JPH0814689B2 - Processing method of silver halide color photographic light-sensitive material excellent in storability of dye image - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it relates to a silver halide color photographic light-sensitive material capable of obtaining a dye image having excellent storage stability. Regarding processing method.

BACKGROUND OF THE INVENTION A silver halide color photographic light-sensitive material is generally exposed and then processed to obtain an image with a color-forming dye. Various efforts have been made for the stable storage of images recorded on silver halide color photographic light-sensitive materials for a long period of time.

One is a method of stabilizing in a photographic processing step for obtaining an image, and a typical method is, for example, a method of performing a final processing with a processing solution containing formalin. On the other hand, efforts have been made to stabilize the image from the side of the light-sensitive material, and particularly, the recently developed 2,5-diacylaminophenol-based, 2-
The improvement of the dark fading property of the cyan dye image obtained from the ureido-5-acylaminophenol cyan coupler is remarkable. However, even these couplers have not yet been satisfactory in image storability. The reason is that the cyan dyes obtained from these diacyl and ureido type cyan couplers are bright and fading. The dark fading property is certainly improved, but the light fading property is still not sufficient.

Thus, at present, no method has been found for obtaining a cyan dye image having a sufficiently satisfactory image storability.

[Object of the Invention] An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material capable of obtaining a dye image which is excellent in image storability, particularly in light fading and dark fading.

[Structure of the Invention] The above object of the present invention is to halogenate at least one cyan coupler selected from a cyan coupler represented by the following general formula [I] and a cyan coupler represented by the following general formula [II]. This can be achieved by a method of processing a silver halide color photographic light-sensitive material, which comprises exposing a silver halide color photographic light-sensitive material having at least one silver emulsion layer imagewise and then processing it with a processing solution containing a hexamethylenetetramine compound.

General formula [I] General formula [II] In the formula, Y is -COR ₂ , -SO ₂ R _2, -CONHCOR ₂ or -CONHSO ₂ R ₂ (R ₂ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₃ is a hydrogen atom, an alkyl group, an alkenyl group, Represents a cycloalkyl group, an aryl group or a heterocyclic group, and R ₂ and R ₃ may combine with each other to form a ring). R ₁ represents a ballast group. Z represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a color developing agent.

[Specific Structure of the Invention] The silver halide color photographic light-sensitive material used in the present invention is at least one selected from the cyan coupler represented by the general formula [I] and the cyan coupler represented by the general formula [II]. It has at least one silver halide emulsion layer containing two cyan couplers.

The cyan couplers represented by the general formulas [I] and [II] will be described.

In the general formulas [I] and [II], Y is -CO
R ₂ , Represents —SO ₂ R ₂ , —CONHCOR ₂ or —CONHSO ₂ R ₂ . Here, R ₂ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, t-butyl group, dodecyl group, etc.), alkenyl group, preferably alkenyl group having 2 to 20 carbon atoms. (Eg, allyl group, heptadecenyl group, etc.), cycloalkyl group, preferably 5 to 7-membered ring (eg, cyclohexyl group, etc.), aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.) or heterocyclic group,
Preferably, a nitrogen atom, an oxygen atom or a sulfur atom is 1
A heterocyclic group of 5 to 6 membered ring containing 4 to 4 (for example, a furyl group,
A thienyl group, a benzothiazolyl group, etc.). R ₃ represents a hydrogen atom or a group represented by R ₂ . R ₂ and R ₃ may combine with each other to form a ring (for example, a 5- to 6-membered heterocycle containing a nitrogen atom). In addition, any substituent can be introduced into R ₂ and R ₃ , and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an aryl group, a halogen atom, a cyano group, a nitro group, and a sulfonamide. Examples thereof include groups, sulfamoyl groups, sulfonyl groups, carbamoyl groups, oxycarbonyl groups, acyl groups, heterocyclic groups (eg pyridyl groups, pyrazolyl groups, etc.), alkoxy groups, aryloxy groups, acyloxy groups and the like.

In the general formulas [I] and [II], the ballast group represented by R ₁ has diffusion resistance to the cyan couplers represented by the general formulas [I] and [II] and the cyan dye formed from the cyan coupler. It is a ballast group necessary for imparting, and is preferably an alkyl group having 4 to 30 carbon atoms, an aryl group or a heterocyclic group.

In the general formulas [I] and [II], Z represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidant of a color developing agent, and examples thereof include a halogen atom, a substituted or unsubstituted alkoxy group, and aryloxy. Group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonamide group, and the like, and more specifically, U.S. Pat. No. 3,741,563. , JP-A-47-374
No. 25, Japanese Patent Publication No. 48-36894, JP-A No. 50-10135, No. 50-
117422, 50-130441, 51-108841, 50-12
No. 0343, No. 52-18315, No. 53-105226, No. 54-14736
No. 54-48237, No. 55-32071, No. 55-65957,
56-1938, 56-12643, 56-27147, 59-
146050, 59-166956, 60-24547, 60-357
No. 31 and No. 60-37557.

Next, specific examples of the cyan couplers represented by the above general formulas [I] and [II] (hereinafter referred to as the cyan coupler of the present invention) are shown, but the present invention is not limited thereto.

Specific examples other than the above include the compounds described on pages 67 to 91 of Japanese Patent Application No. 61-91107.

The cyan coupler of the present invention can be synthesized by various methods, for example, U.S. Pat. Nos. 2,772,162 and 3,7.
58,308, 3,880,661, 4,124,396, 3,
222,176, British Patent No. 975,773, No. 8,011,693,
No. 8,011,694, JP-A-47-21139, 50-112038.
No. 55, No. 55-163537, No. 56-29235, No. 55-99341,
56-116030, 52-69329, 56-55945, 56
-80045, 50-134644, and British Patent 1,011,9
40, U.S. Pat.Nos. 3,446,622, 3,996,253, JP-A-56-65134, 57-204543, 57-204544, 5
7-204545, Japanese Patent Application Nos. 56-131312 and 56-131313,
56-131314, 56-131309, 56-131311, and
57-149791, 56-130459, JP-A-59-146050,
59-166956, 60-24547, 60-35731, 60
It can be synthesized by the synthetic method described in -37557 and the like.

The cyan coupler of the present invention can be used in combination with a cyan coupler other than the present invention as long as the object of the present invention is not impaired. Further, two or more cyan couplers of the present invention can be used in combination.

When the cyan coupler of the present invention is contained in a silver halide emulsion layer, it is usually about 0.000 per mol of silver halide.
It is used in the range of 5 to 2 mol, preferably 0.01 to 1 mol.

In the silver halide color photographic light-sensitive material used in the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photosensitive material for photographic paper, a blue photosensitive silver halide emulsion layer containing a yellow coupler, a green photosensitive silver halide emulsion layer containing a magenta coupler, and a cyan coupler are sequentially contained from the support side. The arrangement is preferably a red-sensitive silver halide emulsion layer. Each of these light-sensitive silver halide emulsion layers may be composed of two or more layers.

Further, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer may be appropriately combined and used as a constituent layer. it can.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds.

Further, as the yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide type yellow coupler which is generally widely used,
A pivaloylacetanilide type yellow coupler can be used.

The amount of the magenta and yellow couplers used in the present invention is generally 0.05 to 2.0 mol per mol of silver in the photosensitive silver halide emulsion layer.

As the silver halide of the silver halide emulsion used in the present invention, any of silver chlorobromide, silver chloride, silver chloroiodobromide, silver iodobromide and the like can be used.

The silver halide emulsions used in the present invention include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine and the like; selenium sensitizers; reduction sensitizers such as the first.
Tin salts, thiourea dioxide, polyamines and the like; noble metal sensitizers such as gold sensitizers may be sensitized chemically alone or in combination.

The silver halide used in the present invention may be optically sensitized by adding an appropriate sensitizing dye in order to impart photosensitivity to a desired light-sensitive wavelength region. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure No. 17643 , A plasticizer, a wetting agent and the like can be used.

In the present invention, the silver halide color photographic light-sensitive material having the above constitution is imagewise exposed and then treated with a processing solution containing a hexamethylenetetramine compound.

The hexamethylenetetramine compound in the present invention is hexamethylenetetramine and its derivatives.
Examples of the hexamethylene tetramine derivative include a halogen addition product of hexamethylene tetramine, an inorganic acid addition product, a metal salt addition product, a phenol derivative addition product, an alkyl sulfonic acid addition product, an aryl sulfonic acid addition product, an alkyl sulfate ester addition product, and an alkyl product. Examples thereof include carboxylic acid adducts, arylcarboxylic acid adducts, and alkyl halide adducts.

Hexamethylenetetramine and its derivatives of the present invention are specifically described by Beilsteins Handbuch.
Dare Organischen Chemie (Beilsteins Handbuc
h der Organischen Chemie) Volume II Supplement 26, p200
To p212. Among them, those soluble in water are preferable in the present invention. Typical examples of the hexamethylenetetramine compound of the present invention (hereinafter referred to as the compound of the present invention) are shown below, but the present invention is not limited thereto.

Is the compound of the present invention readily available as a commercial product,
Alternatively, the synthesis can be easily carried out by using the method described in the above literature.

The compounds of the present invention may be used alone or in combination of two or more. The amount added is preferably 0.05 g or more, and more preferably 0.3 to 20 g, per treatment liquid containing the compound of the present invention.

In the processing method of the present invention, the processing solution containing the compound of the present invention can be applied to all processing solutions for processing silver halide color photographic light-sensitive materials, for example, color developing solution, bleaching solution, fixing solution, bleach-fixing solution, It can be a pre-fixing solution (pre-processing solution having fixing ability), a stabilizing solution as a substitute for washing, a stabilizing solution, etc., and can be applied to a plurality of these processing solutions, most preferably at the final stage of the processing step. This is the case when applied to the processing liquid used. Further, in the treatment method of the present invention, the compound of the present invention can be contained in the treatment liquid used in the case where the water-washing alternative stabilizing treatment and the stabilizing treatment are simultaneously performed in one bath.

Incidentally, the above-mentioned washing substitute stabilizer is a treatment liquid having a fixing ability, for example, a treatment used in the case of performing a direct washing substitute stabilization treatment without substantially washing with a fixing solution or a bleach-fixing solution. Refers to liquid.

The processing solution containing the compound of the present invention is a color developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution, a pre-fixing solution, a water-washing alternative stabilizing solution,
When applied to a stabilizing solution, etc., a normal color developing solution,
Compounds that can be added to the bleaching solution, the fixing solution, the bleach-fixing solution, and the pre-fixing solution can be optionally used, and examples of the compound that can be added to the washing-replacement stabilizing solution and the stabilizing solution include JP-A-61-2779.
Examples thereof include the compounds described on page 107, line 20 to page 138, line 15 of the specification No. 52.

[Effects of the Invention] By the processing method of the present invention, the dye image formed from the cyan coupler of the present invention is excellent in both the light fading property and the dark fading property, and the image storability is improved.

[Examples] Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these embodiments.

Example 1 Following the layer structure adopted for a high-sensitivity silver halide color photographic light-sensitive material in the industry, a halation-preventing layer and a red-light-sensitive halogenation layer were added from the support while interposing various auxiliary layers. A silver emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer were formed, and a monodisperse high-sensitivity silver halide emulsion layer was arranged on the outermost side of the blue light-sensitive silver halide emulsion layer. That is, the sample was prepared according to the following, but the sample was prepared by changing the dried film thickness by changing the gelatin amount by changing the gelatin amount so as to keep the coated silver amount constant. The amount of coated silver is approximately
It was adjusted to be 50 mg / dm ² .

Layer 1: Silver nitrate was reduced using hydroquinone as a reducing agent to prepare 0.8 g of black colloidal silver having high absorptivity for light in the wavelength range of 400 to 700 nm with 3 g of gelatin to form an antihalation layer.

Layer 2 ... An intermediate layer made of gelatin. (Dry film thickness 0.8 μm) Layer 3: 1.5 g of low-sensitivity red light-sensitive silver iodobromide emulsion (AgI; 6 mol%), 1.9 g of gelatin and 0.96 g of the coupler C-2 of the present invention, 0.028 g 1-hydroxy-4- [4- (1
-Hydroxy-8-acetamido-3,6-disulfo-2
-Naphthylazo) phenoxy] -N- [δ- (2,4-di-amylphenoxy) butyl] -2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC-1)
A red light-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved therein.

Layer 4 ... 1.1 g of high-sensitivity red light-sensitive silver iodobromide emulsion (AgI; 8 mol%), 1.2 g of gelatin and 0.41 g of cyan coupler (C-2), 0.026 g of colored cyan coupler (CC-
A high-sensitivity red-sensitive silver halide emulsion layer containing 0.15 g of TCP dissolved in 1).

Layer 5: 0.04 g in which 0.08 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as a stain inhibitor (HQ-1)) was dissolved.
An intermediate layer containing g of dibutyl phthalate (hereinafter referred to as DPB) and 1.2 g of gelatin.

Layer 6 ... 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (AgI; 15 mol%), 1.7 g of gelatin and 0.30 g of 1- (2,4,6-trichlorophenyl) -3- [3- 2,4-di-t-amylphenoxyacetamido) benzenamide] -5-pyrazolone (hereinafter referred to as magenta coupler (M-1)),
20 g of 4,4-methylenebis-11- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacetamido) benzenamide] -5-pyrazolone (hereinafter magenta Coupler (M-2)), 0.066g
1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone (hereinafter referred to as colored magenta coupler ( A low-sensitivity green-sensitive silver halide emulsion layer containing 0.3 g of TCP in which 3 couplers (referred to as CM-1) are dissolved.

Layer 7 ... 1.5 g of high-sensitivity green-sensitive silver iodobromide emulsion (AgI; 11 mol%), 1.9 g of gelatin and 0.093 g of magenta coupler (M-1), 0.094 g of magenta coupler (M-2). , 0.
049 g of colored magenta coupler (CM-1) was dissolved
High speed green light sensitive silver halide emulsion layer containing 0.12 g TCP.

Layer 8: 0.2 g of yellow colloidal silver, 0.2 g of stain inhibitor (HQ-
Yellow filter layer containing 0.11 g of DBP dissolved in 1) and 2.1 g of gelatin.

Layer 9: 0.95 g of low-sensitivity blue-sensitive silver iodobromide emulsion (AgI; 6 mol%), 1.9 g of gelatin and 1.84 g of α- [4- (1-
Benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-2-chloro-5-
[Γ- (2,4-di-t-aminophenoxy) butanamide] acetanilide (hereinafter yellow coupler (Y-
1) a low-sensitivity blue-sensitive silver halide emulsion layer containing 0.93 g of DBP dissolved in).

Layer 10: 1.2 g of high-sensitivity monodisperse blue-sensitive silver iodobromide emulsion (AgI;
High-sensitivity blue-sensitive silver halide emulsion layer containing 0.23 g of DBP in which 7 mol%), 2.0 g of gelatin and 0.46 g of yellow coupler (Y-1) were dissolved.

Layer 11: Second protective layer made of gelatin.

Layer 12 ... A first protective layer containing 2.3 g of gelatin. The dry thickness of the photographic constituent layers of the finished sample was 20 μm.

As further samples, a sample in which the coupler C-2 according to the present invention contained in Layers 3 and 4 was replaced by C-27, a sample by which C-36 was replaced, a sample by which the following comparative cyan coupler (1) was replaced, and A sample in which the following comparative cyan coupler (2) was used was prepared.

The sample produced as described above was subjected to stepwise wedge exposure and processed according to the following processing steps. The compounds of the present invention were added to the treatment liquid (second stabilizing liquid) in the final treatment step as shown in Table 1.

Treated samples at 75 ° C and 75% RH for 3 days using a xenon fade meter (1.5 x 10 ⁷ lux · hour).
Irradiation was carried out for 5 days and 10 days, and the change in maximum cyan density was measured by an optical densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.). The treated sample was stored in the dark at 75 ° C. and 65% RH for 5 days, and the change in the maximum cyan density and the yellow stain were measured in the same manner.

Table 1 shows the obtained results. In the table, a minus (-) sign indicates a decrease in density.

The processing steps were as follows: color development 3 minutes 15 seconds, bleach-fixing 3 minutes 15 seconds, first stable 2 minutes, second stable 30 seconds.

Each treatment was carried out at 37.8 ° C., and each treatment liquid used was a treatment liquid prepared by the following formulation.

[Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) 1.0 g potassium bromide 1.2 g magnesium chloride 0.6 g sodium hydroxide 3.4 g N-ethyl-N-β-hydroxyethyl-3-methyl-
4-Aminoaniline sulfate 4.6 g Water was added to make 1 and the pH was adjusted to 10.1 with sodium hydroxide.

[Bleaching fixer] Ethylenediaminetetraacetic acid diammonium salt 1.5g Ethylenediaminediacetic acid ferric iron complex salt 160g Ammonium sulfite (50% solution) 10.0g Ammonium thiosulfate (70% solution) 200.0g Add water to make ammonium hydroxide 1 PH 7.5
Adjusted to.

[First Stabilizing Solution] 1-Hydroxyethylidene 1,1-diphosphonic acid 3.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g Add water to make 1 and add potassium hydroxide. The pH was adjusted to 7.1.

[Second stabilizing liquid] Finish by adding water.

From the above results, it is understood that the light fastness of the cyan dye when the cyan coupler of the present invention is used is remarkably improved by the treatment with the treatment liquid containing the compound of the present invention. Further, it can be seen that the sample of the present invention is also very excellent in dark fading, and the increase of yellow stain is prevented.

Example-2 The first stabilizing solution in the treatment process of Example-1 was used as a washing tank (350 ml of water was flowed per 1 m of film), and the same evaluation as in Example-1 was carried out. The result is as follows.

From the above results, it can be seen that even if the washing step is used, the same effect as in Example-1 can be obtained.

Example-3 The cyan couplers according to the present invention used in Example-2 are cyan couplers according to the present invention C-37, C-38, C-
It changed into 59 and the same evaluation was implemented, but the effect similar to Example-2 was acquired.

Example-4 Among the processing steps used in Example-1, the bleach-fixing was changed to a processing step in which bleaching and fixing were separated as shown below,
The treatment was carried out in the same manner as in Example-1, and the effects were compared.

(Bleach) Ethylenediaminetetraacetic acid diammonium salt 2.0g Ethylenediaminetetraacetic acid ferric iron complex salt 150g Potassium bromide 140g Add water to make pH 1 5.8 using acetic acid and ammonia.
Adjusted to.

(Fixer) Ammonium thiosulfate (70% solution) 200.0g Ammonium sulfite (50% solution) 10.0g Sodium metabisulfite 3g Add water to make pH 7.0 with acetic acid and ammonia 7.0
Adjusted to.

 The results are shown in Table-3.

As described above, it is understood that the effects of the present invention can be sufficiently exerted even if the treatment is performed separately in the bleaching step and the fixing step.

Example-5 Among the processing steps of Example-1, the first stabilizing solution and the second stabilizing solution were changed to the third stabilizing solution having the following composition, and the processing tank was modified from the bleach-fixing tank to a three-tank cascade. .

In addition, the replenishment amount was 40 mL per 24 EXP in the final tank.

[Third stabilizing liquid] Water was added to 1 and the pH was adjusted to 7.1 with potassium hydroxide.

After adding various compounds of the present invention to the third stabilizing solution as shown in Table 4, each of the third stabilizing solutions was used to prepare Example-1.
The change in the maximum cyan density of the photosensitive material used in Example 1 was processed and treated with a xenon fade meter for 5 days, and the maximum cyan density was changed for 5 days at 75 ° C and 65% RH. In addition, 75
The degree of increase in yellow stain when treated at 65 ° C. and 65% RH for 5 days was also compared. The results are shown in Table-4.

From the above results, it is understood that the effects of the present invention are sufficiently exerted even when the method of image stabilization processing as in this embodiment is used. In addition, when a method of processing a light-sensitive material containing a cyan coupler according to the present invention with a third stabilizing solution containing the compound of the present invention, an increase in yellow stain when stored at 75 ° C. and 65% RH is prevented. I understand.

Example-6 The same evaluations as in Example-1 were carried out by adding various compounds of the present invention to the color developer.

The process after bleach-fixing is the same as in the example, but
The compound of the present invention was not added to the second stabilizing solution. The results are shown in Table-5.

As shown in Table 5, the effects of the present invention are sufficiently exhibited even when the compound of the present invention is added to the color developing solution.

Example-7 An experiment was conducted with the following color paper, processing solution and processing steps.

[Color Paper] The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a light-sensitive material.

The polyethylene-coated paper has an average molecular weight of 10
200 parts by weight of polyethylene with a density of 0.95 and an average molecular weight of 2,
000, a mixture of 20 parts by weight of polyethylene with a density of 0.80 was added with 6.8% by weight of anatase type titanium oxide, and a extrusion coating method was used to form a coating layer with a thickness of 0.035 mm on the surface of fine paper with a weight of 170 g / m ² and a back surface. The thing which provided the coating layer of thickness 0.040 mm only with polyethylene was used for this. After performing a pretreatment by corona discharge on the polyethylene-coated surface of the support, each layer was sequentially applied.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 80 mol% of silver bromide, the emulsion containing 350 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: Sensitizing dye 2,5-di-tert-butylhydroquinone 2 sensitized with 2.5 × 10 ^-3 mol (using isopropyl alcohol as solvent) and dissolved and dispersed in dibutyl phthalate
00 mg / m ² and α- [4- (1-
Benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydyl)] α-bivalyl-2-chloro-5- [γ-
(2,4-di-tert-amylphenoxy) butyramide]
Acetanilide was contained in an amount of 2 × 10 ⁻ mol per mol of silver halide and coated so that the amount of silver was 330 mg / m ² .

Second layer: di-tert-octylhydroquinone 300 mg / m ² dissolved and dispersed in dibutyl phthalate, ^{2 as} an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole 2- (2'-hydroxy-
5'-tert-butylphenyl) benzotriazole, 2
-(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chloro-benzotriazole mixture
A gelatin layer containing 200 mg / m ² was coated so that the gelatin would be 2000 mg / m ² .

Third layer: a green light-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide and the following per mol of silver halide: Structural sensitizing dye Sensitized with 2.5 × 10 ^-3 mol of 2,5-di-tert-butylhydroquinone 1 dissolved and dispersed in a 2: 1 mixed solvent of dibutyl phthalate and tricresyl phosphate.
50 mg / m ² and 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone as a magenta coupler per mol of silver halide Contains 1.5 × 10 ^-1 mol, 300 mg silver
is applied so that the / m ^2. As an antioxidant, 2,2,4-trimethyl-6-lauryloxy-7-ter is used.
0.3 mol of t-octyl chroman was contained per mol of coupler.

4th layer: Di-tert- dissolved and dispersed in dioctyl phthalate
Octyl hydroquinone 30 mg / m ² and 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole as a UV absorber, 2- (2′-hydroxy-5′-tert-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-
Mixture of 5'-methylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-tert-butylphenyl) -5-chloro-benzotriazole (2: 1.5: 1.5: 2) weight gelatin is applied so as to 2000 mg / m ² at 500 mg / m ² gelatin layer containing.

Fifth layer: a red-sensitive silver halide emulsion layer consisting of silver chlorobromide containing 85 mol% of silver bromide, the emulsion containing 500 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: Sensitizing dye Sensitized with 2.5 × 10 ^-3 mol of 2,5-di-tert-butylhydroquinone 150 mg / m ² dissolved and dispersed in dibutyl phthalate and a cyan coupler shown in Table 6 per mol of silver halide. Contains 3.5 × 10 ^-1 mol, 300 mg silver
is applied so that the / m ^2.

Sixth layer: The gelatin layer is coated so that the amount of gelatin is 1400 mg / m ² .

The silver halide emulsion used for each light-sensitive emulsion layer (first, third, fifth layer) was prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used for each. Chemically sensitized, 4-hydroxy-6-methyl- as a stabilizer
It contained 1,3,3a, 7-tetrazaindene, bis (vinylsulfonylmethyl) ether as a hardening agent and saponin as a coating aid.

These samples were subjected to wedge exposure and processed according to the following steps.

Standard processing step [1] Color development 38 ° C 3 minutes 30 seconds [2] Bleach-fixing 33 ° C 1 minute 30 seconds [3] Washing alternative Stabilization 25 ° C-35 ° C 3 minutes [4] Drying 75 ° C-100 ° C About 2 Separation processing composition <Color developer> Benzyl alcohol 15 ml Diethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 1.3 g Sodium chloride 0.2 g Potassium carbonate 30.0 g 3-Methyl-4-amino-N-ethyl-N- (β-metasulfone Amidoethyl) -aniline sulfate 5.0 g Optical brightener (triazinyl stilbene type) 1.0 g Hydroxyamine sulfate 3.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.4 g Hydroxyethyliminodiacetic acid 5.0 g Chloride Magnesium hexahydrate 0.7 g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2 g Water is added to adjust the pH to 1 and the pH is adjusted to 10.20 with KOH and H ₂ SO ₄ .

<Bleaching fixer and replenisher> Ethylenediaminetetraacetic acid ferric ammonium dihydrate
60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% dissolution) 100 ml Ammonium sulfite (40% dissolution) 27.5 ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid.

<Color development replenisher> Benzyl alcohol 20.0 ml Diethylene glycol 20.0 ml Potassium sulfite 3.0 g Potassium carbonate 30.0 g Hydroxylamine sulfate 4.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) ) -Aniline sulfate 7.5g Optical brightener (4,4'-diaminostilbene type) 2.5g Hydroxyethyliminodiacetic acid 5.0g 1,2-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Water To 1 and add pH to 10.70 with KOH.

<Stabilizer and replacement solution for washing with water> Comparative treatment 5-chloro-2methyl-4-isothiazolin-3-one
1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Bismuth chloride 0.2g Ethylene glycol 1.0g Ammonium hydroxide (28% aqueous solution) 3.0g Add water to 1 and add sulfuric acid and potassium hydroxide to pH 7.1.
Adjusted to.

Treatment of the Present Invention In the above-mentioned comparative formulation, 1.
2.0 g per 0 l was added.

The replenishing amount was 200 ml of the color developing replenishing solution, 50 ml of each of the bleach-fixing replenishing solutions A and B, and 350 ml of the washing-replacement stable replenishing solution per 1 m ² of the light-sensitive material.

In addition, the stabilizing tank of the automatic developing machine is a processing tank having first to third layers in the direction of flow of the photosensitive material, replenishment is carried out from the final tank, and overflow from the final tank is allowed to flow into the tank at the preceding stage, Further, a counter current system is adopted in which the overflow liquid is allowed to flow into the tank at the previous stage.

Next, the processed sample is irradiated with light from a halogen lamp (500 W) at 70 ° C and 80% RH (relative humidity) and stored for 3 weeks. The reflection density of the maximum density part is measured using the Sakura optical densitometer PDA-65 (Konishi). It was measured by Rokushoku Kogyo Co., Ltd., and the reduction rate of the cyan dye concentration after storage was calculated as a percentage. Similarly, treat the treated sample at 75 ℃, 6
It was stored in the dark under 5% RH conditions (5 days), and the reduction rate of the cyan dye concentration after storage was calculated as a percentage. The results are shown in Table-6.

From the above results, it can be seen that the effect of the present invention can be sufficiently exerted in the light-sensitive material for photographic paper, as in the light-sensitive material for negative.

Example-8 The compound of the present invention was added to the bleach-fixing solution shown in Example-7, and the same evaluation as in Example-7 was carried out. The results are shown in Table-7.

It can be seen that the effects are sufficiently exhibited even when the compound of the present invention is added to the bleach-fixing solution.

Example-9 The cyan couplers according to the present invention used in Example-7 are cyan couplers C-37 and C- according to the present invention.
38 and C-59 were used, and the same evaluation as in Example-7 was carried out, but the same results as in Example-7 were obtained.

Claims (1)

[Claims] 1. A silver halide emulsion layer containing at least one cyan coupler selected from a cyan coupler represented by the following general formula [I] and a cyan coupler represented by the following general formula [II]. A method of processing a silver halide color photographic light-sensitive material, which comprises exposing the silver halide color photographic light-sensitive material imagewise and then processing it with a processing liquid containing a hexamethylenetetramine compound. General formula [I] General formula [II] [Wherein Y is -COR ₂ , -SO ₂ R _2, -CONHCOR ₂ or -CONHSO ₂ R ₂ (R ₂ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₃ is a hydrogen atom, an alkyl group, an alkenyl group, Represents a cycloalkyl group, an aryl group or a heterocyclic group, and R ₂ and R ₃ may combine with each other to form a ring). R ₁ represents a ballast group. Z represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a color developing agent. ]