JPH0697335B2 - Processing method of silver halide color photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention contains a compound that releases a fogging agent or a precursor thereof or a development accelerator or a precursor thereof imagewise in correspondence with the amount of developed silver during development. The present invention relates to a method for processing a silver halide color light-sensitive material, and more specifically to a processing method in which bleaching or bleach-fixing processing is accelerated.

BACKGROUND OF THE INVENTION In recent years, the demand for high sensitivity of silver halide color light-sensitive materials has been extremely strong, and couplers that release development accelerators and fogging agents in an imagewise manner have been proposed.

A silver halide color photographic light-sensitive material containing a compound (hereinafter referred to as an FR compound) which releases an image fogging agent or its precursor or a development accelerator or its precursor imagewise in accordance with the amount of developed silver during development. Sensitivity can be increased.

However, when a light-sensitive material containing an FR compound is developed, the released fogging agent or development accelerator causes bleaching inhibition when incorporated in a subsequent bleaching bath or bleach-fixing bath.

In a general processing method for continuously processing a large amount of light-sensitive materials, this bleaching inhibition results in defective desilvering, resulting in a decrease in color reproducibility of color photographic images and a decrease in storage stability of dye images. It is a serious problem and improvement is desired.

OBJECT OF THE INVENTION Accordingly, an object of the present invention is to provide a processing method of a silver halide color light-sensitive material having high sensitivity and improved bleaching property or bleach-fixing property.

[Constitution of the Invention] The above object of the present invention is to provide a silver halide color sensitizer containing a compound that releases a fogging agent or a precursor thereof or a development accelerator or a precursor thereof imagewise in correspondence with the amount of developed silver during development. It is achieved by a method of processing a silver halide color light-sensitive material, which comprises subjecting the material to bleaching or bleach-fixing in the presence of a compound which reacts with an oxidized product of a color developing agent to release a bleaching accelerator.

Specific Structure of the Invention In the present invention, examples of the processing solution having a bleaching ability for bleaching or bleach-fixing a light-sensitive material include a bleach-fixing solution and a bleaching solution.

The bleaching agent used in the processing solution having a bleaching ability is preferably a metal complex salt of an organic acid such as ethylenediaminetetraacetic acid.

As the metal ions constituting the complex salt, iron, copper and cobalt are preferable, and ferric ion is particularly preferable.

The amount of the metal complex salt of an organic acid used is preferably 5 to 400 g, and particularly preferably 10 to 200 g, per treatment solution having a bleaching ability.

Additives for the bleaching solution include in particular alkali halides or ammonium halides, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like.

Further, it is known to be added to pH buffers such as borate, acid salt, acetate, carbonate, and phosphate, and to ordinary bleaching solutions such as aminopolycarboxylic acids or salts thereof, alkylamines, and polyethylene oxides. The thing can be added suitably.

When the bleaching step is carried out using a bleach-fixing solution in the present invention, the bleaching-fixing solution contains a metal complex salt of an organic acid as described above (for example, an iron complex salt) as a bleaching agent and a thiosulfate salt, a thiocyanate salt, A liquid having a composition containing a silver halide fixing agent such as thioureas is preferably used. In addition, a bleach-fixing solution comprising a composition containing a small amount of a halogen compound such as potassium bromide in addition to a bleaching agent and the above silver halide fixing agent, or, conversely, a composition containing a large amount of a halogen compound such as potassium bromide. It is also possible to use a bleach-fixing solution of the following, or a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide. As the halogen compound, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide and the like can be used in addition to potassium bromide.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate. Typical examples thereof include thiosulfates, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea, thioethers, high-concentration bromides and iodides.

For the bleach-fixing solution, as in the case of the bleaching solution, boric acid, borax,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
A pH buffering agent consisting of various salts such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide and the like can be contained alone or in combination of two or more kinds. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or a kind of stabilizers such as nitroalcohol nitrate, methanol, dimethylformamide, dimethylsulfoxide. It is possible to appropriately contain an organic solvent and the like.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0.

The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5, most preferably 6.5-8.5.

The FR compounds used in the present invention include the following.

(I) A coupler that couples with an oxidation product of an aromatic primary amine developing agent to release a fogging agent, a development accelerator or a precursor thereof (ii) an oxidation product of an aromatic primary amine developing agent (Iii) Oxidation of a developing agent by forming a diffusible (colored or non-colored) dye, which has a fogging group, a group having a development promoting action, or a precursor thereof. Compounds that cause a redox reaction with a product and release a fogging agent or a development accelerator or a precursor thereof by a hydrolysis reaction subsequent to the oxidation reaction FR compounds (i) (ii) and (iii) are preferable. Are respectively represented by the following general formulas [1], [2] and [3].

[1] COUP-1- (TIME-1) _n- FA [2] FOG (COUP-2) BALL [3] RED-B In the formula of [1], COUP-1 is an aromatic primary amine development. Represents a coupler residue capable of undergoing a coupling reaction with the oxidation product of the main drug, (TIME-1) _n- FA is released by the coupling reaction and has a group or a development accelerator capable of fogging silver halide. It represents a residue containing a group or a precursor thereof.

The coupler residue represented by COUP-1 can be any coupler residue known in the art or already used.

COUP-1 may also be a so-called colorless coupler residue in which the coupling product with the oxidation product of the aromatic primary amine developing agent does not have remarkable visible absorption.

As a timing group represented by TIME-1, US Pat.
No. 248,962, JP 57-56837, etc., which leaves the COUP by a coupling reaction and FA by a post-intramolecular substitution reaction, British Patent 2,072,363A, JP Sho
57-154234, 57-188035, etc., which leave FA by electron transfer through a conjugated system, JP-A-57-111536
And the like, which is a coupling component capable of releasing FA by a coupling reaction with an oxidation product of an aromatic primary amine developing agent as described in No.

n represents 0 or 1.

FA is a group that is released from COUP-1 by a coupling reaction when n is 0, and is a group that is released from TIME-1 when n is 1, and is substantially equivalent to silver halide grains. It is a group having a fog action or a group having a development promoting action.

FA is, for example, a group represented by (L) m-X. Here, L represents a divalent linking group, X is a reducing group or a group capable of forming silver sulfide during development, and m is 0 or 1. When FA is a group represented by (L) m-X, the position to be bonded to TIME-1 may be at any position in (L) m-X.

If L or X can be eliminated by a coupling reaction, these may be bonded to the coupling carbon. What is known as a so-called 2-equivalent leaving group may be interposed between the coupling carbon and L or X.

Among the groups represented by X, some of the groups capable of forming silver sulfide at the time of development are themselves adsorptive to silver halide grains, and can also serve as an adsorptive group described later.

Among the groups represented by FA, those having a group capable of adsorbing silver halide are particularly preferable. These adsorption groups are
It may be linked to either L or X in FA.

Specific examples of the compound represented by the general formula [I] among the FR compounds of the present invention are shown below, but the invention is not limited thereto.

In the formula [2], BALL is a group which is bonded to the coupling position of COUP-2 and can be separated from COUP-2 by the reaction between COUP-2 and the oxidized product of the aromatic primary amine developing agent. Yes, it represents a so-called ballast group sized and shaped to impart non-diffusivity to the coupler.

FOG is a group that shows a fogging action or a development accelerating action in a developing solution after leaving BALL by reacting with an oxidized product of an aromatic primary amine developer, and other than at the coupling position of COUP-2. Are connected.

COUP-2 represents a group capable of undergoing a coupling reaction with an oxidation product of an aromatic primary amine developing agent.
Synonymous with UP-1.

FOG (COUP-2)-is a partial structure of a coupling product having a suitable diffusivity, which is generated by the reaction of an aromatic primary amine developer with an oxidized product, and exhibits a fogging action in a developing solution. .

The appropriate diffusivity referred to here varies depending on the purpose of use or the light-sensitive material, but in the case of a color negative film, for example, to the extent that it does not cause a significant decrease in sharpness or a significant effect on a layer having different color sensitivity (for example, high contrast). Means the diffusivity of.

Examples of the compound represented by the general formula [2] are shown below.

The total molecular weight of FOG (COUP-2)-groups is preferably 500 or less, more preferably 400 or less.

RE in the general formula [3] of the FR compound used in the present invention
D represents a group capable of leaving B by an oxidation-reduction reaction with an oxidized product of a developing agent under alkaline conditions.

B is preferably a group represented by the following general formula [XXX].

Formula _{[XXX] TIME-2 l L} 1 L 2 K A formula TIME-2 represents a so-called timing group which releases -L ₁ L _{2 K} A after B has been released, K is an integer of 0 or 1 Represents Examples of the timing group, U.S. Pat.No. 4,248,962, those utilizing an intramolecular nucleophilic substitution reaction as described in JP-A-57-56837, etc., British Patent 2,072,363A, JP-A-57-154234, the same. 57-188035
And No. 58-98728, which utilize electron transfer via a conjugated system in the molecule.

TIME-2 also includes those containing multi-step reactions.

L ₁ represents a group for leaving B from RED by redox reaction with an oxidant of a developing agent under alkaline conditions when l is 0, and when 1 is 1,
It represents a group for leaving from TIME-2.

L ₂ is a divalent linking group, and K represents 0 or 1.

As for A, B is released from the FR compound of general formula [III]
AL in the liquid_{2 K}L₁ Or AL_{2 K}L₁Exist in the form of -H
When present, it is substantially fogged against the silver halide emulsion.
It is a group that exerts an action.

Examples of the compound of the general formula [III] of the present invention are shown below.

These FR compounds of the present invention, based on generally known compounds, JP-A-57-150845, JP-A-57-138636, U.S. Pat.
214,377, 3,253,924, Japanese Patent Application No. 57-161515, Japanese Patent Application No. 5
It can be synthesized by the method described in, for example, 8-146097 and Japanese Patent Application No. 58-214808.

A known method for introducing the FR compound of the present invention or the coupler described below into a silver halide emulsion layer is known, for example, US Pat.
The method described in No. 7 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl), Benzoic acid ester (eg, octyl benzoate),
Alkyl amides (eg diethyl lauryl amide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate) etc., or a boiling point of about 30
After being dissolved in an organic solvent at ℃ to 150 ℃, for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. Dispersed in colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

When the FR compound of the present invention or the coupler described below has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. The FR compound is preferably added to the silver halide emulsion layer or its adjacent layer, and the addition amount thereof is preferably 10 per mol of silver halide.
^{-8 to} 0.5 mol, more preferably 10 ^{-7 to} 0.05 mol.

On the other hand, the coupler is 0.005 to 2 per mol of silver halide.
It is used by adding mols, preferably 0.01 to 1 mol.

A compound that reacts with an oxidized product of a color developing agent used in the present invention to release a bleaching accelerator (hereinafter referred to as BAR compound)
Is not particularly limited to its structure, but is preferably one represented by the following general formula [A] or [B].

General formula [A] General formula [B] In the formula, Cp represents a coupler residue capable of undergoing a coupling reaction with an oxidized product of a color developing agent, * represents a coupling position of the coupler, TIME represents a timing group, and m and n each represent 0 or 1. represents, R ₁ is (preferably an alkylene group having 1 to 8 carbon atoms) bonded group represents, R ₂ is a hydrogen atom, a cyano group, -COR _3, -csr _3, Heterocyclic group (R ₃ represents an alkyl group or an aryl group,
R ₄ , R ₅ and R ₆ represent a hydrogen atom, an alkyl group or an aryl group. And Rb ₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, or (Wherein L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), and Rb ₂ represents a water-soluble group or a precursor thereof.

Coupler residues represented by Cp include those that produce yellow, magenta, or cyan dyes and those that produce substantially colorless products.

In the coupler residue represented by Cp, a representative yellow coupler residue is represented by U.S. Pat.No. 2,298,443.
No. 2,407,210, 2,875,057, 3,048,19
No. 4, No. 3,265,506, No. 3,447,928, and "Farbukpraeine Literat Wolvergicht Agfamitting (Band II)" {Farbkupplere
ine Literaturuversiecht Agfa Mitteilung (B and I
I)} 112 to 126 (1961). Of these, acylacetanilides such as benzoylacetanilide and pivaloylacetanilide are preferable.

Typical as a magenta coupler residue, U.S. Patent Nos. 2,369,489, 2,343,703, 2,311,182,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3, No. 3,152,896, No. 3,519,429, No. 3,725,06
7, No. 4,540,654, JP-A-59-162548, and Agfa Mitteilung (B and II) 126-156 (1961).
Year) etc. Of these, pyrazolone or pyrazoloazole (eg, pyrazoloimidazole, pyrazolotriazole, etc.) is preferable.

A typical cyan coupler residue is described in US Pat.
2,367,531, No. 2,423,730, No. 2,474,293, No. 2,772,162, No. 2,395,826, No. 3,002,836,
Nos. 3,034,892, 3,041,236, 4,666,999 and Agfa Mitteilung (B and II) pp. 156 to 175 (1961) and the like. Of these, phenols or naphthols are preferable.

Typical coupler residues forming a substantially colorless product are, for example, British Patent No. 861,138, U.S. Pat.Nos. 3,632,345, 3,928,041, and 3,958,99.
No. 3 and No. 3,961,959.
Of these, cyclic carbonyl compounds are preferred.

The timing group represented by TIME is a bleaching accelerator group. -S-Rb ₁ -Rb ₂ ) is a group that enables the release from Cp in a time-controlled manner. This group contains the reaction rate between Cp and the oxidant of the color developing agent, which is released from Cp. Was Or -TIME-S-Rb ₁ -Rb ₂ diffusion rate, and may contain a group capable of controlling the rate of release of bleach accelerator group. A representative timing group is U.S. Pat.
No. 8,962, those releasing a bleaching accelerator group by an intramolecular nucleophilic substitution reaction disclosed in JP-A-57-56837, JP-A-56-114946 and JP-A-57-154234. Examples thereof include those which release a bleaching accelerator group by an electron transfer reaction along a conjugated chain as disclosed in a book or the like. In addition, JP-A-57-188035, JP-A-58-98728, and JP-A-59-206834
No. 60, No. 60-7429, No. 60-214358, No. 50-225844, No. 6
0-229030, 60-233649, 60-237446, 60-237
Also included are the timing groups disclosed in 447.

Specific examples include the following.

In -S-Rb ₁ -Rb ₂ is one of the bleach accelerator group, Rb
₁ is a divalent aliphatic group having 1 to 8 carbon atoms, or (Wherein L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), and more preferably the following formula.

In the formula, R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 1 to 8. n
When is 2 or more, R ₃ and R ₄ may be the same or different.

The alkyl group represented by R ₃ and R ₄ may be linear or branched, and examples thereof include a methyl group, an ethyl group and n.
-Propyl group, iso-propyl group, n-butyl group, and t
An er-butyl group and the like.

As a preferable group of R ₁ in the general formula [A], the above Rb ₁
Shown as a preferred group of And a group synonymous with.

Preferred examples of Rb ₁ are shown below.

Preferred examples of the water-solubilizing group represented by Rb ₂ or its precursor are shown below.

−COOH, −COONa, −COOCH ₃ , -COOC ₂ H ₅ , -NHSO ₂ CH ₃ , -NHCOOC
_{H 3, -NHCOOC 2 H 5,} -SO 3 H, -SO 3 K, -OH, _{-SO 2 NH 2, -NR 5 R} 6 [ wherein represents an alkyl group of R ₅ and R ₆ are each C1-4 hydrogen atom or a carbon atom. ] A particularly preferable bleaching accelerator group represented by -S-Rb ₁ -Rb ₂ is Is.

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

The BAR compound according to the present invention can be contained in any layer of the photographic material, for example, a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer, but is preferably used in the silver halide emulsion layer. Is good. Further, it is preferably used in the red-sensitive silver halide emulsion layer and / or the green-sensitive silver halide emulsion layer.

In order to incorporate the BAR compound of the present invention into the hydrophilic colloid layer of a color light-sensitive material, for example, known high-boiling point solvents such as dibutyl phthalate, tricresyl phosphate, and dinonylphenol, and low-boiling point solvents such as butyl acetate and propionic acid. The BAR compound according to the present invention is dissolved alone or in combination in a liquid mixture with a solvent having a boiling point, and then dissolved in a gelatin aqueous solution containing a surfactant and then mixed with a high-speed rotary mixer or a colloid mill or an ultrasonic disperser. After emulsifying and dispersing using the above, it may be directly added to the emulsion, or after the above emulsified dispersion is set, it may be shredded and washed with water and then added to the emulsion.

The amount of the BAR compound used in the present invention is 0.0005 mol to 5.0 mol, preferably 0.005 mol to 1 mol, per mol of silver halide.
It is in the range of 1.0 mole. The BAR compound according to the present invention may be used alone or in combination of two or more kinds.

The silver halide emulsion used in the light-sensitive material of the present invention includes
Any of ordinary silver halide emulsions can be used.

The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion.

It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened, and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Further, by the coupling with colored couplers, competing couplers and oxidized products of developing agents, which have the effect of color correction, development accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, fog. Compounds that release photographically useful fragments such as inhibitors, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development process may be contained.

A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder and a bleaching accelerator can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like,
Polyethylene terephthalate film, baryta paper, cellulose triacetate and the like can be used.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Conventionally known color photographic processing can be performed.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example 1 A transparent support consisting of an undercoated cellulose triacetate film and having an antihalation layer (containing 0.40 g of black colloidal silver and 3.0 g of gelatin),
Sample 2 was prepared by sequentially applying the following layers. In all the examples below, the amount added to the light-sensitive material is shown per 1 m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver.

The layers are as follows.

Layer 1 ... 1.4 g of low-sensitivity red-sensitive silver iodobromide (containing 7 mol% silver iodide) emulsion red-sensitized and 1.2 g of gelatin and 0.8 g of 1-hydroxy-N-as a cyan coupler.
[Δ- (2,4-di-t- (amylphenoxy) butyl]
-2-naphthamide (hereinafter abbreviated as C-1), 0.075g
1-hydroxy-4- [4- (1-hydroxy-δ-
Acetamide-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2,4-di-t-amylphenoxy) butyl-2-naphthamide disodium (colored cyan coupler), and 0.07 g A slow red sensitive emulsion layer containing 0.65 g of tricresyl phosphate (TCP) in which 4-octadecylsuccinimide-2- (1-phenyl-5-tetrazolylthio) -1-indanone (DIR compound) was dissolved.

Layer 2 ... 1.3 g of high-sensitivity red-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), 1.2 g of gelatin and 0.21 g of cyan coupler C-1 used in Layer 1 and 0.02 g of Layer 1 A high-sensitivity red-sensitive emulsion layer containing 0.23 g of TCP in which 0.1 g of the FR compound shown in Table 1 was dissolved and the colored cyan coupler used in 1.

Layer 3--Intermediate layer containing 0.04 g of n-dibutyl phthalate (DBP) in which 0.07 g of 2,5-di-t-octylhydroquinone (contaminant) was dissolved and 0.8 g of gelatin.

Layer 4 ... 0.80 g of low-sensitivity silver iodide-sensitized silver iodide (containing 6 mol% of silver iodide) emulsion and 2.2 g of gelatin and 0.8 g of 1- (2,4,6- Trichlorophenyl) -3-[(α-2,4-di-t-amylphenoxy) acetamido] benzamido-5-pyrazolone (hereinafter abbreviated as M-1), 0.15 g of 1- (2,4,6- Trichlorophenyl) -4- (1-naphthylazo) -3- (2-
Chloro-5-octadecenylsuccinimide aniline)
-5-pyrazolone (colored magenta coupler), 0.01
A slow green sensitive emulsion layer containing 0.95 g TCP dissolved in 6 g DIR compound (same as above).

Layer 5: 1.8 g of high-sensitivity green-sensitive silver iodobromide (containing 3 mol% silver iodide) emulsion sensitized to green, 1.9 g of gelatin, and 0.20 g of magenta coupler M- used in Layer 4. 1 and 0.049 g of the colored magenta coupler used in Layer 4 and 0.1 g of the FR compound shown in Table 1 were dissolved.
High sensitivity green sensitive emulsion layer containing 0.60 g of n-dinonyl phthalate (DNP).

Layer 6 ... Yellow filter layer containing 0.15 g of yellow colloidal silver, 0.11 g of DBP in which 0.2 g of stain inhibitor (same as contained in layer 3) was dissolved and 1.5 g of gelatin.

Layer 7: 0.2 g of low-sensitivity silver iodobromide (containing 4 mol% of silver iodide) emulsion sensitized to blue and 1.9 g of gelatin and 1.5 g of α-pivaloyl-α- (1 as a yellow coupler. −
Benzyl-2-phenyl-3,5-dioxoimidazolidin-4-yl) -2'-chloro-5 '-[α-dodecyloxycarbonyl) ethoxycarbonyl] acetanilide (hereinafter abbreviated as Y-1) A low-sensitivity blue-sensitive emulsion layer containing 0.6 g of TCP dissolved therein.

Layer 8: 1.0 g of high-sensitivity silver iodobromide (containing 2 mol% silver iodide) emulsion sensitized to blue, 1.5 g of gelatin and 1.30 g
Yellow Coupler Y-1 used in Layer 7 and 0.1 g of the first
High-sensitivity blue-sensitive emulsion layer containing 0.65 g of TCP in which FR compounds shown in the table are dissolved.

Layer 9 ... Protective layer with 2.3 g of gelatin.

Separately, a sample 1 was prepared in which the FR compound was not added to the layers 2, 5 and 8.

Also, the couplers of Layer 1, Layer 2, Layer 4, Layer 5, Layer 7, and Layer 8 of Sample 2 were replaced with BAR compounds as shown in Table 1 and Sample 3 was used.
Created ~ 10.

The samples 1 to 10 thus obtained were subjected to red optical wedge exposure using a KS-7 type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.) and subjected to the treatment shown in Table 2.

In Table 2, Treatment A is a treatment liquid obtained by subjecting Sample A (A represents a sample number) to full exposure with white light and continuously treating 10 m ² per day for 10 days with an automatic processor according to the following steps. To indicate processing.

As the automatic developing machine, a hanging type automatic film developing machine type H4-220W-2 manufactured by Noritsu Tsushinki Co., Ltd. was modified and used.

Processing process (38 ℃) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Small amount of water wash 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water wash 4 minutes 20 seconds Stability 2 minutes 10 seconds The composition of the color developer used is Is the street.

[Color developer] Potassium carbonate 30g Sodium hydrogencarbonate 2.5g Potassium sulfite 5g Sodium bromide 0.1g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N- ( β-hydroxylethyl) aniline sulphate 4.8g potassium hydroxide 1.2g Add water to make 1 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

The composition of the color developing replenishing solution used is as follows.

[Color development replenishing solution] Potassium carbonate 40 g Sodium hydrogen carbonate 3 g Potassium sulfite 7 g Sodium bromide 2.5 × 10 ^-3 mol Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyl Ethyl) aniline sulphate 6.0g Potassium hydroxide 2g Add water to make 1 and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

The composition of the bleaching solution used is as follows.

[Bleach] Ethylenediaminetetraacetate iron ammonium 100 g Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 150 g Glacial acetic acid 10 ml Water is added to adjust to pH 5.8 using aqueous ammonia or glacial acetic acid.

The composition of the bleach replenisher used is as follows.

[Bleach replenisher] Ethylenediaminetetraacetic acid iron ammonium 120g Ethylenediaminetetraacetic acid disodium 12g Ammonium bromide 178g Glacial acetic acid 21ml Add water to adjust to 1 and adjust to pH 5.6 with aqueous ammonia or glacial acetic acid.

The composition of the fixing solution used is as follows.

[Fixing solution] Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Ethylenediaminetetraacetic acid disodium 0.5g Sodium carbonate 10g Add water to make 1.

The composition of the fixing replenisher used is as follows.

[Fixing replenisher] Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Ethylenediaminetetraacetic acid disodium 0.8g Sodium carbonate 14g Add water to make 1.

The composition of the stabilizing solution used is as follows.

[Stabilizer] Formalin (37% aqueous solution) 2 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 5 ml Add water to make 1.

The composition of the stable replenishing solution used is as follows.

[Stable replenisher] Formalin (37% aqueous solution) 3 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7 ml Add water to make 1.

Color developer replenishing solution is replenished in the sample 100 cm ² per 8.0ml color developing bath, bleaching replenishing solution is replenished in the sample 100 cm ² per 18ml bleach bath, fixing replenishing solution, the sample 100 cm ² per 7m
supplemented to l fixing bath, more stable replenishing solution, the sample 100 cm ²
Refilled per 11 ml stabilizing bath. In addition, the small amount of washing bath is supplemented with 3 ml of water per 100 cm ^{2 of the} sample, and the washing bath is
150 ml of water was flowed per 100 cm ² of sample.

Ammonium hydroxide or acetic acid is appropriately added to the fixing replenisher to adjust the pH of the fixing bath during continuous processing of the sample.
I've always been at 6.5.

Table 2 shows the residual silver amount in the maximum exposed areas of the processed samples 1 to 10. The amount of silver was measured by fluorescent X-ray.

As is clear from Table 2, bleaching inhibition occurs when a large amount of a photographic material containing a FR compound is continuously processed. The sample of the present invention containing the BAR compound and the FR compound in the light-sensitive material does not cause bleaching inhibition even in a processing solution in which bleaching inhibition occurs in a sample other than the present invention.

Samples in which BAR-22 of Samples 3, 4, 5 and 10 was replaced with BAR-44 to 56,
Samples in which BAR-9 of Samples 6, 7 and 10 was replaced with BAR-57 to 66,
Similar results were obtained with the samples in which BAR-2 of samples 8, 9 and 10 was replaced with BAR-67 to 72.

Samples 3 to 10 and samples 3, 4, 5 and 10 with BAR-22 replaced by BAR-44 to 56, samples 6, 7 and 10 with BAR-9 replaced by BAR-57 to 66, BAR-2 of samples 8, 9 and 10 was replaced with BAR-67 to 72, and FR compounds of layer 2 of the sample were replaced with I-1, I-4 and I.
-6, I-10, I-11, I-13, II-2, II-7, III
Similar results were obtained with the samples replaced with -1 to III-4 and III-6 to III-10. In addition, the FR compound of Layer 5 is I-2,
I-6, II-3, II-4, III-1 to III-4, III-6
To III-10, the FR compound of layer 8 was replaced with I-3,
I-6, I-7, I-12, II-5, II-6, III-1 to I
Similar results were obtained with the samples replaced with II-4 and III-6 to III-10.

Example-2 Samples 1 to 10 used in Example-1 were exposed in the same manner as in Example-1, and the following treatments were carried out.

The amount of residual silver in the maximum exposed area of each of Samples 1 to 10 after the treatment was determined as an example.
The measurement was performed in the same manner as in 1 and the results are shown in Table 3.

Processing step Processing time Color development 3 minutes 15 seconds Bleach fixing 3 minutes 15 seconds Washing with water 2 minutes Stability 1 minute Drying Each processing uses a processing solution prepared by the following formulation. The processing temperature is 38 ° C.

[Color developer] [Bleaching fixer] [Stabilizer] As is clear from Table 3, a photographic material containing an FR compound is less likely to be bleached by a bleach-fixing process, but it is improved by using a BAR compound as a coupler.

Samples in which BAR-22 of Samples 3, 4, 5 and 10 was replaced with BAR-44 to 56,
Samples in which BAR-9 of Samples 6, 7 and 10 was replaced with BAR-57 to 66,
Similar results were obtained with the samples in which BAR-2 of samples 8, 9 and 10 was replaced with BAR-67 to 72.

Samples 3-10, samples 3, 4, 5 and 10 with BAR-22 replaced with BAR44-56, samples 6, 7 and 10 with BAR-9 replaced with BAR-57-66, sample 8 , 9 and 10 of BAR-2 were replaced with BAR-67 to 72, and the FR compound of layer 2 of the sample was replaced with I-1, I-4 and I.
Similar results were obtained with the samples in which -6, I-10, I-11, and I-13 were replaced. Further, the FR compound of Layer 5 was replaced with I-2, I
-6, the FR compound of Layer 8 was replaced with I-3, I-
Similar results were obtained with the samples substituting 6, I-7, and I-12.

Claims (1)

[Claims] 1. A silver halide color light-sensitive material containing a fogging agent or a precursor thereof or a compound which releases a development accelerator or a precursor thereof in an imagewise manner in correspondence with the amount of developed silver during development. A method of processing a silver halide color light-sensitive material, which comprises performing bleaching or bleach-fixing treatment in the presence of a compound which reacts with an oxidant to release a bleaching accelerator.