but it is also preferred to include traces of silver iodide. However, as described above, it is not preferable to exceed 1 mol% with respect to the total amount of silver halide. Further, these localized phases preferably account for 0.03 mol% or more and 35 mol% or less of the silver halide constituting all silver halide grains of the emulsion, and more preferably 0.1 mol% or more and 25 mol% or more. It is preferable to occupy mol% or less.

The localized phase does not have to consist of a single halogen composition, may have two or more localized phases having distinctly different silver bromide contents, and other than the localized phase. It may be such that the interface with the phase is formed while continuously changing in halogen composition. In order to form a silver bromide localized phase as described above, a water-soluble silver salt and a water-soluble halogen salt containing a water-soluble bromide are simultaneously mixed with an emulsion containing silver chloride or high silver chloride grains already formed. Or deposit a portion of the already formed silver chloride or high silver chloride grains into a silver bromide-rich phase using the so-called halogen conversion method, or silver chloride or high silver chloride grains. It can also be formed by adding fine grained silver bromide or high silver bromide grains or other sparingly soluble silver salt to crystallize the surface of silver chloride or high silver chloride grains by recrystallization. For such a manufacturing method,
For example, it is described in European Patent Application Publication No. 0,273,430A2.

Of these methods, the method of forming a high silver bromide layer particularly useful in the present invention is a method of forming silver bromide and / or silver chlorobromide on the surface of a high silver chloride emulsion during chemical ripening. And is preferable in that high sensitivity and low fog can be obtained. An iron compound containing iron ions is used in the silver halide grains of the present invention. The iron compound used in the present invention is a divalent or trivalent iron ion-containing compound, preferably an iron salt or an iron complex salt having water solubility in the concentration range used in the present invention. Specific compounds are shown below. Ferrous nitrate ammonium basic ferric acetate ferric albumin ferric ammonium acetate ferric bromide ferric chloride ferric chloride ferric citrate ferric fluoride ferric formate Glycero ・ ferric phosphate ferric hydroxide acidic ferric phosphate ferric nitrate ferric phosphate ferric pyrophosphate ferric pyrophosphate sodium ferric cyanide ferric sulfate ferric sulfate ferric sulfate Iron Ammonium Ferrous arsenate Ferrous bromide Ferrous carbonate Ferrous ferrous chloride Ferrous citrate Ferrous ferrous formate Ferrous formate Ferrous gluconate Ferrous ferrous hydroxide Ferrous iodide Ferrous lactate ferrous oxalate ferrous phosphate ferrous succinate ferrous sulfate ferrous thiocyanate ferrous nitrate ferric sulfate guanidine ferric ammonium citrate hexane cyanoferrate (II) acid Potassium benthacyanoammine Ferrous potassium Potassium ethylenedi Ferric trisodium tetraacetate Potassium hexacyanoferrate (III) ferric chloride Tris (dipyridyl) ferric chloride Bentacyanonitrosyl ferric potassium Hexarea ferric chloride Especially hexacyanoferrate (II) acid salt, hexacyanoferrate (III)
Acid salts, ferrous thiocyanate and ferric thiocyanate show remarkable effects. The amount of the Fe compound added is 10 ^-6 mol or more, and preferably 10 ^-6 to 10 ^-3 mol per mol of silver. The iron compound can be appropriately added during the production of the silver halide emulsion and before each step of coating the emulsion, but it is particularly preferable to add it during grain formation and to incorporate it into the silver halide grain.

In the silver halide emulsion used in the present invention, AgCl 90 mol% or more, Br ion 1 × 10 ^{-2 to} 5 × 10 ^-1 mol / liter I ion 5 × 10 ^{-4 to} 5 × 10 ^-2 〃 Fe ions of 1 × 10 ^{−5 to} 3 × 10 ⁻³ 〃 AF agent of 5 × 10 ^{−5 to} 5 × 10 ⁻³ 〃 are more preferable. The silver halide grains used in the present invention include metal ions other than silver ions (for example, the periodic table
VIII group metal ion, group II transition metal ion, group IV lead ion, group I metal ion, copper ion, etc.) or their complex ions are contained under various conditions. It is preferable for better performance. These metal ions or their complex ions may be contained in the whole silver halide grains, the above-described silver bromide localized phase, or any other phase. Among the above metal ions or complex ions thereof, those selected from iridium ion, palladium ion, rhodium ion, zinc ion, platinum ion, gold ion, copper ion and the like are particularly useful. It is often the case that these metal ions or complex ions are used in combination, rather than being used alone, to obtain desirable photographic properties. Especially, it is necessary to change the added ionic species and the added amount between the localized phase and other parts of the particle. Is preferred. In particular,
Iridium ions and rhodium ions are preferably contained in the localized phase.

In order to incorporate a metal ion or a complex ion into the localized phase of the silver halide grain and / or other portions of the grain, the metal ion or the complex ion may be added before, during or after the formation of the silver halide grain. It may be added directly to the reaction vessel during the subsequent physical ripening, or may be added in advance in the addition solution of the water-soluble halogen salt or water-soluble silver salt. When the localized phase is formed of fine grained silver bromide or high silver bromide, it is added to silver bromide or high silver bromide fine grains by the same method as above and added to silver chloride or high silver chloride emulsion. You may. Further, metal ions may be contained while forming a localized phase by adding a bromide other than silver salt, which is relatively sparingly soluble to the above metal ions, as a solid or powder.

The sensitizing dye used in the present invention is disclosed in JP-A-3-11.
No. 336, JP-A-64-40939, Japanese Patent Application No. 2-26
No. 6934, No. 3-121798, No. 3-22874.
No. 1, No. 3-266959 and No. 3-311498.
The sensitizing dyes described in the publication No. etc. can be preferably used.
These sensitizing dyes may be used alone or in combination with each other.
A combination of sensitizing dyes may be used especially for supersensitization.
Often used for the purpose of feeling. With the sensitizing dye,
A dye or visible light that does not have a spectral sensitizing effect
A substance that does not absorb qualitatively and exhibits supersensitization
It may be contained in the emulsion. Shows useful sensitizing dye and supersensitization
The combination of dyes and substances showing supersensitization are
Volume (Research Disclosure) Volume 176 17
643 (issued in December 1978) Page 23, IV, J.
Rui is the above-mentioned Japanese Examined Patent Publication Nos. 49-25500 and 43-493.
3, JP-A-59-19032, JP-A-59-192242, etc.
It is described in. The content of the sensitizing dye of the present invention is a halogen
Grain size of silver halide emulsion, halogen composition, method of chemical sensitization
The degree of the relation between the layer containing the compound and the silver halide emulsion.
Select the optimum amount according to the type of anti-fogging compound
The test method is
This is something that the traders are familiar with. Usually preferred
10 per mol of silver halide^-7Mole to 1x10^-2Mol, special
To 10^-6Mol to 5 × 10 ^-3Used in the molar range
It

The black-and-white photographic light-sensitive material produced by using the present invention may contain a water-soluble dye as a filter dye in addition to hydrophilic coroit, or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

A polyethylene terephthalate film is preferable as the support of the photographic light-sensitive material of the present invention, and it is particularly preferable that it is colored blue. The support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment in order to improve the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex or the like may be provided, and a gelatin layer may be further provided thereon. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided.
By applying a surface treatment to these undercoat layers, the adhesion with the hydrocolloid layer can be further improved.

The total coating amount of gelatin on the silver halide emulsion layer side of the support of the present invention is preferably 4.0 g / m ² or less, more preferably 3.6 g / m ² or less.
Furthermore, 3.3 g / m ² is preferable. The coated Ag amount per one side of the silver halide emulsion of the present invention is 3.0 g / m ^2.
Or less, preferably 2.8 g / m ² or less, and more preferably 2.6 g / m ² or less. Further, the weight ratio of silver to gelatin in the silver halide emulsion layer is also an important factor from the viewpoint of suitability for rapid processing. Increasing the ratio of silver and gelatin in the silver halide emulsion layer, when processed by an automatic processor,
The so-called emulsion pick-off occurs in which the silver halide photographic light-sensitive material is peeled off by the projections of the roller and the image becomes difficult to see. From this viewpoint, the weight ratio of silver to gelatin in the silver halide emulsion layer is preferably 1.4 or less, more preferably 1.2 or less, and further preferably 1.1 or less.

As the various additives and the like used in the photographic light-sensitive material of the present invention, those described in the following relevant parts can be used.

Item 1) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 2) Antifoggants and stabilizers JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column .. 3) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94249, page 6, lower left column, line 15 to Page 11, right upper column, line 19

4) Surfactant, Antistatic JP-A-2-68539, page 11, upper left column, line 14 agent to page 12, upper left column, line 9 5) Matting agent, slipping agent, JP-A-2-68539, page 12, upper left column, line 10 plasticizer to same upper right column, line 10; page 14 lower left column, line 10 to lower right column, line 1 .. 6) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 7) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6

8) Polyhydroxybenze JP-A-3-39948, page 11, upper left column to the same, page 12, lower left column, EP Patent No. 452772A. 9) Layer structure JP-A-3-198041.

The developing agent preferably used in the developing solution of the present invention is a dihydroxybenzene type developing agent. As the dihydroxybenzene type developing agent, hydroquinone,
Chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3
-Dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, etc., but hydroquinone is particularly preferable. The developing agent is usually 0.05 mol / liter
It is preferably used in an amount of 0.8 mol / l.
In the present invention, it is particularly preferable to use 1-phenyl-3-pyrazolidones or p-aminophenols together with the above-mentioned dihydroxybenzene type developing agent.

Examples of 1-phenyl-3-pyrazolidones include 1-phenyl-3-pyrazolidone and 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Examples include pyrazolidone and 1-phenyl-5-methyl-3-pyrazolidone. As p-aminophenols,
There are N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like. However, among them, N-methyl-p-aminophenol is preferable. When a dihydroxybenzene-based developing agent and an auxiliary developing agent such as 1-phenyl-3-pyrazolidones or p-aminophenols are used in combination, the former is 0.
05 mol / liter to 0.5 mol / liter, the latter 0.001 to 0.06 mol / liter (especially 0.003 mol / liter).
˜0.06 mol / liter).

As the sulfite, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite,
Examples include sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.10 mol / liter or more, particularly preferably 0.20 mol / liter or more. The upper limit is preferably 2.5 mol / liter, particularly preferably 1.2 mol / liter.
The developer used in the present invention may contain an amino compound for promoting development. In particular, JP-A-56-106244
No. 6-267759, Japanese Patent Application No. 1-2941
The amino compound described in No. 8 may be used.

The pH value of the developer used in the present invention is 1
It is 0.6 or less. As the alkali agent used for setting the pH value, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, sodium carbonate) can be used. In addition to the developing replenisher of the present invention, boric acid, borax,
PH buffering agents such as dibasic sodium phosphate, dibasic potassium phosphate, monobasic sodium phosphate and monobasic potassium phosphate, in addition to them, the pH buffering agents described in JP-A-60-93433 can be used; Development inhibitors such as potassium bromide and potassium iodide; organic solvents such as dimethylformamide, methylcellosolve, hexylene glycol, ethanol and methanol; 5 as the benztriazole derivative
-Methylbenztriazole, 5-bromobenztriazole, 5-chlorobenztriazole, 5-butylbenztriazole, benztriazole and the like, but especially 5
-Methylbenztriazole is preferred. Examples of nitroindazole include 5 nitroindazole, 6 nitroindazole, 4 nitroindazole, 7 nitroindazole 3 cyano-5-nitroindazole and the like.
Nitroindazole is preferred. In particular, when a compound such as 5-nitroindazole is used, it is dissolved in a part different from the part containing the dihydroxybenzene type developing agent or the sulfite preservative in advance, and both parts are mixed and water is added at the time of use. Is common. Further, if the portion of 5-nitroindazole to be dissolved is made alkaline, it is colored yellow, which is convenient for handling. Further, if necessary, a color tone agent, a surfactant, a water softener, a film hardener, etc. may be contained.

As the chelating agent in the developing solution, it is preferable to contain a chelating agent having a chelate stability constant of 8 or more for ferric ion (Fe ³⁺ ). Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the following compounds. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetramine hexaacetic acid,
Transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,
Examples thereof include 3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Particularly preferable examples include diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and 1,3-. Diaminopropanol tetraacetic acid, glycol ether diamine tetraacetic acid, hydroxyethyl ethylenediamine triacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid , Diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-
1,1-diphosphonic acid, 1-hydroxyethylidene-
There are 1,1-diphosphonic acids and their salts. In the developer of the present invention, for the purpose of silver stain, Japanese Patent Publication No. 62702/1987,
Japanese Patent Publication No. 62-4703, Japanese Patent Application Laid-Open No. 1-20249, Japanese Patent Application No. 3-94955, Japanese Patent Application No. 3-112275, Japanese Patent Application No.
The compounds described in -233718 can be used.

In addition, the developer of the present invention may contain a dialdehyde hardener or a bisulfite adduct thereof. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α. Examples include -n-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaleindialdehyde, and bisulfite adducts thereof. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed cannot be suppressed and that the drying time is not significantly lengthened. Specifically, 1 to 50 g, preferably 3 to 1 per liter of the developing solution.
It is 0 g. Of these, glutaraldehyde or its bisulfite adduct is most commonly used.

Of course, when a bisulfite adduct of a dialdehyde hardener is used, the bisulfite of this adduct is also calculated as the sulfite in the developer. In addition, L.
F. A. Mason, "Photographic Processing Chemistry," published by Focal Press (1966)
226-229, U.S. Pat. No. 2,193,01
5, No. 2,592,364, JP-A-48-649.
You may use the additive as described in No. 33.

In the present invention, the developing treatment is carried out while replenishing the developing solution as described above in an amount of 300 ml or less, particularly 40 ml to 300 ml per 1 m ² of the light-sensitive material. As the developing solution to be injected into the developing tank of the developing machine at the beginning of development, a solution having the same composition as the above developing solution may be used, or a solution having a part of the composition changed may be used.

The fixing solution used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 4.2.
Has 6.0. Sodium thiosulfate as a fixing agent,
Examples include ammonium thiosulfate. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 3 mol / liter. The fixer may contain water-soluble aluminum salts which act as hardeners, such as aluminum chloride, aluminum sulphate, potassium alum and the like. For the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective.

Preservatives (for example, sulfites and bisulfites), pH buffers (for example, acetic acid and boric acid), pH adjusters (for example, sulfuric acid), and chelating agents having the ability to soften water by water are included in the fixing solution, if desired. And compounds described in JP-A-62-78551.

In the present invention, the fixing process is carried out while replenishing the above-mentioned fixing solution in an amount of 300 ml or less, particularly 40 ml to 300 ml per 1 m ² of the light-sensitive material. In the processing method of the present invention, after the development and fixing steps, it is processed with washing water or a stabilizing solution and then dried.

As the automatic developing machine used in the present invention, a roller-conveying automatic developing machine is used. In addition, JP-A 1-1660
No. 40 and Japanese Patent Application No. 63-18631, by using a developing tank developing machine with a small opening ratio, there is little air oxidation and evaporation, stable operation in the processing environment is possible, and the replenishment amount is further increased. It can be reduced. As a method for reducing the replenishment amount of washing water, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time. When this multi-stage countercurrent system is applied to the present invention, the photosensitive material after fixing is processed in a gradually cleaning direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water. For the above water saving treatment or no piping treatment,
It is preferable to provide antifouling means to the washing water or the stabilizing solution.

As an anti-fungus means, Japanese Patent Laid-Open No. 60-263
UV irradiation method described in No. 939, 60-26394
Method using magnetic field described in No. 0, Ibid. 61-13163
A method for producing pure water using the ion exchange resin described in JP-A No. 62-115154 and JP-A No. 62-15395.
No. 2, Japanese Patent Application Nos. 61-63030 and 61-51396.
It is possible to use the method using the antibacterial agent described in No.
Furthermore, LFWest, "Water Quality Criteria" Photo.
Sci. & Eng. Vol.9 No. 6 (1965), MWBeach, "M
icrobiological Crowths in Motion-picture Processin
g "SMPTE Journal Vol.85, (1976), RODeega
n, "Phot Processing Wash Water Biocides" J. Imaging T
ech 10, No. 6 (1984) and JP-A-57-8.
No. 542, No. 57-58143, No. 58-10514.
5, No. 57-132146, No. 58-18631
No. 57-97530, No. 57-157244,
The antibacterial agent, antifungal agent, surfactant and the like described in Japanese Patent Application No. 3-24138 may be used in combination.

Further, the washing bath or the stabilizing bath should have an RT
Kreiman, J. Image.Tech 10, (6) 242 (19).
84) isothiazoline compounds, Research
Disclosure Volume 205, No. 20526 (May 1981 issue), isothiazoline compounds, No. 2
Volume 28, No. 22845 (April 1983), isothiazoline compounds, Japanese Patent Application No. 61-51396.
It is also possible to use the compounds described in No. 1 and the like together as a bacteriostatic agent (Microbiocide). Others, "The Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology", Japanese Society of Antibacterial and Antifungal, Hakuhodo (Showa 61)
May include compounds such as those described in. When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank described in JP-A-63-18350. In addition, JP-A-63-143
It is also preferable to adopt a structure of a water washing step such as No. 548. Further, some or all of the overflow from the washing or stabilizing bath caused by supplementing the washing or stabilizing bath with anti-fouling water according to the method according to the present invention is disclosed in JP-A-60-235133. It can also be used for a processing solution having a fixing ability, which is a processing step before that, as described in No.

In the present invention, the "development process time" or "development time" means the time from the dipping of the tip of the photosensitive material to be processed in the developing tank solution of the developing machine to the dipping of the next fixing solution. "Fixing time" is the time from immersion in the fixing tank liquid to immersion in the next washing tank liquid (stabilizing liquid),
"Washing time" means the time of immersion in the washing tank liquid. In addition, the "drying time" is usually 35 ° C to the automatic developing machine.
A drying zone in which hot air of 100 ° C., preferably 40 ° C. to 80 ° C. is blown is installed, and it means the time in the drying zone. In the development processing in the present invention,
Development time is 5 seconds to 30 seconds, preferably 5 seconds to 20 seconds, and the development temperature is preferably 18 ° C to 50 ° C, 20 ° C to 40 ° C.
C is more preferred. According to the present invention, the fixing temperature and time are preferably about 18 ° C. to about 50 ° C. for 5 seconds to 30 seconds, 20
More preferably, the temperature is from 40 to 40 ° C for 5 to 20 seconds. Within this range, sufficient fixing can be performed, and the sensitizing dye can be eluted to the extent that residual color is not generated. The temperature and time in the water washing (or stabilizing bath) are preferably 0 to 50 ° C and 5 to 30 seconds, and more preferably 15 to 40 ° C and 5 to 20 seconds.

According to the method of the present invention, rinsing water is squeezed out on the light-sensitive material which has been developed, fixed and washed (or stabilized). That is, it is dried through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 30 seconds, and particularly preferably at 40 ° C. to 80 ° C. for about 5 seconds to 2
0 seconds. Dry to Dr with the sensitive material / processing system of the present invention
When developing for 100 seconds or less at y, in order to prevent development unevenness peculiar to rapid processing, JP-A-63-1519
A roller made of a rubber material as described in JP-A-43-43 is applied to a roller at the outlet of the developing tank, and as described in JP-A-63-151944, a developer is stirred in the developing solution tank. The discharge flow rate for this purpose is set to 10 m / min or more, and further, JP-A-63-26475.
As described in JP-A-8, it is more preferable to stir more strongly than during standby at least during the development process. For further rapid processing, it is more preferable that the rollers of the fixing solution tank are opposed rollers in order to increase the fixing speed. By configuring with opposed rollers, the number of rollers can be reduced and the processing tank can be made smaller. That is, it is possible to make the automatic processor more compact.

[0051]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples.

Example 1 1. Preparation of silver halide emulsion A 32 g of gelatin was added to 900 ml of distilled water and the mixture was added at 40 ° C.
After dissolution, adjust the pH to 3.8 with sulfuric acid and add sodium chloride.
3.3 g was added. 32 g of silver nitrate in 200 ml of distilled water
Dissolved liquid and sodium chloride 11g, K₂IrCl₆To
A solution prepared by dissolving 0.02 mg in 200 ml under the condition of 40 ° C.
The above solution was added and mixed in 2 minutes. 64g of silver nitrate
A solution of 280 ml of distilled water and sodium chloride 21.
6 g dissolved in 275 ml and 5 minutes at 40 ℃
The mixture was added and mixed over a period of time. Continuously distill 64g of silver nitrate
Liquid dissolved in 280 ml of water and 22.4 g of sodium chloride,
K _FourFe (CN)₆・ 3H₂0.04g of O to 285ml
Add the dissolved liquid to the solution at 40 ° C for 5 minutes.
It was mixed. When the obtained emulsion was observed with an electron microscope,
The average side length of about 0.21 μm and the particle size distribution
From a cubic particle with a coefficient of variation of 9.8%
Was an emulsion.

After desalting this emulsion, 72 g of gelatin,
2.6 g of phenoxyethanol was added, pH 6.7, N
Chemical sensitization was carried out at 58 ° C. by adjusting the pAg of 7.9 with aCl according to the following procedure. First, average particle size 0.05
A monodisperse silver bromide emulsion having a thickness of 1 μm was added in an amount of 1 mol% with silver halide, and then 7.2 mg of the compound (1) and 9.2 m of chloroauric acid were added.
g, triethylthiourea 1.3 mg, selenium sensitizer (A)
0.72 mg and 0.29 g of nucleic acid were added, and finally 4
162 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added and rapidly solidified to obtain Emulsion A.

[0054]

[Chemical 11]

Selenium sensitizer (A)

[0056]

[Chemical formula 12]

2. Preparation of emulsion coating liquid The following chemicals were added to Emulsion A per mol of silver halide to prepare an emulsion coating liquid.

(Formulation of Emulsion Coating Solution) a. Spectral sensitizing dye [2] 5.5 × 10 ⁻⁵ mol. Supersensitizer [3] 3.3 × 10 ⁻⁴ mol c. Polyacrylamide (molecular weight 40,000) 9.2 g d. Trimethylolpropane 1.4 g e. Poly (ethyl acrylate / methacrylic acid) latex 22g

Spectral sensitizing dye [2]

[0060]

[Chemical 13]

Supersensitizer [3]

[0062]

[Chemical 14]

3. Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer The container was heated to 40 ° C., and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. t-octylphenoxyethoxyethanesulfonic acid sodium salt 1.5 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.3g Ji. C ₈ F ₁₇ SO ₃ K 84 mg li. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. NaOH 0.2 g. Methanol 78cc. 1,2-Bis (vinylsulfonylacetamide) ethane Prepared to be 2.5% by weight based on the total amount of gelatin in the emulsion layer and the surface protective layer. Wa. Compound (8) 52mg

[0064]

[Chemical 15]

4. Preparation of back layer coating liquid

The container was heated to 40 ° C. and the following chemicals were added to prepare a back layer coating solution. I. Gelatin amount 100 g b. Dye [A] 2.38 g

[0067]

[Chemical 16]

C. Sodium polystyrene sulfonate 1.1 g d. Phosphoric acid 0.55 g E. Poly (ethyl acrylate / methacrylic acid) latex 2.9 g f. Compound (8) 46 mg g. Oil dispersion of dye (B) described in JP-A-61-285445 246 mg as dye itself Dye (B)

[0069]

[Chemical 17]

H. Oligomeric surfactant dispersion of dye (C) described in JP-A-62-175639 46 mg as dye itself Dye (C)

[0071]

[Chemical 18]

5. Preparation of back surface protective layer coating liquid

The container was heated to 40 ° C., and the chemicals shown below were added to prepare a coating solution.

B. Gelatin 100 g b. Sodium polystyrene sulfonate 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g f. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.6g bets. C ₈ F ₁₇ SO ₃ K 268 mg h. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 45mg Li. NaOH 0.3 g Nu. 131 ml of methanol 1,2-bis (vinylsulfonylacetamide) ethane based on the total amount of gelatin in the back layer and surface protection layer. Prepared to be 2%. Wo. Compound (8) 45mg

6. Preparation of Photographic Material The back layer coating solution and the surface protective layer coating solution of the back layer were coated on one side of a polyethylene terephthalate support colored in blue, and the gelatin coating amount of the back layer was 2.6.
The coating amount was 9 g / m ² , and the coating amount of gelatin in the surface protective layer of the back layer was 1.13 g / m ² . Followed by the opposite side of the support and the emulsion coating solution and surface protective layer coating solution described above which, and the gelatin coating amount of the emulsion layer coating amount Ag is 1.85 g / m ² is at 1.6 g / m ² The surface protective layer was coated such that the coating amount of gelatin was 1.23 g / m ² . Thus, a photographic material was produced.

When the obtained sample was dipped in a 1.5% by weight aqueous solution of sodium hydroxide at 50 ° C., the time until the hydrophilic colloid layer of this sample began to melt was 50 minutes or more.

Preparation of Developer-A Hydroquinone 20.0 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 5-methylbenztriazole 0.3 g sodium sulfite 35.0 g potassium carbonate 25.0 g Diethylenetriamine pentaacetic acid 2.0 g Diethylene glycol 20.0 g Boric acid 9.0 g Potassium bromide 0.6 g Water is added to 1 liter, and the pH is set to 10.0 with potassium hydroxide.

[0078] fixer -A Preparation Ammonium thiosulfate 145g disodium ethylenediaminetetraacetate dihydrate _{0.03g Na 2 S 2 O 3 ·} 5H 2 O 15g sodium metabisulfite 13.3 g NaOH 12.6 g acetic acid (90 wt% ) 30g Add water to 1 liter

Preparation of Fixer B: 20 g of KBr was added to 1 liter of Fixer A.

Preparation of Fixer-C 0.5 g of KI was added to 1 liter of fixer A.

Automatic processor processing The FPM-1300 was modified to obtain a linear velocity of 27.3 mm / sec, D
Processing was carried out at ry to dry 44 seconds, developing temperature 35 ° C., and fixing temperature 32 ° C. The sample was cut into 10 inches × 12 inches, and subjected to uniform exposure in the above treatment so that the average density was within 1.0 ± 0.1.

Results The results are summarized in Table 1.

[0083]

[Table 1]

As is clear from Table I, it can be seen that development unevenness can be markedly reduced by treatment with a fixing solution containing bromide ions or iodide ions.

Example 2 Preparation of Developer-B A compound [12] was added to Developer-A.

[0086]

[Chemical 19]

129 mg / 1 liter was added to the developer-B.
Was prepared.

Results The same treatment as in Example-1 was carried out to evaluate development unevenness. The results are shown in Table 1. The fixing solutions -A and -B are those of Example-1.
Is the same as. As shown in Table II, it can be seen that development unevenness can be remarkably reduced by processing with a developing solution containing a compound represented by the general formula (I).

[0089]

[Table 2]

[0090]

INDUSTRIAL APPLICABILITY When a black-and-white silver halide photographic light-sensitive material comprising high silver chloride grains containing iron ions containing 80 mol% or more of silver chloride is processed by a roller-conveying type automatic developing machine, (1) bromide ion and / or Alternatively, an image having less development unevenness can be obtained by using a fixing solution containing iodide ions and / or (2) using a developing solution containing a compound represented by the general formula (I).

Claims (2)

[Claims] 1. A high silver chloride grain containing silver chloride in an amount of 80 mol% or more, which comprises a silver halide emulsion containing an iron compound in an amount of 10 ^-6 mol or more per mol of silver halide (silver mol). In the method of processing a black-and-white silver halide photographic light-sensitive material by using a roller-conveying type automatic processor, bromide ion is added in an amount of 1 × 10 ^-2 to 1 mol / liter and
Alternatively, the processing method is characterized by processing with a fixing solution containing 5 × 10 ^{−4 to} 5 × 10 ⁻² mol of iodide ions. 2. A high silver chloride grain containing silver chloride in an amount of 80 mol% or more, which comprises a silver halide emulsion containing an iron compound in an amount of 10 ⁻⁶ mol or more per mol of silver halide (silver mol). In the method of processing a black-and-white silver halide photographic light-sensitive material using a roller-conveying type automatic developing machine, processing is carried out with a developing solution containing a compound represented by the following general formula (I). ) [Chemical 1] Here, Y and Z in the formula may be the same or different, and each is N
Or CR ² (R ² represents an alkyl group / aryl group), R ¹ is —SO ₃ M, —COOM, —OH, —NH
_{^{SO 2 R 3, -SO 2 NR}} 3 R 4 and -NR ⁵ CON
It represents a group in which an alkyl group, an aryl group or a heterocyclic group or an alkyl group, an aryl group or a heterocyclic group substituted with at least one selected from the group consisting of R ³ R ⁴ is formed via a linking group. R ³ , R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom or a carbon number of 1 to 4.
Represents a lower alkyl group. M represents a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium.