JPH08292525A - Development processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material for reversal capable of being rapidly processed and replenished in a low rate, restrained from increase of black spots, reduced in line thickening, and reproduced in high fidelity, and further enhanced in reversed text quality and image density reducibility. CONSTITUTION: The silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer and a nonphotosensitive hydrophilic colloidal layer on a support and it is exposed and developed and processed by using an automatic developing apparatus. At least one of the hydrophilic colloidal layer contains at least one kind of hydrazine derivative and 2 kinds of silver halide grains different from each other in sensitivity and at least one of them have a silver chloride content of >=90mol%, and this photosensitive material is processed with a developing solution containing substantially no dihydroxybenzenes in a pH of 9.5-11.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of developing and processing a silver halide photographic light-sensitive material for printing plate making, and more particularly to a method of developing and processing a silver halide photographic light-sensitive material used in a step called reversion in a plate-making process.

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this step, there is known a method of processing a light-sensitive material containing a hydrazine derivative with an alkali developing solution, which is a photographic technique capable of reproducing an image in ultrahigh contrast. However, in this method, there is a problem that a sandy fog, which is a so-called black spot, is generated in the unexposed portion after the development processing, and the image is deteriorated, so that the satisfactory performance cannot be obtained at present.

Further, in the printing industry, there is a strong demand for efficient work, and it is required to shorten the processing time.
From the viewpoint of environmental protection, reduction of waste liquid has been strongly demanded, and the present system is not satisfactory in these points.

Further, in the plate making process, plate making is rarely done directly from the outputted scanner film, and a plurality of patterns, character images, etc. are printed and composited on the return film in the plate making process to obtain a final plate for printing. It is usually an image. At this time, there is a problem in that a halftone dot is thickened in the reversal light-sensitive material containing the hydrazine derivative, and faithful reproduction cannot be performed. Further, with respect to the nuisance character properties (removing characters in a negative image in a background color solid or halftone plate) required for printing light-sensitive materials, the hydrazine light-sensitive materials described above cannot provide satisfactory performance. Is.

Further, in obtaining a final halftone image or line image, the photosensitive material for plate making is further subjected to a process called a reduction process in order to satisfy the delicate tone reproduction of the image and the artistic expression. Often, the image is partially or wholly finely modified. Therefore, whether or not the photosensitive material for plate-making has a reducing property is one of the extremely important performances.

In the printing plate making process, a method is often used in which the density (tone) of the original image is expressed by the size of the area of minute dots, that is, a halftone dot image.

To reduce the strength of a plate-making photosensitive material on which a halftone dot image or a line image has been formed through exposure and development, a method of bleaching metallic silver forming the halftone dot or line image with an oxidizing agent is used. Etc. are known.

[0008] For example, The Theory of
The Photographic Process (Mees, The Theory
of the Photographic Process) p.738-p.739 (1954 M
(published by acmillan), a reducing liquid using a reducing component such as permanganate, ferric salt, cerium salt, red blood salt, dichromate, and persulfate is described. .

In the end, the reduction processing generally means that the larger the amount of silver per unit area that oxidizes and dissolves the silver image, the wider the range in which the image can be corrected by the reduction processing. That is,
When a halftone dot image is subjected to a reduction process, if the halftone dot area is reduced by the reduction process, the blackening density per halftone dot generally decreases in parallel with the reduction process. At the time of decrease, the smaller the decrease in blackening density per dot area, the wider the range that can be corrected by reduction.

In other words, the measure of the correctable range of the halftone dot image is expressed by indicating how much the halftone dot area can be reduced by keeping the blackening density per halftone dot above a certain value. You can

According to the present invention, when the blackening density of the halftone dots is reduced to the minimum value required in the plate making process by the reduction treatment, how much the halftone dot area is relative to the halftone dot area before the treatment. The amount of reduction will be indicated by the term "reduction width".

In the light-sensitive material containing the above-mentioned hydrazine derivative, this reducing ability is very poor.

[0013]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a reversible silver halide photographic light-sensitive material capable of rapid processing, low replenishment, controlled black spot increase, and faithful reproduction with little overweight. To provide. Another object of the present invention is to provide a silver halide photographic light-sensitive material excellent in bleeding character and reducing property.

[0014]

A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support is subjected to post-exposure development processing using an automatic developing device. In this method, at least one hydrazine derivative and two types of silver halide grains having different sensitivities are contained in the hydrophilic colloid layer, and at least one silver halide composition of the silver halide grains is A.
It can be achieved by processing a silver halide photographic light-sensitive material having gCl ≧ 90 mol% with a developer having a pH of 9.5 to 11.0 and containing substantially no dihydroxybenzenes.

The difference in sensitivity between the two types of silver halide grains can be determined by coating, exposing and developing the grains individually under the same conditions as in the system actually used. The difference in sensitivity between the two types of silver halide grains is preferably 5% or more, more preferably 12% or more. Further, two kinds of grains having different sensitivities require that at least one composition of the two kinds of silver halide grains is AgCl ≧ 90 mol%, and further two kinds of grains can be added at an arbitrary ratio. But A
It is preferable that 50% or more of the particles have gCl ≧ 90 mol%. Further, any method may be used as a method for giving a difference in sensitivity, but a method based on a change in silver halide composition, chemical sensitization, a change in grain size, or a difference in grain shape is preferable. Regarding the method by chemical sensitization, sulfur sensitization, reduction sensitization and noble metal sensitization are preferable, and any of these may be used alone or in combination.

The preferred chemical sensitization method is sulfur sensitization,
As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and the like can be used in addition to the sulfur compound contained in gelatin.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained.

Examples of reduction sensitizers include stannous salts, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used.

There are no particular restrictions on the grain shape, but there is no limitation on the shape of the silver halide grains, and any of tabular, spherical, cubic, tetradecahedral, octahedral and other shapes may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable.

Among the methods based on the change in silver halide composition, chemical sensitization, change in grain size, and difference in grain shape, the method based on change in silver halide grain size is particularly preferable.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles which can be approximated to a sphere. If the particle is a cube

[0022]

[Equation 1]

Let be the particle size. It is determined by an algebraic average or a geometric average based on the average particle projected area. For details on how to determine the average particle size, see (Mies, James: The Theory of the Photographic Process “CE
Mees & T.H. James: The theory of the photographic
process ”), 3rd edition, pp. 36-43 (1966 (published by McMillan“ Mcmillan ”)).

Next, the hydrazine derivative used in the present invention will be described.

In the present invention, the hydrazine derivative may be contained in at least one of the hydrophilic colloid layers existing on the side containing the silver halide emulsion layer with respect to the support, and two or more different layers. May be contained in.
Particularly preferably, it may be contained in at least one of the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula [H].

[0027]

Embedded image

The general formula [H] will be described in detail below.

In the formula, the aliphatic group represented by A is preferably one having 1 to 30 carbon atoms, particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group,
Examples thereof include a benzyl group and the like, which further include suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfoxy group,
Sulfonamide group, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [H] is preferably a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, a pyrrolidine ring, Examples thereof include an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

Further, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group has 8 carbon atoms.
Relatively inert to the above photographic properties, such as alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,
Examples thereof include a substituted phenyl group, a substituted phenoxy group and an alkylphenoxy group.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A 64-90439.

B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), an aryloxycarbonyl Groups (eg phenoxycarbonyl etc.), sulfamoyl groups (eg dimethylsulfamoyl etc.), sulfinamoyl groups (eg methylsulfur) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group or a heterocyclic group (eg pyridine ring, pyridinium ring etc.) Represent

B in the general formula [H] represents A ₂ and the nitrogen atom to which they are attached.

[0038]

Embedded image

May be formed.

R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

Among the hydrazine compounds used in the present invention, particularly preferred are compounds represented by the following general formula [Ha].

[0044]

Embedded image

In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ represents

[0046]

[Chemical 4]

Represents

R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Alternatively, it represents a heterocyclic oxy group, and R ₆ and R ₇ may form a ring together with an N atom. R ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ represent the same meanings groups as A ₁ and A ₂ in formula (H).

The general formula [Ha] will be described in more detail.

The aryl group represented by R ₄ is preferably a monocyclic ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₄ is preferably a monocyclic or condensed 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, such as pyridine. Examples thereof include a ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₄ is a substituted or unsubstituted aryl group. Examples of the substituent include those having the same meaning as the substituent of A in the general formula [H].
When the contrast is increased with a developing solution of 1.2 or less, it is preferable to have at least one sulfamide group.

[0053] A ₁ and A _2, A ₁ and A ₂ of the formula H
And a hydrogen atom are the most preferable.

R ₅ is

[0055]

Embedded image

Wherein R ₆ and R ₇ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.),
Alkenyl groups (allyl, butenyl, etc.), alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl) Nyl, quinolidinyl, N, N-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy, Ethoxy, etc.), alkenyloxy group (allyloxy, etc.), alkynyloxy group (propargyloxy, etc.), aryloxy group (phenoxy, etc.), or heterocyclic oxy group (pyridyloxy, etc.), and R ₆ and R ₇ are nitrogen atoms. A ring (piperidine, morpholine, etc.) may be formed together therewith. R ₈ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocycle Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compounds represented by the general formulas [H] and [Ha] are shown below. However, the present invention is not limited to these.

[0058]

[Chemical 6]

[0059]

[Chemical 7]

[0060]

Embedded image

[0061]

[Chemical 9]

[0062]

[Chemical 10]

[0063]

[Chemical 11]

[0064]

[Chemical 12]

[0065]

[Chemical 13]

The method of synthesizing the compound represented by the general formula [H] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European patent 253,665
No. 333,435, etc. can be referred to.

The amount of the compound represented by the general formula [H] used in the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, when the compound represented by the general formula [H] is contained in the photographic light-sensitive material, it is selected from among the silver halide emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer. Of at least one of the above.

Next, examples of the nucleation accelerator used in the present invention include those represented by the following general formula [Na] or [Nb].

[0070]

Embedded image

In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. A ring can be formed by R ₁ , R ₂ and R ₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is more preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific compounds include those shown below.

[0073]

[Chemical 15]

[0074]

Embedded image

[0075]

[Chemical 17]

[0076]

Embedded image

In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or heteroaromatic ring. R represents an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group or hydrogen atom. Further, Ar and R may be bonded to each other to form a ring. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have a preferable diffusion resistant group, the molecular weight is preferably 120 or more, particularly preferably 300 or more.

Specific compounds include those shown below.

[0079]

[Chemical 19]

[0080]

Embedded image

In the light-sensitive material of the present invention, at least one conductive layer is preferably provided on the support. As a typical method of forming the conductive layer, there are a method of forming using a water-soluble conductive polymer, a hydrophobic polymer and a curing agent, and a method of forming using a metal oxide. For these methods, see, for example, JP-A-3-265842, page 5, lower right column, line 1-
The method described on page 15, upper left column, line 6 can be used.

Various techniques and additives known in the art can be used in the silver halide emulsion used in the present invention. For example, in the silver halide emulsion and backing layer used in the present invention, various toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents, development inhibitors, ultraviolet absorbers,
Irradiation inhibitor dyes, heavy metals, matting agents and the like can be further incorporated by various methods. Further, a polymer latex can be contained in the silver halide emulsion and the backing layer used in the present invention.

These additives are described in more detail in Research Disclosure, Vol. 176, No. 7643 (December, 1978) and Vol. 187, No. 8716 (November, 1979). It is summarized below.

Additive type RD / 7643 RD / 8716 1. Sensitivity enhancer Same as above 2. Spectral sensitizer, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 3. Whitening agent Page 24 4. Antifoggants and stabilizers pages 24 to 25, page 649, right column 5. Light absorbers, filter dyes, pages 25 to 26, page 649, right column to UV absorbers, page 650, left column 6. Anti-staining agent Page 25 Right column Page 650 Left-right column 7. Dye image stabilizer page 25 8. Hardener 26 pages 651 left column 9. Binder page 26 Same as above 10. Plasticizer, lubricant Page 27 Page 650 Right column 11. Coating aid, surface active agent, pages 26 to 27, same as above 12. Antistatic agent page 27 Same as above As a support that can be used in the light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin , Glass, metal and the like. These supports are subjected to a surface treatment if necessary.

Next, the developing solution will be described.

The developer containing substantially no dihydroxybenzenes is a developer containing a compound represented by the general formula [A] as a developing agent or a developing solution containing a transition metal salt as a developing agent. The developing solution containing the compound represented by formula [A] as a developing agent will be described.

[0087]

[Chemical 21]

In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ And R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-.

In the compound represented by the general formula [A], a compound represented by the following general formula [Aa] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0090]

[Chemical formula 22]

In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Amide group, sulfonamide group, Y ₁ represents O or S, Y ₂ represents O, S or NR
Represents ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The alkyl group in the above general formula [A] or general formula [Aa] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Frequently, the substitutable group includes a hydroxy group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula [A] or the general formula [Aa] according to the present invention are shown below.
The present invention is not limited to these.

[0094]

[Chemical formula 23]

[0095]

[Chemical formula 24]

These compounds are typically ascorbic acid or erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

Examples of the auxiliary developing agent exhibiting superadditivity with the compound represented by the general formula [A] according to the present invention include 3-pyrazolidone derivatives and p-aminophenol derivatives. These compounds are conventionally well known as auxiliary developers. Specific compound examples are shown below, but the invention is not limited thereto.

1-Phenyl-3-pyrazolidone 1-phenyl-4,4'-dimethyl-3-pyrazolidone 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1-phenyl-5-methyl-3- Pyrazolidone 1-p-aminophenyl-4,4'-dimethyl-3-pyrazolidone 1-p-tolyl-4,4'-dimethyl-3-pyrazolidone 1-p-tolyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone N-methyl-p-aminophenol N- (β-hydroxyethyl) -p-aminophenol N- (4-hydroxyphenyl) glycine 2-methyl-p-aminophenol p-benzylaminophenol Development according to the present invention The liquid is characterized by containing substantially no dihydroxybenzene-based developer. The dihydroxybenzene-based developer referred to here is the following general formula V-1.
Through V-3.

[0099]

[Chemical 25]

In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a halogen atom or a sulfo group.

Specific compounds include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
Among them are 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone, but the most commonly used one is hydroquinone.

In the present invention, these dihydroxybenzenes are not substantially contained, and the dihydroxybenzenes are not contained at all or are contained in a trace amount such that the developing effect is not exhibited. In the above, those not containing at all are preferable.

The black-and-white silver halide photographic light-sensitive material according to the present invention is processed by using an automatic developing machine, and at that time, it is processed while replenishing a constant amount of developing solution proportional to the area of the light-sensitive material. The development replenishment amount is 1 in order to reduce the amount of waste liquid.
It is 250 ml or less per m ² . It is preferably 75 ml or more and 200 ml or less per 1 m ² . 7 per 1 m ²
If the developer replenishment amount is less than 5 ml, satisfactory photographic performance cannot be obtained due to desensitization and softening.

Next, a developing solution containing a transition metal salt as a developing agent will be described.

The present invention will be specifically described below.

Examples of the developing agent comprising a transition metal complex salt according to the present invention include Ti, V, Cr, Mn, Fe, Co, Ni and C.
a complex salt of a transition metal such as u, preferably Ti, V, C
It is a complex salt of r and Fe. These may be in a form having a reducing power to be used as a developing solution, for example, Ti ³⁺ ,
It is known that they take the form of complex salts such as V ²⁺ , Cr ²⁺ and Fe ²⁺ . Specific ligands include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, and phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid and salts thereof. To be Among these, transition metal complex salts having a ligand such as EDTA and DTPA are particularly preferably used.

Specific examples of preferable ligands are shown below, but the ligands are not limited to these.

(1) Ethylenediaminetetraacetic acid (EDTA) (2) Diethylenetriaminepentaacetic acid (DTPA) (3) Triethylenetetraminehexaacetic acid (TTHA) (4) Hydroxyethylethylenediaminetriacetic acid (HEDTA) (5) Nitrilotriacetic acid ( NTA) (6) 1,2-diaminocyclohexanetetraacetic acid (7) 1,3-diamino-2-propanoltetraacetic acid (8) hexametapolyphosphoric acid (9) tetrapolyphosphoric acid -41899 Publication No.
Compounds described on pages 128 (2) to 129 (3).

The complex according to the present invention can be formed in a developing solution by adding a transition metal salt and a ligand compound. The content of the compound according to the present invention in the developer is preferably 1 to 100 g per liter of the developer.

In the present invention, the developing agent comprising the transition metal complex salt according to the present invention and the developing agents of 3-pyrazolidones and aminophenols can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are usually preferably used in an amount of 0.01 to 1.0 mol per liter of the developing solution.

In the present invention, the developing waste liquid is regenerated by energizing it. Specifically, a cathode is put in the developing waste solution and an anode is put in the electrolyte solution so that the developing waste solution tank and the electrolyte solution tank are in contact with each other through an anion exchange membrane, and both electrodes are energized for regeneration.
It is also possible to process the light-sensitive material while energizing.

The cathode used in the present invention may be an electric conductor or a semiconductor. For example, stainless steel or the like is preferably used, and stainless wool is particularly preferable in order to increase the surface area and increase the efficiency. An insoluble electric conductor is used as the anode. For example, carbon, gold, platinum, titanium and the like are preferable, and platinum plating of titanium is particularly preferable.
As the anion exchange membrane used in the present invention, a commercially available one can be used.

The regenerated developer is returned to the developing tank of the automatic developing machine again and used again for development. At that time, various additives added to the developer, for example, a pH buffer agent, a preservative, which can be added to the developer as described above,
A development inhibitor, a silver sludge inhibitor, etc. can be additionally added. Further, as another embodiment, there is a method of processing the light-sensitive material of the present invention while energizing a developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added.

The energization treatment according to the present invention means that a part of the treatment tank is substantially partitioned by an anion exchange membrane, a cathode and an anode are provided through the anion exchange membrane to energize, and there is no need to pass through the anion exchange membrane. In this treatment method, a substance or a necessary substance is moved to a desired side, and a liquid component is oxidized or reduced by a reaction on an electrode surface. Furthermore, the phenomenon that is carried out by energization is called the electrochemical reaction, which is the reaction between the electrode and the chemical substance in the solution. In this electrochemical reaction, electricity is externally applied to the electrode to promote the reaction (electrolysis). On the other hand, there is one in which electricity can be taken out from the electrode (battery) by the reaction of chemical substances in the solution.

The energization in the present invention means that the above-mentioned development and the mass transfer of the ionic substance are carried out between the diaphragm provided between the electrodes. Therefore, energization = electrolysis + ion selective transfer by diaphragm, that is, a means for simultaneously carrying out mass transfer of electrochemical reaction and chemical engineering.

The number of ions moving through the anion exchange membrane of the ionic compound and the electrode reaction is proportional to the amount of current flowing through the electrode surface according to Faraday's law. A voltage is applied in order to generate this current, but the voltage must be proper, and is usually 0.1 to 10V, preferably 0.3 to 5V. If the voltage is lower than this value, the current does not flow, and if the voltage is higher than this value, an unnecessary electrode reaction occurs and the reaction efficiency (current efficiency) with respect to the target is lowered.

Therefore, if a constant current power supply is used, the energization process can be properly controlled only by the time control, but in the case of a power failure or when the power supply is temporarily cut off, the current will not be supplied as set, so this method is used. Is not suitable, and since such a constant current power source is expensive, it is preferable to use a power source that is as inexpensive as possible (battery or secondary battery).

When a battery or a secondary battery is used as the power source, the current drops due to the voltage drop, making it difficult to manage the current. In this case, it is necessary to energize so that the current value × time becomes constant with respect to the predetermined processing amount of the photosensitive material. To measure current value x time, use an integrating ammeter (ammeter)
May be used to measure the integrated amount of the current value. As the ammeter, when a constant current power supply is used, various commercially available ammeters can be used, and it is sufficient to integrate only the time when the ammeter flows. When it is not a constant current power source, a commercially available coulomb meter or an integrating ammeter can be used.

For example, the developer can be properly regenerated by energizing the developer so that an electric quantity of a predetermined coulomb is applied to the developer for the processing of one film for photographing. In an automatic developing apparatus that has many processing tanks to be energized, the cost of the power supply can be reduced if the energization is not performed simultaneously and the time is staggered. Further, when the anion exchange membrane is continuously used, the membrane resistance may increase due to clogging or the like. In this case, if an attempt is made to flow a constant current value, the applied voltage may rise, which may be undesirable. In order to prevent such a case, it is necessary to keep the film resistance below a certain level. On the contrary, in this case, when a constant voltage is applied, the current value gradually decreases. Also at this time, energization processing becomes possible by controlling so that current × time for a predetermined processing amount of the photosensitive material becomes constant.

As described above, the energization process may be controlled by the amount of current according to Faraday's law, but in some cases, the change in the bulk potential of the developer is detected, and this data and the amount of current are combined to obtain the amount of energization. May be determined. The control means at this time may make a fuzzy decision. To measure the redox bulk potential of the developer, the redox potential measuring instrument described in JP-A-60-195544 and 60-195545 can be used. Moreover, this potential may be detected and controlled by the control method described in the publication.

For example, in the case of a developing solution, energization is controlled so that the oxidation-reduction potential is within a predetermined range, and when the oxidation-reduction potential exceeds a set upper limit value, the energization is interrupted to interrupt the oxidation of the developing solution. . The redox potential of the developing solution decreases as the photosensitive material is processed during interruption of energization, but when the redox potential falls below the lower limit value, energization is started to oxidize the developing solution and raise the potential.

In the present invention, it is preferable to energize during the processing, and by doing so, it becomes possible to maintain the developing activity during the processing. Then, when the processing is completed and, for example, a signal indicating the completion of the processing of the photosensitive material is received, the energization may be terminated.

The cathode used in the present invention may be any electric conductor or semiconductor that can withstand long-term use, but stainless steel is particularly preferable. The anode may be made of an insoluble material and an electric conductor, and specific examples thereof include carbon (graphite), lead dioxide, platinum, gold, titanium and copper, and stainless steel may be used depending on the case. The shape of both electrodes is preferably a mesh-like plate shape or a plate shape with protrusions which is easy to install in the tank. The size may be appropriately selected depending on the tank capacity.

As the anion exchange membrane used in the present invention, any one can be used as long as it selectively permeates anions, and a commercially available one can be used as it is. In this case, the anion exchange membrane to be used can be selected according to the valence of the anion that is preferably moved through the anion exchange membrane. For example, for the purpose of permeating silver halide ions such as Br ⁻ accumulated in the developer, an anion exchange membrane selectively permeating only monovalent anions may be used.

The electrolyte solution used in the present invention is not limited, but the electrolyte may be NaCl, KCl, LiCl, NaBr, KBr, KI.
Such as halide, Na ₂ SO ₄ , K ₂ SO _4, etc. sulfate, KNO ₃ , N
It is preferable to use nitrates such as aNO ₃ and NH ₄ NO ₃ , carbonates such as Na ₂ CO ₃ and K ₂ CO ₃ . At this time, the concentration of the electrolyte in the electrolyte solution is 0.01 to 30%, preferably 0.01 to 20%.
%And it is sufficient. In addition, a diluting solution of the fixing solution can be used.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844, JP-A-4-26838,
No. 4-362942, No. 1-319031 and the like, and more preferably, compounds represented by the following general formula [Pa] or [Pb] can be used.

[0127]

[Chemical formula 26]

In the formula, R ₁₁ and R ₁₂ are hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, mercapto group, carboxy group, sulfo group, phosphono group, amino group, nitro group, cyano group, halogen atom. , An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkoxy group and the like. R ₁₁ and R ₁₂ may be linked to form a ring structure.

In the general formula [Pb], M ₁ and M ₂ are hydrogen atoms,
It represents Na, K or NH ₄ , and X ₁ represents a hydrogen atom or a halogen atom.

Typical examples of the compounds represented by the general formulas [Pa] and [Pb] are shown below.

[0131]

[Chemical 27]

[0132]

[Chemical 28]

[0133]

[Chemical 29]

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

In the developer used in the present invention, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, Alkanol amines etc.), solubilizers (eg polyethylene glycols, their esters, alkanol amines etc.), sensitizers (eg polyoxyethylene-containing nonionic surfactants, quaternary ammonium compounds etc.), surfactants , Antifoaming agents, antifoggants (eg, halides such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediamine) Tetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate Etc.), development accelerators (eg, compounds described in US Pat. No. 2,304,025, JP-B-47-45541), hardeners (eg glutaraldehyde or bisulfite adducts thereof), or defoaming agents. It can be added. The pH of the developer used in the present invention is 9.5 to 11.0.
Is preferably adjusted to

The compounds of the present invention, as a special form of development processing, include a developing agent in a light-sensitive material, for example, an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Such development processing is often used as one of the rapid processing methods for the light-sensitive material in combination with the silver salt stabilization processing with thiocyanate, and can be applied to such processing solutions. In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing solution used in the present invention, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8.
~ 5.8. As a fixing agent, sodium thiosulfate,
Thiosulfates such as potassium thiosulfate and ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, it is possible to use an organic sulfur compound capable of forming a soluble stable silver complex salt, which is known as a fixing agent.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, or the like can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid), pH adjusters (eg, sulfuric acid), and chelating agents capable of softening water. And the like.

The developer used in the present invention may be a mixture of fixed components or an organic aqueous solution containing glycol or amine,
It may be a semi-kneaded viscous liquid having a high viscosity. Further, it may be diluted before use, or may be used as it is.

In the development processing in the present invention, the development temperature can be set in the usual temperature range of 20 to 30 ° C. or can be set in the high temperature processing range of 30 to 40 ° C.

In the present invention, the line speed is 1500 mm when processed by using an automatic processor in order to shorten the developing time.
/ Minute or more, and the total processing time (Dry to Dry) until the film front end is inserted into the automatic processor and comes out of the drying zone is preferably 20 to 120 seconds. The total processing time referred to here includes the total process time required for processing the light-sensitive material, and specifically, necessary for the processing.
For example, it is a time including all the time of steps such as development, fixing, bleaching, washing, stabilizing treatment, and drying, that is, Dry to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 20 to 45 seconds.

[0143]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Latex Lx-A) 1.0 kg of gelatin was added to 60 liters of water.
A mixture of 0.01 kg of sodium dodecylbenzene sulfonate and 0.05 kg of ammonium persulfate was stirred at a liquid temperature of 60 ° C. under a nitrogen atmosphere while a mixture of styrene 3.0 kg, methyl methacrylate 3.0 kg and ethyl acrylate 3.2 kg and 2-
Sodium acrylamido-2-methylpropanesulfonate (0.8 kg) was added over 1 hour, and the mixture was stirred for 1.5 hours and then steam distilled for 1 hour to remove residual monomers. After cooling to room temperature, pH was adjusted with ammonia. Adjusted to 6.0. The obtained latex liquid was made up to 75 kg with water. As described above, a monodisperse latex having an average particle size of 0.1 μm was obtained.

(Emulsion preparation) A silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × rhodium hexachloride complex.
The solution added to 10 ^-5 mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate, and then desalted according to a conventional method to give an odor with a particle size of 0.10 μm, 0.13 μm, 0.16 μm, 0.20 μm. Four cubic and monodisperse silver chlorobromide emulsions containing 1 mol% of silver halide were obtained.

These emulsions were sulfur sensitized in the usual way and 6-methyl-4-hydroxy-1,3,3a, 7 tetrazaindene was added as a stabilizer. The four emulsions were mixed as shown in Table 1 to prepare emulsions. Further, the following compounds were added, and then the following additives were added to prepare an emulsion coating solution.

Hydrazine derivative H45 1 × 10 ^-4 mol / mol Ag p-nonylphenol / ethylene oxide 35 mol adduct 100 mg / m ² (C ₅ H ₁₁ N-CH ₂ CH ₂ OCH ₂ CH ₂ ) ₂ S 1 × 10 ^-3 mol / molAg Silver sludge inhibitor (VIII-1) 1.7mg / m ² Emulsion coating liquid Potassium bromide 5mg / m ² 2,5-Dimethyl-4-isothiazolin-3-one 1mg / m ² 0.5N sodium hydroxide aqueous solution Adjusted to pH 5.6 Saponin (20%) 0.5cc / m ² Sodium dodecylbenzenesulfonate 20mg / m ² 5-Methylbenzotriazole 10mg / m ² 1-Phenyl-5-mercaptotetrazole 2mg / m ² 2,5-di (Carboxymethylthio) -1,3,4-thiadiazole 10 mg / m ² 3,3,3 ', 3'-tetramethyl-5,6,5', 6'-tetrahydroxy-1,1'-spirobiindane 6 mg / m ² latex Lx-A 0.5 g / m ² Styrene-maleic acid copolymer (thickener) 90 mg / m ^{2 When} the emulsion was coated, the amount of gelatin was 1.2 g / m ^2. It was adjusted to be m ² .

Then, an emulsion protective layer coating solution, a backing layer coating solution, and a backing protective layer coating solution were prepared with the following compositions.

Emulsion protective layer coating solution Gelatin 1.1 g / m ² compound (b) 40 mg / m ² compound (d) 100 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² 〃 (3 μm) 10 mg / m ² gall Acid allyl ester 100 mg / m ² Compound (a) 1 mg / m ² Citric acid Adjusted to pH 5.8 Latex Lx-A 0.5 g / m ² Styrene-maleic acid copolymer (thickener) 50 mg / m ² Formaldehyde (cured Agent) 10 mg / m ² backing layer coating solution 1.0 g / m ² compound (c) 80 mg / m ² compound (d) 15 mg / m ² compound (e) 150 mg / m ² calcium chloride 0.3 mg / m ² saponin (20 % Aqueous solution) 0.6cc / m ² citric acid adjusted to pH 5.5 Latex (m) 300mg / m ² 5-methylbenzotriazole 10mg / m ² 5-nitroindazole 20mg / m ² polyethylene glycol (molecular weight 1540) 10mg / m ² styrene - maleic acid copolymer (thickener) 45 mg / m ² Guriokiza (Curing agent) 4 mg / m ² Compound (n) 80mg / m ² Backing protective layer coating liquid Gelatin 1.18 g / m ² Compound (a) (1% aqueous solution) 2 ml / m ² Compound (c) 20mg / m ² Compound ( d) 4mg / m ² compound (e) 50mg / m ² spherical polymethylmethacrylate (4μm) 25mg / m ² sodium chloride 70 mg / m ² compound (a) 1mg / m ² glyoxal 22 mg / m ² bisvinylsulfonylmethylether ( Curing agent) 5 mg / m ²

[0150]

Embedded image

[0151]

[Chemical 31]

[0152]

Embedded image

Each coating solution prepared as described above was coated on the emulsion side with a thickness of 10 by undercoating as shown in JP-A-59-19941.
After applying corona discharge at 10 W / m ² · min to the backing surface side of 0 μm polyethylene terephthalate base, use the roll-fit coating pan and air knife with the following composition so that the coating amount will be 10 cc / m ^2. Applied and dried.

Drying was performed at 90 ° C., and overall heat transfer coefficient was 25 kcal (m ²
・ Hr ・ ° C) parallel flow drying condition for 30 seconds, then 140 ° C ・
It took 90 seconds. The thickness of the layer after drying was 1 μm, and the surface specific resistance of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0155]

[Chemical 33]

Ammonium sulfate 0.5 g / liter Polyethylene oxide compound (average molecular weight 600) 6 g / liter Curing agent 12 g / liter

[0157]

Embedded image

On this base, first, from the side closer to the support as the emulsion surface side, the emulsion layer and the emulsion protective layer were sequentially coated in layers by the slide hopper system while maintaining the temperature at 35 ° C. while adding a hardener solution, and then cold air was applied. After passing through the set zone (5 ° C.), a backing layer and a backing protective layer were coated on the side opposite to the emulsion surface with a slide hopper while adding a hardening agent, and set with cold air (5 ° C.). The coating liquid exhibited sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the backing surface side, it was conveyed in a state in which there was no contact with the roller or the like until winding up. The coating speed at this time was 120 m / min.

(Drying conditions) After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of water / gelatin reached 800%, and then 800 to 20.
Dry 0% with 35 ° C (30%) dry air, apply the air as it is, and 30 seconds after the surface temperature reaches 34 ° C (it is considered that the drying is completed), use 48 ° C / 2% air. It was dried for 1 minute. At this time, the drying time is from start of drying to water / gelatin ratio of 800%.
0 second, 35% from 800% to 200%, 5 seconds from 200% to the end of drying.

This light-sensitive material was wound at 23 ° C. and 40%, then cut under the same environment, and placed in a barrier bag which was conditioned for 3 hours at 40 ° C.
After humidity was adjusted to 10% for 8 hours, it was sealed together with cardboard which had been adjusted to humidity at 23 ° C. and 40% for 2 hours.

The silver coating amount of the light-sensitive material produced as described above was 3.5 g / m ² .

The sample prepared as described above was output with a scanner SG-747 (manufactured by Dainippon Screen Co., Ltd.) and a high-definition (600 lines / inch) halftone dot image was used as an original for the printer P-627GM (Dainippon Contact-exposure using a screen (manufactured by K.K.), rapid processing automatic processor GR-26S manufactured by Konica.
R was developed according to the following processing conditions. (45 sec processing) (developing condition) Step Temperature Time Replenishment rate development 38 ° C. 12 sec 160 cc / m ² fixing 35 ° C. 10 sec 190 cc / m ² washing room temperature 10 seconds Drying 50 ° C. 13 seconds developer formulations formula (A) Compound A-17 0.2 mol / l sodium sulfite 0.14 mol / l dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone) 2.3 g / l potassium carbonate 0.8 mol / l 5-methylbenzotriazole Adjust the pH to 10.3 with 0.25 g / l potassium bromide 7.5 g / l Pa-16 200 mg / l KOH.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5 W / V% aqueous solution) 240 cc Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium oxalate dihydrate 2.0 g (Composition B) Pure Water (ion-exchanged water) 17cc Sulfuric acid (50W / v% aqueous solution) 4.7g Aluminum sulphate (Al2o3 equivalent content of 8.1W / V% aqueous solution) 26.5g When used, 500cc water dissolves composition A and composition B in this order Finished to 1 liter. The pH was adjusted to 4.8 with acetic acid. At this time, the appropriate exposure amount was the exposure amount at which the density of the inverted (blackened) image portion with respect to the non-image portion of the document was 4.6, and the blackened area of the halftone image at this exposure amount was measured. Concentration is PD
A-65 densitometer (manufactured by Konica Corporation), halftone dot area is X-Rite361T
Was measured with ortho light. Manuscript dot area is 43.8%
Met.

The black spots in the unexposed area were also evaluated using a magnifying glass of 40 times. The highest rank is "5" when black spots are not generated at all, and the rank is gradually lowered to "4", "3", "2", "1" according to the degree of occurrence of black spots. It shall be evaluated. Rank "1" and "2"
The black spots are also levels that are not practically preferable.

The reduction treatment was performed with the following reduction liquid.

20% aqueous cerium sulfate solution.

In the evaluation of the results, the reduction characteristics were evaluated based on the halftone dot concentration and how much the halftone% decreased when 4.0 or more before reduction decreased to 3.0. The larger the net percentage, the wider the reduction range and the better.

The results are also shown in Table 1.

[0169]

[Table 1]

From Table 1, it can be seen that the present invention suppresses black spots, has a small halftone dot size, has good faithful reproducibility, and is excellent in reducing power.

Example 2 In the emulsion preparation of Example 1, the prepared grain size was 0.13 μm.
Using the emulsion of m, the amount of sulfur was changed in the same manner as in Example 1 to perform sulfur sensitization to obtain three types of emulsions (1), (2) and (3) having different sensitivities. Like (1) ~
(3) was mixed, and an emulsion coating solution was prepared and coated in the same manner as in Example 1. The sensitivity of emulsions (1), (2) and (3) was (1)>(2)> (3).

Development processing was performed as follows.

As the automatic processor, the one described below was used. The Konica GR-27 was improved as shown in FIG.
That is, an energization regeneration tank 4 connected by a pump 2 and a hose 3 is provided in the developing tank 1 of an automatic developing machine equipped with a developing tank 1, a fixing tank, a washing tank, a drying zone and the like so as to be circulated. The energization regeneration tank 4 is divided at the center by an anion exchange membrane 5,
The developer 6 is put into the side which is connected to the developing tank 1 by the pump 2 and the hose 3 so as to be able to circulate, and the electrolyte solution 7 is put into the other side. A cathode is installed on the side of the developer 6 and an anode is installed on the side of the electrolyte solution 7 so that electricity can be supplied.

Anion Exchange Membrane: Tokuyama Soda AM-3 Cathode: Stainless SUS316, 2mm thickness, 20cm × 13cm Anode: Kureha Chemical Creca Sheet, 3mm thickness, 20cm × 13cm Electrolyte solution: 0.3% Na ₂ CO ₃ solution, GP060-20 DC PowerSupply Energization condition: 2V, 1A (current density 0.4A / dm ² ) The rack and line speed of each processing tank were also improved so that the following processing conditions could be achieved.

Development processing conditions Process temperature Time Complement amount Current image 38 ° C. 12 seconds 160 cc / m ² Settlement 35 ° C. 10 seconds 160 cc / m ² Water wash Normal temperature 10 seconds Dry 50 ° C. 13 seconds Start The developer and fixer in the tank of the automatic processor were as shown below.

<Developer> Pure water (ion exchanged water) 600 ml EDTA / 2Na 60 g Citric acid 40 g KBr 2 g TiCl ₃ 30 g NaOH 30 g

[0177]

Embedded image

Pure water (ion-exchanged water) was added to make 1 liter.

PH
6.0 <Fixer> Ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Pure water (ion exchanged water) 20 ml Sodium sulfite 20 g Boric acid 10 g Tartaric acid 3 g Acetic acid (90% W / V) 0.5 mol Aluminum sulfate (Al ₂ Aqueous solution having an O ₃ converted content of 8.1% W / W) 25 ml Sulfuric acid (50% W / W) Amount to adjust pH to 4.8 Pure water (ion exchanged water) was added to make 1 liter.

[0180]

[Table 2]

From Table 2, it can be seen that black spots are suppressed in the present invention, the halftone dots are small, the faithful reproducibility is good, and the reducing ability is excellent.

[Brief description of drawings]

FIG. 1 is a schematic view of an automatic processor according to the present invention.

[Explanation of symbols]

 1 developing tank 2 pump 3 hose 4 energization regeneration tank 5 anion exchange membrane 6 developing solution 7 electrolyte solution

Claims (4)

[Claims] 1. A method of developing a silver halide light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer on a support after exposure using an automatic developing apparatus, Halogenated having at least one hydrazine derivative and two or more kinds of silver halide grains having different sensitivities in the hydrophilic colloid layer, and at least one silver halide composition of the silver halide grains is AgCl ≧ 90 mol% Silver photographic light-sensitive material, pH 9.5-1
A method of developing a silver halide photographic light-sensitive material, which comprises processing with a developing solution containing substantially no dihydroxybenzenes at 1.0. 2. The silver halide grain having the highest sensitivity and the silver halide grain having the lowest sensitivity among two or more kinds of silver halide grains have a sensitivity difference of 12% or more. A method for developing and processing a silver halide photographic light-sensitive material as described above. 3. The developing solution is 200 m per 1 m ^{2 of the} light-sensitive material.
The method of developing a silver halide photographic light-sensitive material according to claim 1 or 2, wherein the replenishment is performed in an amount of 1 or less. 4. The line speed of the automatic developing device is 150.
4. The development processing method for a silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the processing time is 0 mm / min or more and the total processing time from the start of penetration into the developing solution to the drying is within 45 seconds. .