JPH07120027B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a processing method of a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material) which omits a water-washing processing step, and more specifically, it improves storage durability under irradiation of light under high temperature and high humidity by continuous processing. The present invention relates to a method for washing an exposed light-sensitive material with water.

[Prior art]

Generally, a light-sensitive material is subjected to processing steps such as color development, bleaching, fixing, stabilizing, bleach-fixing and washing after image exposure.
In such a treatment process, the depletion of water resources and the increase in the cost for washing water due to an increase in the price of crude oil have become more and more serious problems in recent years. Therefore, as a method of omitting the washing treatment step or reducing the amount of washing water extremely, a multistage countercurrent stabilization treatment technique as described in JP-A-57-8543 and JP-A-58-58
A treatment technique using a water-washing alternative stabilizing solution containing a bismuth complex salt as described in JP-A-134636 has been proposed. However, in the treatment using the stabilizing solution as a substitute for washing with water, the total amount of the replenishing solution to the stabilizing tank solution is 6 times the stable tank capacity.
~ 7 times more than continuous processing for a long time,
It was found that the processed light-sensitive material was stained to cause color stain. It has been found that the generation of this stain is a serious defect that deteriorates the storage durability particularly when the dye image is stored, under the irradiation of light under high temperature and high humidity. Further, it was found that the above stain was generated when the processing solution having fixing ability contained iodide ions.

[Object of the Invention]

Therefore, an object of the present invention is to provide a processing method for preventing deterioration of storage stability of a dye image when continuously processed using a water-washing alternative stabilizing solution, particularly deterioration of photobleaching property under high temperature and high humidity. .

[Constitution of the invention]

 As a result of earnest studies, the present inventor found that one surface of the support was
The total dryness of the photosensitive silver halide emulsion layer and the non-photosensitive layer
2 equivalents of pyrazoloazole type with dry film thickness of 10 μm or more
A silver halide color photographic light-sensitive material containing no coupler
Substantially free of benzyl alcohol after imagewise exposure
After processing with color developer, add 10 parts of iodide.^-3Contains more than mol / l
Treated with a treatment solution that has fixing ability, and subsequently the surface tension
8 to 50 dyne / cm, containing formaldehyde substantially
Special feature is to treat with a stabilizing solution instead of washing with water and then dry.
The method of processing silver halide color photographic light-sensitive materials
Therefore, it has been found that the object of the present invention is achieved. The present inventor has also found that as a preferred embodiment of the present invention,
The optical material contains a sensitizing dye represented by the following general formula [I]
Found that the effect of the present invention is more remarkable when
It was General formula [I]Where Z₁And Z₂Are the benzoxazole nucleus and naphtho
Xazole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, naphthoselenazole nucleus,
Nzoimidazole nucleus, naphthimidazole nucleus, pyridine
Represents the atomic group necessary to form a nucleus or a quinoline nucleus,
R₁And R₂Are alkyl, alkenyl or aryl
Represents a group, R₃Represents a hydrogen atom, a methyl group or an ethyl group
Then X₁ Represents an anion, and l represents 0 or 1. The present invention will be further described below. In the conventional washing process after development, bleaching and fixing,
Depending on the amount of washing water,
Emulsion composition and processing liquid composition (color developing agent,
(Including dill alcohol, bleach, thiosulfate, etc.) or
All of those reactants and oxidants have been washed away.
It was Therefore, treatment with a stabilizing solution that is an alternative to washing without the washing process
The reason is that all these components are eluted and accumulated in the stable solution.
Will be. Especially when the supplement amount of the stabilizing solution for washing is small.
In this case, the accumulated concentration of the substance to be cleaned increases. More water
It is stored for a long period of time due to a decrease in the liquid renewal rate of the wash replacement stabilizer.
Coloring of the substance in the stabilizing solution as a substitute for washing with water.
Since it is an ingredient, the stabilizing solution for washing with water is considerably colored and
Adsorption of these coloring components to the light-sensitive material in the wash-stabilizing solution
Or that washout from the photosensitive material is suppressed
Therefore, the photosensitive material is contaminated and deterioration of image storage is accelerated.
It is presumed that. Benzyl alcohol has long been a popular development accelerator.
It has been used in color developers. Also, normal color processing
The final step in the process is the formalin aldehyde compound.
Is used in the final stabilizer for image stability
Is also well known. In the present invention, after color development, a processing solution having fixing ability is used.
Processing means photosensitive material after processing with a normal color developer.
Of fixing bath or bleach-fixing bath for the purpose of fixing the dye
It refers to the process of using. That is, the present invention is to bleach after color development.
Bath-An alternative to washing with water after treatment with a fixing bath or a bleach-fixing bath
This is a solution to the problem of constant solution.
It is particularly effective for processing in a bleach-fixing bath. In the present invention, iodine contained in the processing solution having fixing ability
Compounds are potassium iodide, sodium iodide, ammonium iodide
It produces iodine ions such as ammonium and silver iodide. The method of addition is to add directly to the tank solution and replenisher solution.
Or, by incorporating it in a light-sensitive material, it can be processed continuously.
A method of incorporating an iodide into a fixing solution or a bleach-fixing solution.
It The present invention uses iodide as a processing solution having a fixing ability.^-3Mole
/ l or more, but preferably 10^-3~ 5x
Ten^-2Mol / l range, most preferably 2 × 10^-3~ 2
× 10^-2Mol / l. In the present invention, treatment with a treatment liquid having fixing ability
Subsequent treatment with a stabilizing solution instead of washing with water
When fixing, wash directly with the fixing bath or bleach-fixing bath.
This indicates that treatment with an alternative stabilizer is required.
The process is based on the conventionally known fixing bath or bleach-fixing bath.
After that, it is completely different from the process of washing with water and treating with a stabilizing solution
ing. As described above, in the present invention, treatment with a stabilizing solution as a substitute for washing with water
Is a stabilization treatment immediately after treatment with a treatment solution having fixing ability.
Of stabilization treatment that does not actually wash with water.
The treatment liquid used for the stabilization treatment is washed with water.
The alternative stabilizing solution is called the stabilizing bath or stabilizing bath. In the present invention, when the number of stabilizing tanks is 1 to 5, the effect of the present invention
The fruit is large, and particularly preferably 1 to 3 tanks. That is, supplement
If the filling volume is the same, the more stable the tank, the more stable the final stability will be.
The effect of the present invention is weak because the concentration of dirt components in the bath is low.
Become. Surface tension of water-washing substitute stabilizer used in the treatment of the present invention
"Analysis of surfactants and test methods" (Fumio Kitahara, Hayano
Shigeo and Ichiro Hara, published March 1, 1982, Kodansha Ltd.
It is measured by the general measurement method described in
Therefore, in the present invention, it is possible to use the usual general measurement method at 20 ° C.
It is the value of the surface tension. The stabilizer of the present invention has a surface tension of 8 to 50 dyne / cm (20 ° C).
Anything can be used as long as it gives
The following general formula [II], general formula [III] and water-soluble
At least one compound selected from organic siloxane compounds
Compound is particularly preferable from the viewpoint of the effect for the purpose of the present invention.
Used well. General formula [II] A-O- (B) m-X₂ In the formula, A is a monovalent organic group, for example, having 6 to 20 carbon atoms,
Preferably, it is an alkyl group of 6 to 12, hexyl, hep
Chill, octyl, nonyl, decyl, undecyl or dode
Represents sill, etc. Or an alkyl group having 3 to 20 carbon atoms
It is a substituted aryl group, and the substituent is preferably
Alkyl groups having 3 to 12 carbon atoms, such as propyl and bromo.
Chill, pentyl, hexyl, heptyl, octyl, noni
It represents le, decyl, undecyl, dodecyl, or the like. Ants
Groups include phenyl, tolyl, xylyl, biphenyl.
And naphthyl, and preferably phenyl or triphenyl.
It is Le. As the position where the alkyl group is bonded to the aryl group
Any of the ortho, meta, and para positions may be used. B is et
Represents lenoxide or propylene oxide, m is 4 to
Represents an integer of 50. X₂Is a hydrogen atom, SO₃Y or PO₃Y₂Shows
However, Y is a hydrogen atom, an alkali metal (Na, K or Li, etc.)
Represents an ammonium ion. General formula (III)Where R_Four, R_Five, R₆And R₇Are hydrogen atom and alkyl
Group, phenyl group, but R_Four, R_Five, R₆And R₇Carbon atom
The total number is 3-50. X₃Is a halogen atom, hydroxyl group,
Sulfate group, carbonate group, nitrate group, acetate group, p-toluenesulfo
An anion such as an acid group is shown. The water-soluble organosiloxane compound of the present invention is, for example,
Kaisho 47-18333, Japanese Patent Publication 55-51172, Japanese Patent Publication 51-3753
No. 8, JP-A-49-62128 and U.S. Pat.
General water-soluble organic shiroki as described in
Means a sun-based compound. Next, a compound represented by the general formula [II] or [III] of the present invention
And specific representative examples of water-soluble organosiloxane compounds
However, the compounds according to the present invention are not limited to these.
There is no. (Example of compound represented by general formula [II]) II-1C₁₂H_{twenty five}O (C₂H_FourO)_10H II-2C₈H₁₇O (C₁₃H₆O)₁₅H II-3C₉H_TenO (C₂H_FourO)_FourSO₃Na II-4C_TenH_{twenty one}O (C₂H_FourO)₁₅PO₃Na₂  (Example of compound represented by general formula [III]) (Water-soluble organosiloxane compound) Among the water-soluble organosiloxane compounds,
The compound represented by the general formula [IV] has the effect of the object of the present invention.
In the present invention, it is more preferably used in order to produce good results.
To be General formula (IV)Where R₈Is a hydrogen atom, a hydroxy group, a lower alkyl group,
An alkoxy group,Represents R₉, R_TenAnd R₁₁Are each a lower alkyl group (preferably
More preferably, it is an alkyl group having 1 to 3 carbon atoms and is methyl,
Examples include ethyl and propyl. ) Represents the R₉, R_TenOver
And R₁₁May be the same or different. n represents an integer of 1 to 4, p and q represent an integer of 1 to 15.
You In the present invention, the surface tension of the second stabilizing liquid is 8 to
Among those given to 50 dyne / cm, especially 15-40 dyne /
What gives a surface tension of cm is the point of the effect on the present invention.
Therefore, it is particularly preferably used. Compounds represented by the above general formulas [II] and [III]
And water-soluble organosiloxane compounds are used alone
Alternatively, they may be used in combination. In addition,
When using in the range of 0.01 to 20 g per stabilizer,
Has a good effect on. In the present invention, formaldehyde is not substantially contained.
An alternative stabilizer for washing with water is used in the treatment process that involves conventional washing.
In order to improve the storage stability of the dye image in the final stabilizer, 1.
5 ~ 2.0g / l The added formaldehyde concentration is 0.1
It refers to a stabilizing solution that is g / l or less and is an alternative to washing with water. About 0.02g / l
However, it is particularly preferable that
It is not to contain at all. Sensitized color represented by the general formula [I] used in the present invention
In prime, Z₁And Z₂Even if the nucleus represented by
Often, the substituents are halogen atoms (eg chlorine),
Alkyl group (eg methyl, ethyl), alkoxy group (eg
Eg methoxy, ethoxy), alkoxycarbonyl groups
(Eg methoxycarbonyl, ethoxycarbonyl),
Aryl groups (eg phenyl), cyano groups, etc.
It R₁And R₂An alkyl group and an alkenyl group represented by
Preferably having 5 or less carbon atoms, preferably R₁And R₂Is al
It is a kill group. Specific compounds of the sensitizing dye represented by the general formula [I] are shown below.
However, the present invention is not limited to these. Amount of sensitizing dye represented by the general formula [I] added to the emulsion
Is 2 × 10 per mol of silver halide^-6~ 1 x 10^-3Mole
A suitable enclosure is 5 × 10^-6~ 5 x 10^-FourIn moles
is there. Many of the above light-sensitive materials are green-sensitive or blue-sensitive in light-sensitive materials.
In the wavelength range called sensitivity, the above-mentioned increase is possible within the limit permitted by the spectral sensitizing ability.
It is desirable that the dye be spectrally sensitized with a dye.
At least green-sensitive emulsion and blue-sensitive emulsion
Most of the sensitizing dyes (50 mol% or more) are the above sensitizing dyes.
And are preferred. The stabilizing solution for washing with water of the present invention may contain an antifungal agent.
preferable. Antifungal agents preferably used are salicylic acid,
Sorbic acid, dehydroacetic acid, hydroxybenzoic acid compounds
Compounds, alkylphenol compounds, thiazole compounds
Compounds, pyridine compounds, guanidine compounds, carbamate
Ito compounds, morpholine compounds, quaternary phosphonium
Compounds, ammonium compounds, urea compounds, iso
Xazole compounds, propanolamine compounds, su
Lufamide derivatives and amino acid compounds. The hydroxybenzoic acid compound is hydroxybenzoic acid.
Acid and hydroxybenzoic acid ester compounds
Chill ester, ethyl ester, propyl ester, de
There are chill esters and the like, but preferably hydroxybenzoic
N-Butyl ester, isobutyl ester of acid, propyl ester
And a hydroxyester, more preferably the hydroxybenzoate
It is a mixture of three fragrance esters. Alkylphenol compounds have an alkyl group with 1 carbon atom
A compound having an alkyl group of ~ 6 as a substituent,
More preferably orthophenylphenol and orthocyclohexyl
Xyphenol. A thiazole-based compound has a nitrogen atom and a sulfur atom in the 5-membered ring.
And is preferably 1,2-benzisothia.
Zolin-3-one, 2-methyl-4-isothiazoline 3-
On, 2-octyl-4-isothiazolin-3-one, 5
-Chloro-2-methyl-4-isothiazolin-3-one,
2- (4-thiazolyl) benzimidazole. Pyridine compounds are specifically 2,6-dimethylpyrididinium
1,2,4,6-trimethylpyridine, sodium-2-pyriline
Zinthiol-1-oxide, etc., but preferably
Sodium-2-pyridinethiol-1-oxide
It The guanidine compounds are specifically cyclohexidine and
Lihexamethylene Biguanidine Hydrochloride, Dodecyl Guani
Gin hydrochloride, etc., preferably dodecylguanidine
And its salts. The carbamate compound is specifically methyl-1- (butyrate).
Lucabamoyl) -2-benzimidazole carbamay
And methyl imidazole carbamate. The morpholine compound is specifically 4- (2-nitrobutyrate).
) Morpholine, 4- (3-nitrobutyl) morpholine
Etc. Quaternary phosphonium compounds are tetraalkylphosphonium
There are various salts, such as tetra-alkoxyphosphonium salt, but
More preferably, it is a tetraalkylphosphonium salt.
Physically preferred compound is tributyl tetradecylphos
Fonium chloride and triphenyl nitrophenyl
It is phosphonium chloride. The quaternary ammonium compound is specifically benzalkonium
Salt, benzethonium salt, tetraalkylammonium
There are salts, alkylpyridinium salts, and the like. More specifically,
Dodecyldimethylbenzyl ammonium chloride, do
Decyl dimethyl ammonium chloride, lauryl pyri
For example, dinium chloride. The urea-based compound is specifically N- (3,4-dichlorophenyl)
) -N '-(4-chlorophenyl) urea, N- (3-
Trifluoromethyl-4-chlorophenyl) -N'-
(4-chlorophenyl) urea and the like. The isoxazole-based compound is specifically 3-hydroxy-
5-methyl-isoxazole and the like. Propanolamine-based compounds include n-propanols
There are isopropanols, specifically DL-2-benz
Luamino-1-propanol, 3-diethylamino-1
-Propanol, 2-dimethylamino-2-methyl-1
-Propanol, 3-amino-1-propanol, id
Propanolamine, diisopropanolamine, NN-
Dimethyl-isopronol amine and the like. The sulfamide derivative is specifically fluorinated sulfamide.
De, 4-chloro-3,5-dinitrobenzene sulfami
De, sulfanilamide, acetosulfamine, sulf
Pyridine, sulfaguanidine, sulfathiazo
Le, sulfadiazine, sulfamelazine, sulfame
Tadine, sulfisoxazole, homosulfami
, Sulfisomidine, sulfaguanidine, sulfa
Methizole, sulfapyrazine, phthalisosulfaty
Examples include azole and succinylsulfathiazole. The amino acid compound is specifically N-lauryl-β-ara.
There is nin. Among the above antifungal agents, the antifungal agent is preferably used in the present invention.
Compounds are pyridine compounds, guanidine compounds and
And quaternary ammonium compounds. The amount of antifungal agent added to the stabilizing solution for washing is
It is used in the range of 0.002 g to 50 g per 1 and preferably
Used in the range of 0.005g-10g. The pH of the stabilizing solution for washing with water in the present invention is more effective in the present invention.
In order to achieve the goal, preferably in the range of 3.0 to 10.0
, More preferably pH 5.0 to 9.5, particularly preferably
The pH is preferably in the range of 6.0 to 9.0. An alternative to washing with water according to the present invention
The pH adjuster that can be contained in the constant solution is generally known.
You can use any of the alkaline or acid agents
It The present invention is applicable to the case where the stabilizing bath replacement stabilizing solution replenishment amount is small.
The effect is large, and the replenishment amount of the photosensitive material
Range of 1 to 50 times the amount brought in from the previous bath per unit area
Is preferable, and the effect of the present invention is particularly preferable in the range of 2 to 20 times.
Is remarkable. The treatment temperature for stabilizing treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ~ 45 ℃ is good. Also, is the processing time a point of view for rapid processing?
The shorter the time, the better.
It is also preferably 1 to 3 minutes, and is suitable for multi-tank stabilization treatment.
In the case of
It is preferably long. 20% to 50% increase in treatment of the previous tank
It is desirable to process sequentially in time. Supply of a substitute liquid for washing with water in the stabilization treatment process according to the present invention
When the method is a multi-tank counter current method, a post-bath
It is preferable to supply it to
Yes. Of course, it can also be processed in a single tank. The above compound
As a method of adding, add as a concentrated liquid to the stabilizing tank.
Or use a stabilizing solution as a substitute for rinsing that is supplied to the stabilization tank.
Add the above compounds and other additives, and wash this with water.
There are various methods such as whether to use the supply liquid for the constant replenisher.
However, they may be added by any addition method. The bleaching solution or bleach-fixing solution used in the present invention contains a bleaching agent and
It is preferable that the organic acid ferric complex salt is contained. Organic acids Organic acids that form ferric complex salts are listed below.
Is a typical example. (1) Diethylenetriamine pentaacetic acid (MW = 393.27) (2) Diethylenetriamine pentamethylenephosphonic acid (MW
= 573.12) (3) Cyclohexanediaminotetraacetic acid (MW = 364.35) (4) Cyclohexanediaminetetramethylenephosphonic acid
(MW = 508.23) (5) Triethylenetetramine hexaacetic acid (MW = 364.35) (6) Triethylenetetramine hexamethylenephosphonic acid
(MW = 710.72) (7) Glycol ether diamine tetraacetic acid (MW = 380.3
5) (8) Glycol ether diamine tetramethylene phosphone
Acid (MW = 524.23) (9) 1,2-Diaminopropanetetraacetic acid (MW = 306.27) (10) 1,2-Diaminopropanetetramethylenephosphonic acid (M
W = 450.15) (11) 1,3-Diaminopropan-2-ol tetraacetic acid (MW
= 322.27) (12) 1,3-diaminopropan-2-ol tetramethylene
Phosphonic acid (MW = 466.15) (13) Ethylenediaminedioltohydroxyphenyl vinegar
Acid (MW = 360.37) (14) Ethylenediamine dioltohydroxyphenylmeth
Tylene phosphonic acid (MW = 432.31) (15) Ethylenediaminetetramethylenephosphonic acid (MW = 43
6.13) (16) Ethylenediaminetetraacetic acid (MW = 292.25) (17) Nitrilotriacetic acid (MW = 191.14) (18) Nitrilotrimethylenephosphonic acid (MW = 299.05) (19) Iminodiacetic acid (MW = 133.10) (20) Iminodimethylenephosphonic acid (MW = 205.04) (21) Methyliminodiacetic acid (MW = 147.13) (22) Methyliminodimethylenephosphonic acid (MW = 219.0)
7) (23) Hydroxyethyliminodiacetic acid (MW = 177.16) (24) Hydroxyethyliminodimethylenephosphonic acid
(MW = 249.10) (25) Ethylenediaminetetrapropionic acid (MW = 348.
35) (26) Hydroxyethylglycidin (MW = 163.17) (27) Nitrilotripropionic acid (MW = 233.22) (28) Ethylenediaminediacetic acid (MW = 176.17) (29) Ethylenediaminedipropionic acid (MW = 277.15) Organic acid The ferric complex salt is not limited to these, but these
One of them can be selected and used, and
If necessary, two or more types can be used in combination.
It Of the organic acids forming the ferric salt of the organic acid used in the present invention,
The following are particularly preferred. (1) Diethylenetriaminepentaacetic acid (MW = 393.27) (3) Cyclohexanediaminotetraacetic acid (MW = 364.35) (5) Triethylenetetraminehexaacetic acid (MW = 394.45) (7) Glycoletherdiaminetetraacetic acid (MW = 380.3)
5) (9) 1,2-Diaminopropanetetraacetic acid (MW = 306.27) (11) 1,3-Diaminopropan-2-ol tetraacetic acid (MW
= 322.27) (19) Iminodiacetic acid (MW = 133.10) (21) Methyliminodiacetic acid (MW = 147.13) (23) Hydroxyethyliminodiacetic acid (MW = 177.16) (28) Ethylenediaminediacetic acid (MW = 176.17) Book The organic acid ferric complex salt used in the invention is a free acid (hydrogen acid).
Salt), sodium salt, potassium salt, lithium salt, etc.
Potassium metal salt, ammonium salt, or water-soluble salt
Used as a min salt such as triethanolamine
Preferably potassium salts, sodium salts and ammonium salts
Umm salt is used. These bleaching agents are 5-450 g / l, more preferably 20-250 g
Use with / l. In addition to the bleaching agents mentioned above, the bleach-fix solution
Contains a silver halide fixing agent, and as a preservative, if necessary
A liquid having a composition containing sulfite is applied. Also,
Iron (III) complex salt bleaching agent and the above silver halide fixing agent
Other small amount of halide such as ammonium bromide
Bleach-fix solution of the same composition, or conversely, ammonium bromide.
Consists of a composition in which a large amount of halide such as nickel is added
A bleach-fix solution, and moreover an organic acid iron (III) complex salt bleach
Amount of a halide such as ammonium bromide
It is also possible to use a special bleach-fix solution with a composition of
Wear. As the halide, ammonium bromide
Hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide
Lithium, potassium bromide, sodium iodide, potassium iodide
It is also possible to use aluminum, ammonium iodide and the like. As a silver halide fixing agent contained in fixer and bleach-fixer
And silver halide as used in normal fixing processing
Compounds that react to form water-soluble complex salts, such as thiol
Potassium sulfate, sodium thiosulfate, ammonium thiosulfate
Thiosulfates such as um, potassium thiocyanate, thiocyanate
Thie such as sodium anion and ammonium thiocyanate
Typical examples are cyanate, thiourea, thioether, etc.
It is something. These fixing agents can dissolve more than 5g / l
Used in a range of amounts, but generally 70g-250g / l
It In the fixing solution and the bleach-fixing solution, the above-mentioned fixing agent and the iodine of the present invention are used.
Compounds other than compounds such as boric acid, borax, sodium hydroxide
, Potassium hydroxide, sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
There are various pH buffer agents such as ammonium and ammonium hydroxide
Alternatively, two or more kinds may be combined and contained.
Furthermore, various fluorescent whitening agents, antifoaming agents or surface active agents
An agent can also be included. Also hydroxylami
Organic killer such as amine, hydrazine and aminopolycarboxylic acid
Stabilizer or stabilizer such as nitro alcohol, nitrate,
Methanol, dimethyl sulfamide, dimethyl sulfoxide
An organic solvent such as side can be appropriately contained. The bleach-fixing solution used in the present invention is described in JP-A-46-280,
Kosho 45-8506, 46-556, Belgian Patent 770,910
No. 5, Japanese Patent Publication No. 45-8836, No. 53-9854, JP-A-54-7163
No. 4 and 49-42349, etc.
A promoter may be added. The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally
Used at pH 5.0 to pH 9.5, preferably pH 6.0 to pH
Used below 8.5, further stated the most preferred pH is 6.5
Processed above 8.5. Processing temperature is below 80 ℃
3 ° C or higher, preferably 5 ° C, higher than the temperature of the processing solution in the color developing tank
It is used at lower temperatures, but it is desirable to steam below 55 ° C.
Use while suppressing the generation. The light-sensitive material used in the method of the present invention has a halogen on a support.
Coated with a silver halide emulsion layer and a non-photosensitive layer (non-emulsion layer)
The silver halide emulsions are silver chloride and bromide.
Silver, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide
Whichever silver halide is used
Yes. These emulsion layers and non-light sensitive layers are known in the photographic industry.
Incorporation of all applicable couplers and additives
, For example, yellow dye-forming coupler, magenta
Dye-forming coupler, cyan dye-forming coupler, stabilizer,
Sensitizing dye, gold compound high boiling organic solvent, antifoggant, color
Elementary image fading prevention agent, color stain prevention agent, fluorescent whitening agent, antistatic
Anti-static agents, hardeners, surfactants, plasticizers, wetting agents and UV
A ray absorbent or the like can be appropriately contained. The light-sensitive material used in the method of the present invention is
An emulsion layer containing various photographic additives as described above and
And each non-photosensitive layer, etc., corona discharge treatment, flame
On a support that has been treated or treated with UV irradiation, or
By coating on a support through an undercoat layer and an intermediate layer,
Manufactured. As the support used advantageously, for example,
Bavaria paper, polyethylene coated paper, polypropylene compound
Paper, glass plate, cellulose acetate, cellulose
Itate or polyethylene terephthalate
Stell film, polyamide film, polycarbonate
There are to film, polystyrene film and the like. Most of the silver halide emulsion layer and the non-light-sensitive layer are transparent.
Normally, it is a hydrophilic colloid layer containing a hydrophilic binder.
ing. As the hydrophilic binder, gelatin,
Or acylated gelatin, guanidylated gelatin, flux
Phenylcarbamylated gelatin, phthalated gelatin, shea
Zera such as noethanol gelatin and esterified gelatin
A tin derivative is preferably used. As a hardening agent for hardening this hydrophilic colloid layer
Is, for example, chromium salt (chromium alum, chromium acetate,
Th), aldehydes (formaldehyde, glyoxer)
Compound, glital aldehyde, etc.), N-methylol compound
Thing (dimethylol urea, methylol dimethyl hydantoy
Dioxane derivative (2,3-dihydroxydio
Active vinyl compounds (1,3,5-triacryl)
Royl-hexahydro-s-triazine, 1,3-vinyl
Sulfonyl-2-propanol, etc.), active halogenation
Compound (2,4-dichloro-6-hydroxy-s-triazi
), Mucohalogenates (mucochloric acid, mucofe
(Noxic acid, etc.), etc., alone or in combination
Used. In the present invention, the light-sensitive material uses a coupler as a high-boiling organic solvent.
So-called oil pro that contains the dispersed ones
This is especially effective in the case of tect type. This high boiling organic
As a solvent, organic acid amides, carbamates, ester
, Ketones, urea derivatives, especially dimethylphthale
, Diethyl phthalate, di-propyl phthalate,
Di-butyl phthalate, di-n-octyl phthalate,
Diisooctyl phthalate, diamyl phthalate, dino
Phthales such as nyl phthalate and diisodecyl phthalate
Acid ester, tricresyl phosphate, triphenyl
Phosphate, tri- (2-ethylhexyl) phosphate
Phosphate, trinonyl phosphate, etc.,
Dioctyl sebacate, di- (2-ethylhexyl) se
Sebacic acid such as bacate and diisodecyl sebacate
Stell, glycerol tripropionate, glycero
Glycerin esters such as rutributyrate, which
Others, adipate, glutarate, amber
Curic acid ester, maleic acid ester, fumaric acid ester
, Citric acid ester, di-tert-amylphenol,
Using phenol derivatives such as n-octylphenol
In this case, the effect of the present invention is great. The layer structure of the light-sensitive material used in the present invention is a color negative film.
Media, color paper and reverse color film
Can be of known construction, eg yellow on one side of the support
Blue-sensitive silver halide emulsion containing dye-forming coupler
Layer, a green-sensitive halogen containing magenta dye-forming coupler
Red containing silver halide emulsion layer and cyan dye forming coupler
Sensitive silver halide emulsion layer (each of these color-sensitive layers is one layer or
Is composed of two or more layers)
It The light-sensitive material used in the present invention has the following general formula [V] or
Or it is preferable to use the cyan coupler represented by [VI].
Good General formula [V]General formula [VI]In the formula, Y'is -COR '₂,−CONHCOR ′₂Or-CONHSO₂R '₂(R '₂Is alkyl
Group, alkenyl group, cycloalkyl group, aryl group or
Represents a heterocyclic group, R '₃Is a hydrogen atom, alkyl group,
Lucenyl group, cycloalkyl group, aryl group or hetero
Represents a ring group, R '₂And R '₃And are combined with each other 5 or
A 6-membered ring may be formed. ), And R ′₁Ballast
Represents a group, Z'is a hydrogen atom or an aromatic primary amine coloring
The group that can be released by coupling with the oxidized form of the developing agent
Represent Where R '₂Is an alkyl group, preferably 1 to 20 carbon atoms
Alkyl groups (eg, methyl, ethyl, t-butyl,
Decyl etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms.
Lucenyl group (eg, allyl group, heptadecenyl group, etc.),
A cycloalkyl group, preferably of 5 to 7 membered ring (eg
Eg cyclohexyl), aryl groups (eg phenyl)
Group, tolyl group, naphthyl group, etc.), heterocyclic group, preferably
Contains 1 to 4 nitrogen, oxygen or sulfur atoms
A 5- to 6-membered heterocyclic group (for example, a furyl group, thieny
Group, benzothiazolyl group, etc.). R '₃Is hydrogen
Child or R '₂Represents a group represented by. R '₂And R '₃When
Is a 5- to 6-membered heterocycle containing a nitrogen atom bonded to each other
May be formed. In addition, R '₂And R '₃To any position
A substituent can be introduced, for example, an alkyl group having 1 to 10 carbon atoms.
Kill group (eg ethyl, i-propyl, i-butyl, t
-Butyl, t-octyl, etc.), aryl groups (eg,
Nyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, odor)
Element), cyano, nitro, sulfonamide groups (for example,
Tansulphonamide, butanesulphonamide, p-tolu
Ensulfonamide etc.), sulfamoyl group (eg
Tilsulfamoyl, phenylsulfamoyl, etc.),
Rufonyl group (eg methanesulfonyl, p-toluene)
(Eg, sulfonyl), fluorosulfonyl, carbamoyl group
(For example, dimethylcarbamoyl, phenylcarbamoyl
Etc.), an oxycarbonyl group (eg, ethoxycarbonyl
, Phenoxycarbonyl, etc.), an acyl group (eg
Tyl, benzoyl, etc.), heterocyclic groups (eg pyridyl)
Group, pyrazolyl group, etc.), alkoxy group, aryloxy
Group, acyloxy group and the like. In the general formulas [V] and [VI], R '₁Is the general formula
Cyan couplers represented by [V] and [VI], and
Diffusion resistance for cyan dyes formed from cyan couplers
Represents a ballast group necessary for imparting. Preferably carbon
An alkyl group, an aryl group or a heterocyclic group having the number of 4 to 30
is there. For example, a linear or branched alkyl group (for example, t-
Butyl, n-octyl, t-octyl, n-dodecyl
Etc.), alkenyl group, cycloalkyl group, 5-membered or
Examples include 6-membered heterocyclic groups. In the general formulas [V] and [VI], Z ′ is a hydrogen atom or
During the coupling reaction with the oxidation product of the color developing agent
Represents a releasable group. For example, a halogen atom (eg salt
Elemental, bromine, fluorine, etc.), substituted or unsubstituted alkoxy
Group, aryloxy group, heterocyclic oxy group, acyloxy group
Si group, carbamoyloxy group, sulfonyloxy group, a
Rukylthio group, arylthio group, heterocyclic thio group, sulphyl group
Examples include honamide group, and more concrete examples
U.S. Pat.No. 3,741,563, JP-A-47-37425, JP-B-48-
36894, JP-A-50-10135, 50-117422, 50-
130441, 51-108841, 50-120343, 52-18
No. 315, No. 53-105226, No. 54-14736, No. 54-48237
No. 55, No. 55-32071, No. 55-65957, No. 56-1938, No.
56-12643, 56-27147, 59-146050, 59-
166956, 60-24547, 60-35731, 60-3755
Those described in each publication of No. 7 are listed. In the present invention, the compound represented by the general formula [V] or [VI] is
Among the cyan couplers to be used, the following general formulas [VII], [V
Cyan couplers represented by III] or [IX] are more preferable.
Good General formula (VII)General formula [VIII]General formula [IX]In the general formula [VII], R '_FourIs a substituted or unsubstituted ally
Group (particularly preferably a phenyl group). The aryl
When the group has a substituent, the substituent is -SO.
₂R '₆, Halogen atoms (eg fluorine, bromine, chlorine
Etc.), -CF₃, -NO₂, -CN, -COR '₆, −COOR ′₆, -S
O₂OR ′₆, At least one substituent selected from is included. Where R '₆Is an alkyl group, preferably 1 to 20 carbon atoms
An alkyl group of (for example, methyl, ethyl, tert-butyl,
Each group such as dodecyl), alkenyl group, preferably carbon number
2 to 20 alkenyl groups (eg allyl groups, heptadeceni
Group, etc.), cycloalkyl group, preferably 5- to 7-membered ring group
(Eg cyclohexyl group), aryl group (eg
Phenyl group, tolyl group, naphthyl group, etc.) and R '₇Is
Hydrogen atom or R '₆Is a group represented by. Phenolic cyan coupler represented by general formula [VII]
Preferred compounds of R '_FourIs a substituted or unsubstituted phenyl
And a phenyl or cyano group as a substituent to the phenyl group.
B, -SO₂R '₈(R '₈Is an alkyl group), halogen source
A compound that is trifluoromethyl. In the general formulas [VIII] and [IX], R_FiveIs alkyl
A group, preferably an alkyl group having 1 to 20 carbon atoms (eg methyl group).
, Ethyl, tert-butyl, dodecyl, etc.), alkenyl
A group, preferably an alkenyl group having 2 to 20 carbon atoms (for example, an alkenyl group).
Ryl, oleyl, etc.), a cycloalkyl group, preferably 5
~ 7-membered ring group (eg cyclohexyl), aryl group
(Eg phenyl group, tolyl group, naphthyl group, etc.), het
B ring groups (nitrogen atom, oxygen atom, or sulfur atom
5 to 6 membered heterocycles containing 4 to 4 are preferred, for example
Furyl group, thienyl group, benzothiazolyl group, etc.
Is represented). R '₆, R ′₇And of the general formulas [VIII] and [IX]
R '_FiveIn addition, an optional substituent can be introduced into
Specifically, in the general formulas [V] and [VI],
R '₂Or R '₃Substituents that can be introduced into
Is. And as a substituent, a halogen atom (salt
(Atom atom, fluorine atom, etc.) are preferable. In the general formulas [VII], [VIII] and [IX], Z'and
And R '₁Are the same meanings as in general formulas [V] and [VI], respectively.
Have a taste. R '₁The preferred ballast group represented by
Another example is a group represented by the following general formula [X]. General formula [X]In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group.
, K represents an integer of 0 to 4, l represents 0 or 1, and
When k is 2 or more, there are two or more R '._TenAre the same but different
R'can be₃Is a straight chain having 1 to 20 carbon atoms or
Show branched and substituted alkylene groups such as aryl groups.
And R '_TenRepresents a monovalent group, preferably a hydrogen atom or
Rogen atoms (eg chromium, bromine), alkyl groups,
Preferably, it is a linear or branched alkyl group having 1 to 20 carbon atoms.
(For example, methyl, t-butyl, t-pentyl, t-oct
Chill, dodecyl, pentadecyl, benzyl, phenethyl
Etc.), aryl groups (eg phenyl groups), heterocycles
Groups (preferably nitrogen-containing heterocyclic groups), alkoxy groups,
More preferably, it is a linear or branched alkoxy group having 1 to 20 carbon atoms.
(For example, methoxy, ethoxy, t-butyloxy, octa
Each of tyloxy, decyloxy, dodecyloxy, etc.
Group), aryloxy group (eg, phenoxy group), hydr
Roxy, acyloxy group, preferably alkylcarbonyl
Ruoxy group, arylcarbonyloxy group (for example,
Toxy group, benzoyloxy group), carboxy, alk
Ruoxycarbonyl group, preferably a straight chain having 1 to 20 carbon atoms
Or a branched alkyloxycarbonyl group, arylo
A oxycarbonyl group, preferably phenoxycarbonyl,
An alkylthio group, preferably 1 to 20 carbon atoms, an acyl group,
Preferably, a linear or branched alkyl group having 1 to 20 carbon atoms
Rubonyl group, acylamino group, preferably having 1 to 20 carbon atoms
Linear or branched alkyl carboxamide, benzene
Ruboamide, sulfonamide group, preferably 1 to 1 carbon atoms
20 linear or branched alkyl sulfonamide groups or
Benzene sulfonamide group, carbamoyl group, preferably
Linear or branched alkylaminocarbo having 1 to 20 carbon atoms
Nyl group or phenylaminocarbonyl group, sulfamoy
Group, preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms.
Killaminosulfonyl group or phenylaminosulfonyl
Represents a group or the like. Next, a cyan coupler represented by the general formula [V] or [VI]
Specific examples of the compound are shown below, but the invention is not limited thereto. [Compound example] These cyan couplers are synthesized by a known method.
For example, U.S. Patents 2,772,162 and 3,758,308
No. 3, No. 3,880,661, No. 4,124,396, No. 3,222,176,
British Patents 975,773, 8,011,693, 8,011,694,
JP-A-47-21139, 50-112038, 55-163537
No. 56-29235, No. 55-99341, No. 56-116030,
52-69329, 56-55945, 56-80045, 50
-134644, British Patent 1,011,940, U.S. Patent 3,4
46,622, 3,996,253, JP-A-56-65134, 57-
04543, 57-204544, 57-204545, Japanese Patent Application No. 56
-131312, 56-131313, 56-131314, 56-
131309, 56-131311, 57-149791, 56-13
0459, JP-A-59-146050, 166956, 60-2454
No. 7, No. 60-35731, No. 60-37557, etc.
Can be synthesized by the method. In the present invention, the shear represented by the general formula [V] or [VI]
The coupler is within a range not deviating from the object of the present invention.
It can be used in combination with a conventionally known cyan coupler.
it can. In addition, cyan couplers of general formulas [V] and [VI]
Can also be used together. Cyan of the present invention represented by the general formula [V] or [VI]
When the coupler is contained in the silver halide emulsion layer,
Usually about 0.005 to 2 mol per mol of silver halide, preferably
Or 0.01 to 1 mol. The stabilizing solution for washing with water in the present invention has the following general formula [XI] to
It is preferable to contain a chelating agent represented by [XXII].
Yes. General formula [XI] MmPmO₃m General formula [XII] Mn₊₂PnO₃n₊₁ General formula [XIII] A¹-R¹−Z¹-R²-COOH general formula (XIV)In the formula, E is a substituted or unsubstituted alkylene group, cycloalkyl
Xylene group, phenylene group, -R⁷-OR⁷−, −R⁷-OR⁷OR⁷
-Or-R⁷Z¹R⁷Represents-, Z₁Is> N-R⁷−A⁶Or> N-
A⁶Represents R¹~ R⁷Each is a substituted or unsubstituted alkylene group
Represents A¹~ A⁶Is a hydrogen atom, --OH, --COOM or --PO, respectively.₃
M₂And M represents a hydrogen atom or an alkali metal atom,
m represents an integer of 3 to 6, and n represents an integer of 2 to 20. General formula [XV] R⁸N (CH₂PO₃M₂)_Two Where R⁸Is a lower alkyl group, an aryl group, an aralkyl group
Or a nitrogen-containing 6-membered ring group (as a substituent, -OH, -OR or -CO
May have OM), M is a hydrogen atom or an ar
Represents a potassium metal atom. General formula [XVI]Where R⁹~ R¹¹Are hydrogen atom, -OH, lower alkyl (
-OH, -COOM or -PO as a substituent or substituent₃M₂Have
B)³~ B^FiveIs a hydrogen atom, --OH, --COOM,
-PO₃M₂Or-NJ₂Represents a hydrogen atom, lower alkyl
Group, -C₂H_FourOH or −PO₃M₂Represents a hydrogen atom or
Represents a Lucari metal atom, n₁And m₁Represents 0 or 1 respectively
You General formula (XVII)Where R¹²And R¹³Are hydrogen atom, alkali metal atom,
C₁~ C₁₂Alkyl group of C₁~ C₁₂Alkenyl group or cyclic
Represents an alkyl group, M is as defined in the general formula [XVI]
Is. General formula (XVIII)Where R¹⁴Is C_1-12Alkyl group of C_1-12Arco
Xy group, C_1-12Monoalkylamino group, C_2-12of
Dialkylamino group, amino group, C_1-24Aryloxy
Base, C_6-24The arylamino group and amyloxy group of
Represent, Q¹~ Q³Is -OH, C_1-24Alkoxy group of
Rukyroxy group, allyloxy group, -OM '₃(M 'is
Thione), amino group, morpholino group, cyclic amino
Group, alkylamino group, dialkylamino group, aryl
An amino group or an alkyloxy group is shown. General formula [XIX]General formula [XX]Where R¹⁵， R¹⁶， R¹⁷And R¹⁸Are hydrogen atom and halogen
Atoms, sulfonic acid groups, substituted or unsubstituted carbon atoms 1 to
7 alkyl group, -OR¹⁹, -COOR²⁰，Alternatively, it represents a substituted or unsubstituted phenyl group. R₃₉，
R²⁰， R^{twenty one}And R^{twenty two}Are each hydrogen atom or carbon atom number 1-18
Represents an alkyl group. General formula (XXI)Where R^{twenty three}And R^{twenty four}Is a hydrogen atom, a halogen atom or sulfo
Represents an acid group. General formula (XXII)Where R^{twenty five}And R²⁶Are a hydrogen atom, a phosphate group, and a carvone, respectively.
Acid group, -CH₂COOH, −CH₂PO₃H₂Or a salt thereof, X
₁Represents a hydroxyl group or a salt thereof, W, Z²And Y¹Is hydrogen source
Child, halogen atom, hydroxyl group, cyano group, carboxylic acid group,
Phosphoric acid group, sulfonic acid group or their salts, alkoxide
Represents an alkyl group or an alkyl group. Also m₂Is 0 or 1, n₂Is 1
~ 4, l is 1 or 2, p is an integer from 0 to 3, q is 0
Represents an integer of 2; A chelating agent represented by the general formula [XI] to [XXII]
The following are examples of body examples. [Exemplary chelating agent] (1) Na_FourP_FourO₁₂(2) Na₃P₃O₉ (3) H_FourP₂O₇ (4) H_FiveP₃O_Ten (5) Na₆P_FourO₁₃  (15) (HOC₂H_Four)_TwoNCH₂COOH In the present invention, the general formula [XI], [XII], [XV] or
It is effective to use the chelating agent represented by [XVI]
It Particularly preferred chelating agents (1), (3),
(5), (31), (44), (46), (48), (81),
The chelating agent represented by (82) is used. this
These chelating agents can be used in combination of two or more.
It Any of the above general formulas [XI] to [XXII] used in the present invention
The chelating agent shown here is per wash stabilizing substitute solution
1 x 10^-FourIt can be added in the range of 1 mol to 1 mol.
It ’s 2 × 10^-Four~ 1 x 10^-1Add in molar range
And more preferably 5 × 10^-Four~ 5 x 10^-2Molar range
Can be added at. In the light-sensitive material used in the present invention, one surface of the support is
The total dry film thickness of the photosensitive silver halide emulsion layer is 10 μm.
In the above case, the effect of the present invention is exerted, preferably 30 μm
Below, especially when it is in the range of 15 to 25 μm,
The effect is particularly remarkable. The total dry film thickness is less than 10 μm
Then, the effect of improving the pollution of the present invention is small. In the color development in the present invention, aromatic primary amine color development is used.
An image base is used, and various color photographic prints are used as the developing base.
Known items that are widely used in
Included. These developers are aminophenol-based and
A p-phenylenediamine derivative is included. these
Compounds are more stable than free and are generally in salt form, eg
Used in the form of hydrochloride or sulphate. Also these changes
In general, the amount of the compound is about 0.1 g to about 30 g for the color developer 1.
Of about 1, preferably about 1 g to about 1.
Use at a concentration of 5g. Examples of the aminophenol-based developer include o-amino.
Phenol, p-aminophenol, 5-amino-2-
Hydroxytoluene, 2-amino-3-hydroxytolu
Ene, 2-hydroxy-3-amino-1,4-dimethyl ester
It is included. Particularly useful aromatic primary amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups can be replaced by any
May be. Among them, examples of particularly useful compounds
NN′-diethyl-p-phenylenediamine hydrochloride,
N-methyl-p-phenylenediamine hydrochloride, N, N-di
Methyl-p-phenylenediamine hydrochloride, 2-amino-
5- (N-ethyl-N-dodecylamino) -toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-Β-hydroxyethylaminoaniline, 4-amino-3
-Methyl-N, N'-diethylaniline, 4-amino-N
-(2-Methoxyethyl) -N-ethyl-3-methyla
Nilin-p-toluene sulfonate and the like can be mentioned.
it can. In the present invention, benzyl alcohol is substantially contained.
No color developer is a normal color developer containing 10 to 20 ml / l.
When the concentration of benzyl alcohol is less than 1 ml / l
Yes, almost none. Of course, a concentration of about 0.5 ml / l
Is in a region containing substantially no, but particularly preferred is
This is the case when it contains no benzyl alcohol. The color developer contains the aromatic primary amine-based color developer.
In addition, various components that are usually added to color developers are added.
Minutes, for example sodium hydroxide, sodium carbonate, carbonate
Alkaline agents such as helium, alkali metal thiocyanates
Salts, alkali metal halides, water softeners and thickeners
Agents and the like can be optionally contained. Color developer
Color development using aromatic primary amine color developing agent as medicine
The pH value of the developer is usually 7 or higher, most commonly about
10 to about 13. Stabilizer and bleaching substitute for washing used in the treatment method of the present invention
The soluble silver complex salt contained in the fixer was recovered by a known method to recover silver.
May be. For example, electrolysis method (French Patent 2,299,667
Listed), precipitation method (described in JP-A-52-73037, German Patent 2,33).
1,220), ion exchange method (JP-A-51-17114, Germany)
National patent 2,548,237) and metal substitution method (UK patent 1,3
53,805) can be effectively used. The processing method of the present invention includes a color negative film and a reverse color.
Film, color negative paper, color positive paper
And it is advantageous to apply to the processing of reversal color paper
is there. In addition, as a treatment step in which the present invention is particularly effective, the following (1)
And (2). (1) Color development-bleach-fixing-water washing alternative stabilizing treatment (2) Color development-bleaching-fixing-water washing alternative stabilizing treatment [Example] The present invention will be specifically described with reference to the following examples.
However, the embodiment of the present invention is not limited thereto. Example 1 Antihalation layer on triacetate film base
And a gelatin layer are provided, and red-sensitive silver halide milk is provided on this.
Agent layer, green-sensitive silver halide emulsion layer, yellow colloidal silver
Having a filter layer and a blue-sensitive silver halide emulsion layer
100cm silver on the body²It is applied so that it will be 70 mg per
It was created. The above emulsion layers are made of silver iodobromide in which the mol% of silver iodide is about 10%.
At this time, the yellow color is not formed in the blue-sensitive silver halide emulsion layer.
Α- (4-nitrophenoxy) -α-piva as puller
Ryl-5- [γ- (2,4-di-t-aminophenoxy)
Butyramide] -2-chloroacetanilide
As a magenta coupler for the sensitive silver halide emulsion layer.
1- (2,4,6 trichlorophenyl) -3-{[α- (2,4
-Di-t-amylphenoxy) acetamide] benza
Mido} -3-pyrazolone and 1- (2,4,6-trichloro
Phenyl) -3-{[α- (2,4-di-t-amylphe
(Noxy) acetamido] benzamido} -4- (4-me
Toxiphenylazo) -5-pyrazolone, red-sensitive
C-59 is used as a cyan coupler in the silver halide emulsion layer.
Each emulsion layer contains a sensitizing dye, a hardener and a spreading agent.
The extender additive was added. However, blue-sensitive silver halide emulsion
The exemplified compound (I-16) was used as a sensitizing dye in the layer. The dry film thickness of the color negative film thus obtained
Was 23 μm. Experiment-1 After exposing the above-mentioned light-sensitive material by a conventional method, the following processing was carried out.
Experiments were conducted according to the process and the processing solution. Processing process Processing temperature (℃) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 Bleach fixing 37.8 6 minutes 30 seconds 3 Washing with water 30-40 3 minutes 15 seconds 4 Stability 30-34 1 minute 37 seconds 5 Drying <coloring Development tank liquid> Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.2g Potassium bromide 1.2g Diethylenetriaminepentaacetic acid 2.0g Sodium hydroxide 3.4g N-ethyl-N-β-hydroxyethyl-3-methyl-4-amino Aniline sulfate 4.6 g Water was added to adjust the pH to 1 and the pH was adjusted to 10.06 with potassium hydroxide. <Color development replenisher> Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.2g Potassium bromide 1.2g Diethylenetriaminepentaacetic acid 2.0g Sodium hydroxide 3.4g N-ethyl-N-β-hydroxyethyl-3-methyl-4 -Aminoamylin sulfate 5.2 g Water was added to adjust the pH to 1 and the pH was adjusted to 10.35 with potassium hydroxide. <Bleach-fixing tank solution and replenisher> Ethylenediaminetetraacetic acid ferric complex salt 0.31 mol Nitrilotriacetic acid 5.0 g Ammonium sulfite 15 g Ammonium thiosulfate 150 g Water was added to 1 and adjusted to pH 7.0 with ammonium water (28% solution). . <Stable tank liquid and replenisher> Formalin (35% aqueous solution) 7.0 ml Exemplified compound IV-4 0.5 g The above-mentioned color developing tank solution and bleach-fixing tank in the automatic processor
Liquid, flush water and stabilizing tank liquid, fill the color negative
While processing the film, the color development supplement described above is performed every 3 minutes.
Filling solution, bleach-fixing replenisher and stable replenisher through metering cup
The continuous treatment was performed while replenishing it. Replenishment amount is color negative
Film 1m²Replenishment amount to each color development tank
As 1475 ml, as a replenishing amount to the bleach-fixing tank 926 ml
926 ml of stable replenisher was added to the stabilizing bath.
Filled. The amount of washing water in the washing process is 1m²30 liters per flow was applied. Experiment-2 to Experiment-8 Using the above color negative film,
More experiments were conducted. Processing step Processing temperature (℃) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 Bleach fixing 37.8 6 minutes 30 seconds 3 Washing alternative stability 30-34 4 minutes 52 seconds 4 Drying In the direction of flow
A stable tank consisting of 1 to 3 tanks, and replenishment from the last tank
The overflow from the last tank to the previous tank.
Then, this overflow liquid flows into the tank at the previous stage again.
The multi-tank countercurrent method was adopted. Both the color developing solution and the bleach-fixing solution were the same as in Experiment-1.
The wash substitute stabilizer is prepared by adding the compounds shown in Table 1 to the following formulation.
Using the obtained one, perform the same continuous treatment as Experiment-1
It was The amount of replenishment of the stabilizing solution as a substitute for washing was the same as that in Experiment-1.
I'm sorry. <Stabilizing tank replacement solution and replenisher> 5-chloro-2-methyl-4-isothiazoline-3-
On 0.02g 2-Methyl-4-isothiazolin-3-one 0.02g Ethylene glycol 1.0g 2-Octyl-4-isothiazolin-3-one 0.01g Add water to make the pH 1 and add pH 7.5 with sulfuric acid and potassium hydroxide.
adjust. Experiment-11 In Experiment-8, color development tank solution and color development replenishment
Use the solution with 10 ml / l of benzyl alcohol added.
The same experiment was performed. Experiment-12 to Experiment-20 After the continuous processing of Experiment-8, the iodine elution from the light-sensitive material was carried out.
Use the bleach-fix replenisher instead of the accumulated bleach-fix.
A model containing 100 ml / l of color developing tank solution and 10 g / l of silver bromide.
The amount of potassium iodide in the Dell continuous treatment liquid was varied as shown in Table 1.
Experiment using model continuous processing bleach-fix solution
I went. The surface tension of the stabilizing solution used in the experiment and the stabilizing solution as a substitute for washing with water
It was measured by a usual method and shown in Table 1. For the cyan image part of the sample obtained in each experiment
Light resistance test with xenon arc lamp under the conditions of 40 ℃ and 80% RH
Perform the test for 200 hours and adjust the density of the dye image before and after the lightfastness test.
Red light from optical densitometer (PDA-65, manufactured by Konishi Rokusha Kogyo Co., Ltd.)
Then, the fading rate was obtained. These results are shown in Table-1.
You The drift after the continuous treatment used in Experiment-1 to Experiment-11
Table 1 shows the iodide concentration in the white fixing tank as KI.
did. Ion chromatography was used to measure the concentration.
It was As is clear from the results in the table, the normal value of Experiment-1 (comparison)
Washing with running water-Stability in Experiments-2 and 3 (comparing both)
Has deteriorated the light resistance of the cyan dye under high humidity.
In contrast, in Experiments 4 to 8 (all of the present invention), high humidity
The light resistance below is equal to or higher than that of Experiment-1 and is extremely high.
It turns out that it is preferable. Experiment-12, 13 (both ratios
Comparative), 14 to 20 (all of the present invention), the present invention
The iodide concentration in the bleach-fixing solution is 0.001 mol / l or less.
Effective when above, in the range of 0.002-0.02 mol / l
At some point it turns out to be particularly effective. Example 2 In the preparation of the light-sensitive material of Example 1, red-sensitive halogenated
1-hydroxy instead of cyan coupler C-59 in the silver emulsion layer
Ci-N- {α- (2,4-t-amylphenoxy) buty
Photosensitized in the same manner as above except that it used ru} -2-naphthamide.
Created the material. Repeat Experiments 1, 2 and 8 with this color negative film.
I returned. As a result, the cyan dye fading rate was 42% in Experiment-1.
-2 was 48%, and Experiment-8 was 38%.
It was far below the result in. This is used in Example 1
Cyan coupler represented by the general formula [V] or [VI]
Indicates that the effect of the present invention is promoted.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having a total dry film thickness of a photosensitive silver halide emulsion layer and a non-light-sensitive layer of 10 μm or more on one side of a support and containing no 2 equivalent pyrazoloazole coupler. After imagewise exposure, after treatment with a color developer containing substantially no benzyl alcohol,
After processing with a processing solution containing 10 ⁻³ mol / l or more of iodide and having a fixing ability, and subsequently with a washing substitute stabilizer having a surface tension of 8 to 50 dyne / cm and containing substantially no formaldehyde. A method of processing a silver halide color photographic light-sensitive material, which comprises drying. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material contains a sensitizing dye represented by the following general formula [I]. Material processing method. General formula [I] [In the formula, Z ₁ and Z ₂ are each a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus,
Represents an atomic group necessary to form a benzimidazole nucleus, a naphthimidazole nucleus, a pyridine nucleus or a quinoline nucleus, R ₁ and R ₂ each represent an alkyl group, an alkenyl group or an aryl group, and R ₃ is a hydrogen atom, methyl Represents a group or an ethyl group, X ₁ represents an anion, and 1 represents 0 or 1. ]