JPH0675180B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention

 [Industrial field of application] The present invention relates to a method for processing a silver halide color photographic light-sensitive material.
Concerned. More specifically, a halogen with rapid silver bleaching ability.
Silver photographic material (hereinafter referred to simply as "photosensitive material")
U) regarding the processing method. [Prior Art] Generally, a light-sensitive material exposed imagewise is processed to form a color image.
In order to obtain it, after the color development step, the produced metallic silver is washed.
Treated with a treatment solution with whiteness, followed by washing with water
Processing steps such as fixing and stabilizing are provided. As a processing solution having a bleaching ability, a bleaching solution and a bleach-fixing solution are available.
Are known. If bleaching solution is used, usually bleacher
And then fixing the silver halide with a fixing agent
However, bleaching and fixing can be done with the bleach-fixing solution.
It will be done in a time. A processing solution having a bleaching ability in the processing of light-sensitive materials contains
Red blood salt and heavy chromium as oxidants for bleaching image silver
Inorganic oxidants such as acid salts are widely used. However, it has a bleaching ability that contains these inorganic oxidants.
There are some serious drawbacks pointed out in the processing solutions used.
It Red blood salt and dichromate, for example,
Although it is relatively good in terms of terms,
Generates cyanide and hexavalent chromium ions, which are harmful to the body
It has a property that is unfavorable for pollution prevention.
It Also, because these oxidizing agents have extremely strong oxidizing power,
In addition, a silver halide solubilizer (fixing agent) such as thiosulfate
It is difficult to coexist in the same processing solution, and the bleach-fix bath
It is almost impossible to use these oxidants for
Therefore, the purpose of speeding up and simplifying the processing is achieved.
Making it difficult. Further contains these inorganic oxidants
The treatment liquid can be reused without discarding the waste liquid after treatment.
It has the drawback of being difficult to obtain. On the other hand, there are few pollution problems, and the processing is quick and easy.
Meet the request for basification and reusability of waste liquid
, Metal complexes of organic acids such as aminopolycarboxylic acid metal complex salts
Treatment liquids that use salt as an oxidant have come to be used.
It was However, the treatment liquid using the metal complex salt of organic acid is
Due to its slow conversion, the image silver (gold
It has the disadvantage that the bleaching rate (oxidation rate) of (general silver) is slow.
ing. For example, if the bleaching power is strong among the organic acid metal complex salts,
Ethylenediaminetetraacetic acid iron (III) complex salt considered
Partly used in combination with bleaching solution and bleach-fixing agent thiosulfate
For bleach-fixing of color paper using silver chlorobromide emulsion
It is used, but it has a high feeling mainly of silver bromide and silver iodobromide emulsion.
Degree silver halide color photographic light-sensitive material, especially silver halide
A color negative film for photography containing silver iodide as
Lum and color reversal film lack bleaching power
However, even after processing for a long time, a trace of image silver remains and desilvering property
Becomes defective. This tendency is due to oxidants and thiosulfates and
Redox potential decreases in bleach-fix bath containing sulfate
Therefore, it is particularly noticeable. In addition to the silver iodide high-sensitivity emulsion described above, it has high sensitivity and
Is it a child, and silver is effectively used to meet the demand for resource protection?
What has recently been developed as a silver halide emulsion
There are core / shell emulsions. This is a leading silver halide
Using the emulsion as crystal nuclei, successively deposit the next precipitate on top of this
By intentionally controlling the composition of each precipitate or the progress environment
It is a monodisperse core / shell emulsion made. Of these
A core / shell type high-speed emulsion containing silver iodide
Has extremely favorable characteristics for the above photographic performance.
I know that However,
As a result, the emulsion containing silver iodide was found to be sensitive to conventional bleach-fix solutions.
When applied to optical materials, the desilvering performance of developed silver is extremely poor.
Desilvered compared with developed silver in general silver halide emulsions.
It turns out that it has a difficult property. For example, silver halide composition, grain structure, amount of silver used, or various
Core / she prepared by using emulsion technology such as addition of additives
Photosensitive materials using emulsions are generally color negative photosensitive materials.
C-41 prescription (E
Milk using Stman Kodak Company's prescription; 38 ° C, 3'15 ")
As a result of the three technical systems of agent preparation-exposure-photochemical processing
If the developed silver amount in the high density area is 50% or less of the applied silver amount, feel
If the degree and graininess are increased, the desilvering property will be greatly deteriorated.
It That is, in order to obtain high sensitivity, the content of silver iodide of 3.5 mol% or more, which is convenient, is contained.
High sensitivity of existing core / shell emulsion to limit the amount of developed silver
-If it is included in the technical system of high graininess,
Silver halide and developed silver were different from those outside the technical system
It seems that it will be put in a situation, and it is thought that it will fall into desilvering poorness
It Ethylenediamine tetrachloride known as a particularly good bleach
A ferric salt of acetic acid or nitrilotriacetic acid was used as a fixing agent for thiol.
The desilvering property is greatly deteriorated in the bleach-fix solution containing a combination of sulfates.
It turned out that Therefore, it has a silver iodide content of 3.5 mol% or more, and the maximum concentration
Technology to limit the amount of developed silver in a part to 50% or less of the coated silver amount
High sensitivity in the system-core with excellent qualities of high granularity
/ Good desilvering and fast bleach-fixing for shell emulsion
A strong bleach-fix solution is strongly desired. [Object of the Invention] The present invention is, firstly, to achieve both ultra-high sensitivity and good graininess.
Excellent drift against silver halide color photographic light-sensitive materials.
Secondly, to provide a white fixing processing method, and secondly
Is a bleach-fix processing method that enables rapid processing of the light-sensitive material
The purpose is to provide the law. [Constitution of Invention] The above-mentioned object of the present invention contains silver iodide in an amount of 3.5 mol% or more.
Photosensitive silver halide emulsion layer containing core / shell emulsion
Silver halide color photographic light-sensitive material having at least one layer
, The maximum density of the light-sensitive material after exposure and color development
If the developed silver amount in the main part is 50% or less of the applied silver amount, then
Bleach-fixing based on ferric and thiosulfate organic acids
Bleaching with at least two bleach-fixing tanks using a liquid
When bathing, bleach-fix in the final bleach-fixing tank
The iodide concentration in the solution was adjusted to the iodide concentration in the bleach-fixing solution in the first tank.
Silver halide photography characterized by being kept below 50% of the degree
This is achieved by the method of processing the light-sensitive material. In addition, in the embodiment of the present invention, the compound represented by the general formula
Compounds represented by [I] to [VII], more preferred ingredients
The bleach-fix solution should contain the above-mentioned compounds as examples.
The release of ferric salts of organic acids that are suitable for bleaching
The molecular weight of the acid is preferably 300 or more. There are 2 to 4 baths in the bleach-fix bath treatment, and there are 2 baths.
It is practically the most preferable. Aspects of the invention are for each bath
The bleach-fixing replenisher may be added, or only in the final tank.
In addition, a multi-stage retrograde overflow method may be used, but
The backward overflow method is practically preferable. Further, the concentration of iodide in the bleach-fixing solution in the final tank is the first
50% or less of the concentration in the tank, preferably 30% or less
It is 10% or less. The absolute concentration of iodide in the first tank is
0.002-0.03 mol / l, preferably 0.003-0.02 mol / l
is there. Adjustment of the iodide concentration depends on the photosensitive material to be processed.
Depending on the replenishment amount of white fixing replenisher and the inflow amount of retrograde overflow
Is done. The light-sensitive material targeted by the present invention is silver iodide of 3.5 mol% or less.
Having a core / shell emulsion layer containing the above,
The emulsion is a sensitizing dye represented by the above general formula [VIII] and is optically
It is preferable to be sensitized. The coated silver amount is 35 mg / dm.²
The above is preferable. Next, the present invention will be described in detail. Technical system that limits the developed silver amount to 50% or less of the coated silver amount
The silver iodide-containing core / shell emulsion is extremely difficult to desilver
However, a small amount of iodide is present in the bleach-fix solution.
I got the unique finding that desilvering would proceed if
The present invention was made by advancing. From the conventional wisdom of photochemistry, iodide is very insoluble.
Since it produces silver iodide, it has a negative effect on desilvering.
Is believed to be. Practically for example bleaching containing iodide
When the color paper made of silver chlorobromide is treated with the fixer, it is removed.
Silver speed is greatly delayed, and desilvering is completely completed within the standard processing time.
I can't let you do it. Also, a multi-stage bath treatment with a bleach-fixing solution containing iodide
Is unlikely to lead to quick bleach-fixing. Chlorinated
Divide the color paper consisting of silver emulsion into two tanks,
The overflow method has been used, but in this case
Leuco cyanation by increasing the pH of the first tank relatively
This means is to prevent and to bleach-fix in the second tank in earnest.
The objective and technical means for leuco cyanation
Since it has advanced, NR method (Eastman Kodak Company method) etc. 1
It has been returned to the tank type small amount replenishment type. Incidentally, the iodide according to the present invention has an extremely high concentration in order to form a complex salt.
However, its mechanism of action is unknown. It contains silver iodide used in the photographic light-sensitive material of the present invention.
Summarizing the features of core / shell emulsions,
It is as in (1) to (8). (1). Core / shell type halo with a high iodine shell inside
By using an emulsion containing silver gentide grains (non-core
High sensitivity, wide exposure range, excellent graininess
Is obtained. (2). Intermediate between high-iodity shell and low-iodity shell (outermost shell layer) on the surface
By providing an intermediate shell with an intermediate iodine content in
And higher sensitivity can be obtained. (3). The iodine content of the high-iodity shell is preferably 6-40 mol%
The content is higher than the outermost shell layer by 6 mol% or more.
If it is less than 6 mol% (or less than 6 mol% than the outermost shell layer)
If it is not too much), the sensitivity will decrease and exceed 40 mol% again.
Then, it becomes polydisperse and exceeds 40 mol% from the viewpoint of sensitivity and sharpness.
Preferably not. (4). Iodine content in middle shell and outermost shell or high iodine shell
The difference in the rates should be 3 mol% or more, respectively.
Is the effect of the intermediate shell lessened if this difference is too small?
(Sensitivity decreases). In addition, this iodine content
The upper limit of the difference is 35 mol% because of the effect of the intermediate shell (sensitivity,
Effectively draw out monodispersity, fog-sensitivity relationship, and sharpness
It is desirable from the viewpoint of (5). The iodine content in the entire silver halide grain is high.
, The developability deteriorates, the sensitivity decreases, and
Too sharp, the gradation is too hard, the exposure area becomes narrow, and the graininess
Degradation tends to occur and it is preferable to select a specific range
Yes. (6). Monodisperse emulsions are more sensitive and sharper than polydisperse emulsions.
Excellent fog-sensitivity relationship. That is, in polydispersity, the shell
Due to the non-uniform reaction that forms, an ideal core / shell structure
Structure is difficult to form, and there are fine particles that deteriorate sharpness.
Presence, chemical sensitization after grain formation depends on individual grains.
Therefore, the sensitivity is low and the fog-sensitivity
The monodisperse emulsion is preferably used because it tends to be unsatisfactory.
It (7). Multi-layer color light-sensitive material
The result is that the sensitivity is lower than that of a single layer.
Occurs (which is referred to as a multi-layer desensitizing effect), the emulsion of the present invention
Not only the sensitivity of a single layer is high, but also this multi-layer desensitization effect is received.
Difficult to resist and more effective in multi-layer color photosensitive materials
Can be used. (8). The core / shell type silver halide grain of the present invention is
Higher sensitivity when combined with an ureido cyan coupler
Granularity, stability over time, etc. can be obtained. The silver iodide-containing core / shell emulsion according to the present invention has the above-mentioned constitution.
In this case, the content of silver iodide can be 3.5 mol% or more. The inner nucleus of the silver halide grain of the present invention has a
Simie Physik Photographer by P.Glafkides
Photo (Chimie et Physique.Photohraphique)
・ Montel (Paul Montel), 1967), GE
Photographic by G.F.Duffin
Immal John Chemistry (Photographic Emulsion Ch
imistry (The Focal Pres
s), 1966), V.L. Zelikmann (V.L.Zelik)
man) et al. Making and coating fo
Graphic and Immersion (Making and Coating Pho
tographic Emulsion (The Focal Press)
Focal Press), 1964) etc.
Can be prepared. That is, acidic method, neutral
Method, ammonia method, etc., and soluble silver salt
One-sided mixing is the method of reacting the soluble halogen salt with
Method, simultaneous mixing method, combination thereof, etc.
May be. Method of forming particles in the presence of excess silver ion
It is also possible to use the loose back mixing method). One of the simultaneous mixing method
PAg in the liquid phase where silver halide is produced as one of the forms
To keep constant, that is, so-called controlled
The double jet method can also be used. By this method
Then, the crystal form is regular and the particle size is close to uniform.
A silver halide emulsion is obtained. Mixing two or more types of silver halide emulsions formed separately
May be used, but double jet method or control
It is preferable to use the Le Double Jet method. The pAg used to prepare the inner core includes the reaction temperature and the halo.
Depending on the type of silver genide solvent, it is preferably 2
Is ~ 11. In addition, when a silver halide solvent is used, grain formation
It is preferable because the time can be shortened. For example ammoni
Well-known silver halides such as a and thioether
A solvent can be used. The shape of the inner core may be plate-like, spherical, or twinned.
Also, use octahedron, cube, dodecahedron or mixed system
You can In addition, in order to make the particle size uniform, British Patent 1,535,01
No. 6, JP-B-48-36890, 52-16364
So that the addition rate of silver nitrate or alkali halide aqueous solution
And US Pat. No. 4,
242,445, as described in JP-A-55-158124
Exceeding critical saturation using the method of changing aqueous solution concentration
It is preferable to grow quickly in a range where there is no. this
These methods do not cause re-nucleation, and each silver halide grain
Are uniformly coated, so any shell, high-iodity shell, intermediate shell
It is also preferably used when introducing the shell and the outermost shell. Between the high-iodity shell and the inner shell of the silver halide grain of the present invention
Can have one or more optional shells if desired
It This high-iodity shell is the inner shell formed or an arbitrary shell
After applying a desalting process to the applied inner shell, if necessary
Do not use ordinary halogen substitution method or silver halide coating method.
It can be provided by the person. Halogenation as the final product after outermost shell formation of the present invention
Silver particles consist of excess halogen compounds or
Salts of nitrates, ammonia, etc. that are by-produced or are no longer needed
The compounds, compounds may be removed from the dispersion medium of the particles.
The removal method is the Nudel water washing that is commonly used in general emulsions.
Method, dialysis method, inorganic salts, anionic surfactant
Agents, anionic polymers (eg polystyrene sulphate)
Acid), or a gelatin derivative (eg acylase)
Coagulation using latin, carbamoylated gelatin, etc.)
A precipitation (flocculation) method or the like can be appropriately used.
Wear. The core / shell type silver halide crystals of the present invention can be used in general emulsions.
Various chemical sensitization methods applied thereto can be applied. H.Friesew for chemical sensitization
Hen, Dee Grundtragen der Photokrafit
Shen Protse Semit Silver Halogen Niden
(Die Grundlagen der Photographische Prozesse mit
Silberhalogeniden) (Academy Michel Ferluk
Skagel shaft (Akademische Verlagsgesellschaf
t), 1968) pages 675-734 can be used.
Wear. That is, a compound containing sulfur that can react with silver ions.
Sensitizing method using chemicals and activated gelatin, using reducing substances
Noble gold using reduction sensitization method, gold and other noble metal compounds
The genus sensitization method can be used alone or in combination.
It Sulfur sensitizers include thiosulfates, thioureas and thiocyanates.
Use azoles, rhodanines and other compounds.
And specific examples thereof are U.S. Pat.No. 1,574,944,
2,410,689, 2,278,947, 2,728,668, 3,6
56,955, 4,032,928, 4,067,740
There is. As reduction sensitizers, primary tin salts, amines, hydrides
Lazin derivative, formamidine sulfinic acid, silanization
Compounds and the like can be used.
Xu No. 2,487,850, No. 2,419,974, No. 2,518,698, No.
2,983,609, 2,983,610, 2,694,637, 3,93
0,867 and 4,054,458. Precious metal sensitization
For gold complex salts, platinum, iridium, palladium
It is possible to use complex salts of Group VIII metals such as
Specific examples are U.S. Pat.Nos. 2,399,083 and 2,448,060.
And British Patent No. 618,061. The silver salt grains of the present invention can be produced by combining two or more of these chemical sensitization methods.
An oyster can be used. The coated silver amount is arbitrary, but preferably 35 mg / dm²More than 100m
g / dm²It is the following. When forming each shell of the core / shell type emulsion of the present invention,
A seed dopant can be doped. This internal drive
Examples of panto include silver, sulfur, iridium,
Gold, platinum, osmium, rhodium, tellurium, selenium
Mu, cadmium, zinc, lead, thallium, iron, antimony
Bismuth, arsenic, etc. are included. These dopants
Each water-soluble salt during the formation of each shell to dope
Alternatively, a complex salt can coexist. The above-mentioned silver iodide-containing core / shell type halo according to the present invention is used.
The present invention can be used with silver halide emulsions other than silver genide emulsions.
It can be used in combination in the range without. Optical sensitization of silver iodide-containing core / shell emulsion according to the present invention
The sensitizing dye used for is represented by the following general formula [VIII]
It General formula [VIII]Where Z₁And Z₂Is a benzene ring fused to a heterocycle
Alternatively, it represents an atomic group necessary for forming a naphthalene ring.
The heterocyclic nucleus formed may be substituted with a substituent. R₁
And R₂Is an alkyl group, an alkenyl group or an aryl, respectively.
R group, R₃Is a hydrogen atom or an alkyl having 1 to 3 carbon atoms
Represents a group. X₁ Represents an anion, p represents 0 or 1.
You Y₁And Y₂Is oxygen atom, sulfur atom, selenium atom, nitrogen
Represents an atom and a terium atom. Preferred among the substituents for the heterocyclic nucleus formed above
Substituents include halogen atoms, aryl groups, alkenyl groups, and
A rualkyl group and an alkoxy group. More preferred substituents
Is a halogen atom, a phenyl group and a methoxy group.
Also preferred substituents are phenyl groups. Preferably Z₁And Z₂Fused together with the oxazole ring
Benzene ring or thiazole ring
5-position of at least one benzene ring in the ring is phenyl
Or substituted at the 5-position of one benzene ring
Nyl group, 5th position of other benzene ring is replaced by halogen atom
It is what has been. R₁And R₂Is an alkyl group or
A group selected from a alkenyl group and an aryl group, which is preferable.
Or an alkyl substituted with a carboxyl group or a sulfo group, respectively.
A killed group, most preferably a sulfo group having 1 to 4 carbon atoms.
And a sulfoethyl group, and most preferably a sulfoethyl group.
is there. R₃Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
It is preferably a hydrogen atom or an ethyl group. Sensitizing dye represented by the general formula [VIII] used in the present invention
Is a so-called supersensitizing combination in combination with other sensitizing dyes.
Can also be used as In this case, each
Dissolve the sensitizing dye in the same or different solvent,
Mix these solutions or add them separately prior to addition.
It may be added to the emulsion. If adding separately,
The order and time interval of can be arbitrarily determined according to the purpose
It Specific compounds of the sensitizing dye represented by the general formula [VIII]
As shown below, the sensitizing dyes used in the present invention are
It is not limited to the compound. The addition represented by the general formula [VIII] used in the present invention
The amount of the sensitizing dye added to the emulsion is 2 × per mol of silver halide.
Ten^-6~ 1 x 10^-3Mol is preferable, more preferably 5 × 10
^-6~ 5 x 10^-FourIt is a mole. The emulsion layer of the light-sensitive material of the present invention can be used for color development processing.
, An aromatic primary amine developer (for example, p-phenylamine
(Diamine derivative, aminophenol derivative, etc.)
Dyes that form a dye by coupling reaction with oxidants of
Forming couplers are used. Each of the dye-forming couplers is
Absorbs light in the light-sensitive spectrum of the emulsion layer
Usually selected to form a pigment, blue
Yellow dye-forming coupler is used in the sensitive emulsion layer
Magenta dye-forming coupler in the agent layer, in the red-sensitive emulsion layer
Is a cyan dye-forming coupler. However
Depending on the purpose, different combinations of the above combinations may be used.
A silver halide color photographic light-sensitive material may be prepared. These dye-forming couplers are called ballast groups in the molecule.
Has a group with 8 or more carbon atoms that makes the coupler non-diffusing
Is desirable. Also, these dye-forming couplers consist of one molecule
4 molecules of silver ions are reduced to form the dye
Even if it is necessary to have 4 equivalence, 2 molecules of silver ion
It may be either dimeric, which only needs to be reduced. Pigment
The forming coupler has a color detector that has the effect of color correction.
By coupling with oxidant of puller and developing agent
Development inhibitor, development accelerator, bleaching accelerator, developer, halogen
Silver halide solvent, toning agent, hardener, antifoggant, antifoggant
Like chemicals, chemical sensitizers, spectral sensitizers, and desensitizers
Include compounds that release biologically useful fragments
It Among these, the development inhibitor is released with the development,
A coupler that improves image sharpness and image graininess is a DIR
Called the puller. Instead of DIR coupler,
When a colorless compound is formed by a coupling reaction with an oxidant,
It is also possible to use a DIR compound which releases a development inhibitor at the same time.
Yes. The DIR couplers and DIR compounds used are
When the inhibitor is directly bonded to the position
Is coupled to the coupling position via
Intramolecular nucleophilic reactions within the group that is released by
Bound so that the inhibitor is released by the child transfer reaction etc.
Things (Timing DIR coupler and Timing DIR combination
(Referred to as a thing) is included. In addition, the inhibitor is also diffusible after withdrawal.
Depending on the application, those that are not so diffuse
Can be used alone or in combination. Aromatic first
Coupling reaction with the oxidation product of the primary amine developer,
Colorless couplers that do not form dyes (also called competing couplers
U) can also be used in combination with a dye-forming coupler.
It As a yellow dye-forming coupler, a known acylacetate can be used.
Toanilide type couplers can be preferably used.
Of these, benzoylacetanilides and pivalo
Ilacetanilide compounds are advantageous. As a magenta dye-forming coupler, a known 5-pyrazo
Ron coupler, pyrazolobenzimidazole coupler
-, Pyrazolotriazole couplers, open-chain acyl ace
Uses trinitrile couplers, indazolone couplers, etc.
Can be Known cyan dye-forming couplers include phenols and
Alternatively, a naphthol coupler can be used. The cyan coupler used in the light-sensitive material of the present invention is
A coupler represented by the following general formula [1] or [2]
Preferably there is. General formula [1]General formula [2]In the general formula [1] and the general formula [2], Y isIs a group represented by. Where R₁And R₂Are each alkyl
A group, preferably an alkyl group having 1 to 20 carbon atoms (eg methyl group).
Group, ethyl, t-butyl, dodecyl groups, etc.), alke
Nyl group Preferably an alkenyl group having 2 to 20 carbon atoms (allyl
Groups, heptadecenyl groups, etc.), cycloalkyl groups are preferred
Is a 5- to 7-membered ring (eg cyclohexyl), ant
Group (eg phenyl group, tolyl group, naphthyl group
Etc.), a heterocyclic group, preferably a nitrogen atom, an oxygen atom
Or a 5- to 6-membered ring group containing 1 to 4 sulfur atoms (for example,
(Furyl group, thienyl group, benzothiazolyl group, etc.)
You R₃Is a hydrogen atom or R₂Represents a group represented by. R₂When
R₃May be bonded to each other to form a 5- or 6-membered heterocycle
Yes. Note that R₁And R₂Any substituent can be introduced into
, For example, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group).
, I-propyl, i-butyl, t-butyl, t-oct
Tyl, etc.), aryl groups (eg phenyl, naphthyl)
Etc.), halogen atom (fluorine, chlorine, bromine, etc.), shear
No, nitro, sulfonamide groups (eg methane sulfone
Amide, butanesulfonamide, p-toluene sulfone
Amide, etc.), sulfamoyl group (methylsulfamoy)
Group, phenylsulfamoyl, etc.), sulfonyl group (eg,
For example, methanesulfonyl, p-toluenesulfonyl, etc.)
Luorosulfonyl group, carbamoyl group (eg dimethyl
Carbamoyl, phenylcarbamoyl, etc.), oxycal
Bonyl groups (eg ethoxycarbonyl, phenoxycal
Bonyl), acyl groups (eg acetyl, benzoyl)
Etc.), heterocycle (eg pyridyl group, pyrazolyl group)
Etc.), alkoxy group, aryloxy group, acyloxy
A group etc. can be mentioned. In general formula [1] and general formula [2], R₁Is the general formula
A cyan coupler represented by [1] and a general formula [2], and
Diffusion resistance to cyan dyes formed from the cyan coupler
Represents a ballast group necessary for imparting. Preferably charcoal
An alkyl group, an aryl group, an alkenyl group having a prime number of 4 to 30,
It is a cycloalkyl group or a heterocyclic group. For example, straight chain
Or a branched alkyl group (eg, t-butyl, n-octyl)
Le, t-octyl, n-dodecyl, etc.), 5 members or 6
A membered-ring heterocyclic group etc. are mentioned. In the general formulas [1] and [2], Z is a hydrogen atom.
Or N-hydroxyalkyl-substituted-p-phenylenedia
During the coupling reaction with the oxidant of the color developing agent
Represents a group capable of splitting off. For example, a halogen atom (for example,
Chlorine, 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
Honamide group and the like, and more specific examples include rice
National Patent 3,741,563, JP-A-47-37425, JP-B-48-3689
4, JP-A-50-10135, 50-117422, 50-130441
No. 51, No. 51-108841, No. 50-120343, No. 52-18315, No.
53-105226, 54-14736, 54-48237, 55-3207
No. 1, 55-65957, 56-1938, 56-12643, 56
-27147, 59-146050, 59-166956, 60-24547
No. 60-35731, No. 60-37557, etc.
Can be mentioned. In the present invention, a cyan coupler represented by the general formula [3]
Is preferred. General formula [3]In the general formula [3], R_FourIs a substituted or unsubstituted aryl group
(Particularly preferably a phenyl group). The aryl group is
When it has a substituent, the substituent is SO₂R_Five, Halo
Atom (fluorine, chlorine, bromine, etc.), -CF₃, -NO₂, -CN, -COR
_Five, -COOR_Five, -SO₂OR_Five，At least one substituent selected from is included. Where R_FiveIs an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms.
Alkyl group (eg methyl, ethyl, t-butyl, dodecyl)
Each group), an alkenyl group, preferably having 2 to 20 carbon atoms.
Alkenyl group (allyl group, heptadecenyl group, etc.), siku
A lower alkyl group, preferably of 5 to 7 membered ring (eg
Chlorhexyl group, etc.), aryl group (eg phenyl group,
Tolyl group, naphthyl group, etc.), R₆Is a hydrogen atom
Is R_FiveIs a group represented by. Preferred Cyan Coupler of the Present Invention Represented by General Formula [3]
R compound_FourIs a substituted or unsubstituted phenyl group
, Cyano, nitro, -SO as a substituent to the phenyl group₂
R₇(R₇Is an alkyl group), halogen atom, trifluorome
A compound that is chill. Z and R in the general formulas [1], [2] and [3]₁Is each
Each has the same meaning as in general formulas [1] and [2].
R₁Preferred examples of the ballast group represented by
It is a group represented by [4]. General formula [4]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 K
If there are two or more, there are two or more R₉Are the same or different
You may stay, R₈Is a straight or branched chain having 1 to 20 carbon atoms, and
Represents a substituted alkylene group such as a reel group, R₉Is monovalent
Group, preferably a hydrogen atom or a halogen atom (for example,
Chromium, bromine), alkyl groups, preferably linear or
Various alkyl groups having 1 to 20 carbon atoms (eg, methyl, t-butene)
Chill, t-pentyl, t-octyl, dodecyl, penta
Decyl, benzyl, phenethyl and other groups), aryl groups
(Eg phenyl group), heterocyclic group (eg containing nitrogen compound)
(Cyclic group), alkoxy group, preferably linear or branched carbon
Alkoxy groups having a prime number of 1 to 20 (eg methoxy, etoxy)
Ci, t-butyloxy, octyloxy, decyloxy
Si, dodecyloxy and other groups), aryloxy groups (eg
Phenoxy group), hydroxy group, acyloxy group,
Preferably an alkylcarbonyloxy group, an arylcarl
Bonyloxy groups (eg acetoxy group, benzoyl group
Xy group), carboxy, alkyloxycarbonyl group,
Preferably, a straight chain or branched alkylcarc having 1 to 20 carbon atoms.
Bonyl group, preferably phenoxycarbonyl group, alkyl group
Ruthio group, preferably acyl group having 1 to 20 carbon atoms, preferably
Or a straight-chain or branched alkylcarbonyl having 1 to 20 carbon atoms
Group, an acylamino group, preferably a straight-chain or
Is a branched alkylcarbamido group, benzenecarboami
Group, a sulfonamide group, preferably a straight chain having 1 to 20 carbon atoms.
Chain or branched alkyl sulfonamide group or benzene
Ruphonamide group, carbamoyl group, preferably having 1 carbon atom
~ 20 linear or branched alkylaminocarbonyl groups or
Phenylaminocarbonyl group, sulfamoyl group, preferred
Or a straight-chain or branched alkylaminos having 1 to 20 carbon atoms
Represents a sulfonyl group, a phenylaminosulfonyl group or the like. Next, the cyan of the present invention represented by the general formula [1] or [2]
Specific compound examples of the coupler are shown below, but the compounds are not limited to these.
I can't. [Exemplified compound] These cyan couplers of the present invention are combined by a known method.
For example, U.S. Pat.Nos. 3,222,176 and 3,4
46,622, 3,996,253, British Patent No. 1,011,940,
Kaisho 47-21139, 56-65134, 57-204543, 57-
No. 204544, Japanese Patent Applications No. 56-131309, No. 56-131311, No. 56-1
31312, 56-131313, 56-131314, 56-130459
No. 60-24547, No. 60-35731, No. 60-37557, etc.
It can be synthesized by the synthetic method described in 1. Shear of the present invention represented by the general formula [1] and / or [2]
The couplers may be used alone or in combination of two or more.
When the general formulas [1] and [2] are used in combination,
The cyan coupler of the present invention represented by [1]: (general formula
The cyan coupler of the present invention represented by [2]) = 1: 9 to 9: 1
Good. Then, the cyan coupler of the present invention is used as a silver halide.
When it is contained in the emulsion layer, it is usually 1 mol of silver halide.
About 0.005 to 2 mol, preferably 0.01 to 1 mol
Is. The magenta coupler used in the present invention has the following general formula
It is represented by [5]. General formula [5]Ar: a phenyl group, especially a substituted phenyl group
It As a substituent, a halogen atom, an alkyl group, an alkoxy
Group, aryloxy group, alkoxycarbonyl group, sia
Group, carbamoyl group, sulfamoyl group, sulfonyl
A group, a sulfonamide group or an acylamino group, with Ar
The represented phenyl group may have two or more substituents.
Yes. Specific examples of the substituent will be given below. Halogen atom: chlorine, bromine, fluorine Alkyl group: methyl group, ethyl group, iso-propyl group,
A butyl group, a t-butyl group, a t-pentyl group and the like,
Particularly, an alkyl group having 1 to 5 carbon atoms is preferable. Alkoxy group: methoxy group, ethoxy group, butoxy group,
sec-butoxy group, iso-pentyloxy group, etc.,
Particularly, an alkoxy group having 1 to 5 carbon atoms is preferable. Aryloxy group: phenoxy group, β-naphthoxy group, etc.
However, the aryl part has a phenotype
It may have the same substituents as those mentioned for the nyl group. Alkoxycarbonyl group: the above-mentioned alkoxy group
Carbonyl group, methoxycarbonyl group, pliers
The number of carbon atoms in the alkyl moiety of the
Those of 1 to 5 are preferable. Carbamoyl group: carbamoyl group, dimethylcarbamoy
Alkylcarbamoyl group such as a group, sulfamoyl group: sulfamoyl group, methylsulfa group
Moyl group, dimethylsulfa Moyl group, ethylsulfa
Alkylsulfamoyl group such as moyl group Sulfonyl group: methanesulfonyl group, ethanesulfonyl group
Group, an alkylsulfonyl group such as butanesulfonyl group,
Reel sulfonyl group, etc. Sulfonamide group: Methane sulfonamide group, Toluene
Alkyl sulfonamide groups such as sulfonamide groups, ants
Arylamino group: acetamino group, pivaloylamino group
Group, a benzamide group and the like, particularly preferably a halogen atom, of which chlorine is
Most preferred. Y: Oxide and coupling agent of aromatic primary amine color developing agent
Represents a group that leaves when a dye is formed by aging. Specifically, for example, a halogen atom, an alkoxy group, an aryl
Luoxy group, acyloxy group, arylthio group, alkyl group
Luthio group,(Z is a nitrogen atom, oxygen atom, nitrogen atom and nitrogen atom.
Form a 5- or 6-membered ring with an atom selected from among
Represents a group of atoms required for formation. ) Specific examples are given below. Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, benzyloxy group, methoki
Ciethylcarbamoylmethoxy group, tetradecylcarba
Moyl methoxy group, etc. Aryloxy group: phenoxy group, 4-methoxypheno
Xyl group, 4-nitrophenoxy group, etc. Acyloxy group: acetoxy group, myristoyloxy
Group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5-
Octylphenylthio group, 2,5-dihexyloxyphene
Nylthio group, etc. Alkylthio group: methylthio group, octylthio group, hex
Sadecylthio group, benzylthio group, 2- (diethylamido)
No) ethylthio group, ethoxycarbonylmethylthio group,
Ethoxyethylthio group, phenoxyethylthio group, etc.: Pyrazolyl group, imidazolyl group, triazolyl group, te
Trazolyl group, etc. When R: R is an acylamino group
Group, isobutylamino group, benzamide group, 3- [α
-(2,4-di-tert-amylphenoxy) butylami
De] benzamide group, 3- [α- (2,4-di-tert-amino)
Milphenoxy) acetamide] benzamide group, 3-
[Α- (3-pentadecylphenoxy) butyramide]
Benzamide group, α- (2,4-di-tert-amylpheno
Xy) Butyramide group, α- (3-pentadecylpheno
Xy) butyramide group, hexadecane amide group, isos
Thearoylamino group, 3- (3-octadecenyl succinate
Nimido) benzamide group or pivaloylamino group, etc.
And R is an anilino group, an example is anilino
Group, 2-chloroanilino group, 2,4-dichloroanilino
Group, 2,5-dichloroanilino group, 2,4,5-trichloroaniline
Reno group, 2-chloro-5-tetradecanamide anilino
Group, 2-chloro-5- (3-octadecenylsuccinyl
(Mido) anilino group, 2-chloro-5- [α- (3-tert
-Butyl-4-hydroxy) tetradecanamide) ani
Reno group, 2-chloro-5-tetradecyloxycarboni
Luanilino group, 2-chloro-5- (N-tetradecyls
Rufamoyl) anilino group, 2,4-dichloro-5-teto
Radecyloxyanilino group, 2-chloro-5- (tetra
Decyloxycarbonylamino) anilino group, 2-chloro
Ro-5-octadecylthioanilino group or 2-chloro
-5- (N-tetradecylcarbamoyl) anilino group, etc.
And when R is an ureido group, examples include 3-
{(2,4-di-tert-aminophenoxy) acetamide}
Phenylureido group, phenylureido group, methyluree
Id group, octadecyl ureido group, 3-tetradecane group
Midphenyl ureido group or N, N-dioctyl urei
There are some groups. Among the compounds represented by the general formula [5],
A preferred compound is represented by the following general formula [6]. General formula [6]In the formula, Y and Ar have the same meanings as in the general formula [5]. X: represents a halogen atom, an alkoxy group or an alkyl group. Specific examples are given below. Halogen atom: chlorine, bromine, fluorine Alkoxy group: methoxy group, ethoxy group, butoxy group,
Carbon atom such as sec-butoxy group, iso-pentyloxy group
An alkoxy group having a number of 1 to 5 is preferable. Alkyl group: methyl group, ethyl group, iso-propyl group,
Carbon atom such as butyl group, t-butyl group, t-pentyl group
An alkyl group having a number of 1 to 5 is preferable. A halogen atom is particularly preferable, and chlorine is particularly preferable.
Good R₁: Represents a group capable of substituting on the benzene ring, and n is 1 or 2
Represents an integer. When n is 2, R may be the same or different
Good. The group which can be substituted on the benzene ring represented by R is halo.
Gen atom, R'-, R'O-, Etc. R ', R "and R may be the same or different from each other.
A hydrogen atom or an alkyl group which may have a substituent.
Represents an alkyl group, an alkenyl group or an aryl group. these
Of these, R'CONH-, R'SO is preferable._TwoNH-, andIs. Specific examples of the magenta couplers of the above type are shown below.
It is not limited to these.Examples of R in the above formula include the following. M-1 -NHCOC₁₃H₂₇ M-2 -NHCOC₁₄H₂₉  Examples of Y in the above formula include the following. M-9-SC₁₂H_{twenty five}  These magenta couplers of the present invention are disclosed in JP-A-56-38043.
Described in Nos. 57-14837, 57-204036, 58-14833, etc.
It can be easily synthesized according to the above method. In the present invention, the magenta coupler represented by the general formula [5]
Are conventionally known within a range not deviating from the object of the present invention.
Can be used in combination with the magenta coupler
It Further, as color-free couplers that can be used in combination with the present invention,
Patents 861,138, 914,145, 1,109,963, Japanese Patent Publication No. 4
5-14033, U.S. Pat.No. 3,580,722 and Mitt Tilton
Gen Ausden Forshening Laboratory
Endea Agfa Revelkusen Volume 4 352-367
You can choose from those listed on page (1964) etc. Halogenated magenta coupler represented by the general formula [5]
When it is contained in the silver emulsion layer, it is usually 1 mol of silver halide.
About 0.005 to 2 mol, preferably 0.01 to 1 mol
Used in a range. Still other types of magenta that are preferably used in the present invention
The puller is represented by the following general formula [7]. General formula [7]In the magenta coupler represented by, Z is a nitrogen-containing complex
Represents a group of non-metal atoms necessary for forming a ring,
The ring formed may have a substituent. X is a hydrogen atom or a reaction with an oxidized product of a color developing agent.
Represents a substituent capable of splitting off. R represents hydrogen or a substituent. Examples of the substituent represented by R include a halogen atom and
Alkyl group, cycloalkyl group, alkenyl group, cycloalkyl group
Lucenyl group, alkynyl group, aryl group, heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl
Group, carbamoyl group, sulfamoyl group, cyano group, sulfur
Pyro compound residue, bridged hydrocarbon compound residue, alkoxy
Group, aryloxy group, heterocyclic oxy group, siloxy
Group, acyloxy group, carbamoyloxy group, amino
Group, acylamino group, sulfonamide group, imide group,
RAID group, sulfamoylamino group, alkoxycarbo
Nylamino group, aryloxycarbonylamino group,
Lucoxycarbonyl group, aryloxycarbonyl group,
Examples include alkylthio group, arylthio group, and heterocyclic thio group.
You can Detach by reaction with the oxidant of the color developing agent represented by X
Examples of the substituent include halogen atom (chlorine atom, odor
Other than carbon atom, oxygen atom, sulfur
Groups which substitute via an atom or a nitrogen atom are mentioned. Most preferred of these substituents represented by X
Is a halogen atom. Also, as a nitrogen-containing heterocycle formed by Z or Z ′
Is a pyrazole ring, an imidazole ring, or a triazole ring.
Or a tetrazole ring, etc., and the ring may have
Examples of the substituent include those described for R above.
It In the general formula [7] and the general formulas [8] to [14] described later,
A substituent on the heterocycle (eg, R, R₁~ R₈)But Part (where R ″, X and Z ″ are R,
Synonymous with X and Z. ) Has a so-called screw type color
It forms a poo and is of course included in the present invention. Also Z, Z ′,
Z ″ and Z described below₁The ring formed by is another ring
Even if (for example, a 5- to 7-membered cycloalkene) is condensed
Good. For example, in the general formula [11], R_FiveAnd R₆But general
In [12], R₇And R₈And are linked together to form a ring (eg
Even if it forms a 5- to 7-membered cycloalkene, benzene)
Good. More specifically, those represented by the general formula [7] are, for example,
It is represented by the general formulas [8] to [13]. General formula [8]General formula

[9]General formula (10)General formula (11)General formula (12)General formula (13)In the general formulas [8] to [13], R₁~ R₈And X is
It is synonymous with R and X. Among the general formula [7], the following general formula is preferable.
It is represented by [14]. General formula (14)R in the formula₁, X and Z₁Is the same as R, X and Z in the general formula [7].
Righteous. Magenta couplers represented by the above general formulas [8] to [13]
Among them, particularly preferred is a maze represented by the general formula [8].
It is an input coupler. Also, in the substituents on the heterocycle in the general formulas [7] to [14],
Incidentally, in the general formula [7], R is
In formulas [8] to [14], R₁Satisfies the following condition 1
It is preferable that the following conditions 1 and 2 are satisfied.
The following conditions 1, 2 and
This is the case where 3 is satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 Only one hydrogen atom is bonded to the carbon atom
Or no binding at all. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.
It is the case. Substituents R and R on said heterocycle₁Most preferred as
Is represented by the following general formula [15]. General formula (15)R in the formula₉, R_TenAnd R₁₁Are hydrogen atom and halogen atom respectively
Child, alkyl group, cycloalkyl group, alkenyl group,
Chloalkenyl group, alkynyl group, aryl group, hetero
Ring group, acyl group, sulfonyl group, sulfinyl group, phosphine
Honyl group, carbamoyl group, sulfamoyl group, cyano
Group, spiro compound residue, bridged hydrocarbon compound residue, al
Coxy group, aryloxy group, heterocyclic oxy group, silo
Xy group, acyloxy group, carbamoyloxy group, amine
Group, acylamino group, sulfonamide group, imide group,
Ureido group, sulfamoylamino group, alkoxycal
Bonylamino group, aryloxycarbonylamino group,
Alkoxycarbonyl group, aryloxycarbonyl
Group, alkylthio group, arylthio group, heterocyclic thio group
Represents R₉, R_TenAnd R₁₁At least two of which are hydrogen atoms
There is no. Also, the R₉, R_TenAnd R₁₁Two out of, for example R₉And R_TenIs a bond
Saturated or unsaturated ring (eg cycloalkane,
(A alkene, a heterocycle) may be formed on the ring.
R₁₁May combine to form a bridged hydrocarbon compound residue.
Yes. R₉~ R₁₁The group represented by may have a substituent, R₉
~ R₁₁Specific examples of the group represented by and in the general formula [15]
But preferred are (i) R₉~ R₁₁When two of are alkyl groups, (ii) R₉~ R₁₁One of, eg R₁₁Is a hydrogen atom
And the other two R₉And R_TenBond with the root carbon atom
When forming a croalkyl, Further preferred among (i) is R₉~ R₁₁Two of
Is an alkyl group and the other is a hydrogen atom or
This is the case of a kill group. Here, the alkyl and the cycloalkyl further have a substituent.
Optionally the alkyl, the cycloalkyl and their substitutions
A specific example of the group is represented by R in the general formula [7].
Specific examples of alkyl, cycloalkyl and their substituents are listed.
You can Further, a ring formed by Z in the general formula [7] and a ring
Z in general formula [14]₁May have a ring formed by
Substituents and R in the general formulas [8] to [13]₂~ R₈
Is preferably represented by the following general formula [16]. General formula [16] -R¹-SO₂-R² R in the formula¹Is alkylene, R²Is alkyl, cycloalkyl
Or represents aryl. R¹Preferred specific examples of the alkylene represented by
YouR²The alkyl group represented by may be linear or branched. Particularly preferred among the compounds represented by the general formula [7]
Is represented by the following general formula [17]. General formula (17)In the formula, R and X have the same meanings as R and X in the general formula [7],
R¹, R²Is R in the general formula [16]¹, R²Is synonymous with. Further, substituents on the heterocycle in the general formulas [7] to [14]
In general formula [7], R is
In general formulas [8] to "[14], R₁Satisfies the following condition 1
The following conditions 1 and 2 are more preferable.
Is satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 At least two hydrogen atoms are bonded to the carbon atom
Present or not at all. Substituents R and R on said heterocycle₁Most preferred as
Is represented by the following general formula [18]. General formula [18] R₁₂-CH₂-Where R₁₂Are hydrogen atom, halogen atom, alkyl
Group, cycloalkyl group, alkenyl group, cycloalkene
Group, alkynyl group, aryl group, heterocyclic group, acyl
Group, sulfonyl group, sulfinyl group, phosphonyl group,
Lubamoyl group, sulfamoyl group, cyano group, spiro group
Compound residue, bridged hydrocarbon compound residue, alkoxy group,
Reeloxy group, heterocyclic oxy group, siloxy group, acyl
Luoxy group, carbamoyloxy group, amino group, acyl
Amino group, sulfonamide group, imide group, ureido group,
Sulfamoylamino group, alkoxycarbonylamino
Groups, aryloxycarbonylamino groups, alkoxy groups
Rubonyl group, aryloxycarbonyl group, alkyl group
Represents an o group, an arylthio group, or a heterocyclic thio group. R₁₂The group represented by may have a substituent, further R₁₂
Preferred as is a hydrogen atom or an alkyl group. Specific examples of the compound used in the present invention are shown below. In addition, the synthesis of the above-mentioned coupler is performed by Journal of Chemical
・ Society (Journal of the Chemical Societ
y), Perkin I (1977), 2047-2052, USA
Patent 3,725,067, JP-A-59-99437, JP-A-58-42045
JP-A-59-162548, JP-A-59-171956, JP-A-60
-33552 and JP-A-60-43659, etc.
It was. The coupler of the present invention usually contains 1 × 10 5 mol / mol of silver halide.
^-3Mol to 1 mol, preferably 1 x 10^-2Mole to 8 × 10
^-1It can be used in the molar range. In the present invention, a DIR compound other than the diffusible coupler is
It is preferably used. In addition to the DIR compound, a development inhibitor with development.
Also included in the present invention are compounds that release
3,297,445, 3,379,529, West German patent application (OLS) 2,4
17,914, JP-A Nos. 52-15271, 53-9116, and 59-1238
38, 59-127038 and the like. The DIR compound used in the present invention is a color developing agent.
Reacts with an oxidant to release a development inhibitor
It is a combination. A typical example of such a DIR compound is an active site
Form a compound with development inhibitory effect when released from
DIR coupler in which a possible group is introduced at the active site of the coupler
, For example, British Patent No. 935,454, U.S. Patent No. 3,2
27,554, 4,095,984, 4,149,886, etc.
ing. The above-mentioned DIR coupler is an oxidant of the color developing agent and capry.
When the coupling reaction occurs, the coupler nucleus forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Also in the present invention
Are U.S. Pat.Nos. 3,652,345, 3,928,041, and 3,958,99.
3, 3,961,959, 4,052,213, JP-A-53-110529
No. 54-13333, No. 55-161237, etc.
When a coupling reaction occurs with an oxidant of a color developing agent such as
, A compound that releases a development inhibitor but does not form a dye
Is also included. Furthermore, JP-A Nos. 54-145135, 56-114946 and
57-154234 and the oxidant of the color developing agent as described in
When reacted, the mother nucleus forms a dye or colorless compound.
On the other hand, the released timing group is an intramolecular nucleophilic substitution reaction.
A compound that releases a development inhibitor by reaction or desorption reaction.
The so-called timing DIR compound which is an object is also included in the present invention.
It Further, it is described in JP-A Nos. 58-160954 and 58-162949.
Diffuses completely when it reacts with the oxidant of the color developing agent
The above-described thymine is present in the mother nucleus of the coupler which forms a dye having a volatile property.
Containing a timing DIR compound having a pendant group attached
Is. The amount of the DIR compound contained in the light-sensitive material is 1 mol of silver.
Then 1 x 10^-FourMol ~ 10 × 10^-1A molar range is preferably used
To be Dye formation without the need for adsorption on the silver halide crystal surface
Coupler, colored coupler, DIR coupler, DIR combination
Objects, image stabilizers, antifoggants, UV absorbers, fluorescent
Among the whitening agents, hydrophobic compounds are solid dispersion method, LATEC
Dispersion method, oil-in-water emulsion dispersion method, etc.
Can be dispersed as a hydrophobic compound such as a coupler.
It can be appropriately selected depending on the chemical structure of the product. water
The medium oil drop type emulsion dispersion method uses a hydrophobic additive such as a coupler.
A conventionally known method of dispersing can be applied, and the boiling point is usually about 150.
High boiling point organic solvent of ℃ or higher, low boiling point if necessary, and
Dissolves in water with a water-soluble organic solvent,
Agitating with surfactant in which hydrophilic binder
Vessel, homogenizer, colloid mill, flow jit Miki
Emulsified and dispersed using a dispersion means such as a sir, ultrasonic device, etc.
After that, it may be added to the desired hydrophilic colloid solution.
Step of removing low boiling point organic solvent after or simultaneously with dispersion
May be included. As a high boiling point solvent, a solvent that does not react with the oxidant of the developing agent.
Nole derivative, phthalic acid alkyl ester, phosphoric acid
Steal, citrate, benzoate, alk
Lamide, fatty acid ester, trimesic acid ester, etc.
An organic solvent is used. Low-boiling or water-soluble with or instead of high-boiling solvents
Organic solvents can be used. It has a low boiling point and is practically insoluble in water.
Ethyl acetate, propyl acetate as machine solvent
Butyl acetate, butanol, chloroform, four
Carbon chloride, nitromethane, nitroethane, benzene, etc.
And water-soluble organic solvents include acetone and methyl ether.
Sobutyl ketone, β-ethoxyethyl acetate, meth
Xyglycol acetate, methanol, ethanol,
Acetonitrile, dioxane, dimethylformamide,
Dimethyl sulfoxide, hexamethylphosphoric acid
Liamide, diethylene glycol monophenyl ether
And phenoxyethanol. Dye forming coupler, DIR coupler, Colored coupler, D
IR compounds, image stabilizers, anti-foggants, UV absorption
Acid such as carboxylic acid and sulfonic acid
In the case of having a group, a hydrophilic coke solution
It can also be introduced into Lloyd. Hydrophobic compounds may be used alone or in combination with high boiling solvents.
Dissolved in different solvents and dispersed in water using mechanical or ultrasonic waves
As an auxiliary agent for dispersion, an anionic surfactant,
Nonionic surfactant, cationic surfactant and amphoteric field
A surface active agent can be used. The silver halide emulsion layer of the present invention is usually used according to the purpose.
Various additives may be included. For example, this
Ndenes, triazoles, tetrazoles, imidazo
Lithium salt, tetrazolium salt, polyhydroxy compound, etc.
Stabilizers and antifoggants; aldehydes, aziridine
Type, inoxazole type, vinyl sulfone type, acrylo
Ile-based, alpodiimide-based, maleimide-based, methane-sulfur
Hardeners such as phosphonates and triazines; benzyl
Development acceleration of alcohol, polyoxyethylene compounds, etc.
Agents: Chroman-type, Klamant-type, Bisphenol-type, Lignite
Acid ester-based image stabilizers; wax, higher fatty acid
Glyceride, higher alcohol esters of higher fatty acids, etc.
There are lubricants, etc. Further, a coating aid as a surfactant,
Penetration improver, antifoaming agent or photosensitizer
A material for controlling various physical properties of the material
The anion type, cation type, non-ion type or both
Various types of sex can be used. Zia as an antistatic agent
Cetyl cellulose, styrene perfluoroalkyl lithi
Ummaleate copolymer, styrene-maleic anhydride copolymer
The reaction product of the polymer and p-aminobenzenesulfonic acid
Lucari salt etc. are effective. Polymethac as matting agent
Methyl phosphate, polystyrene and alkali-soluble polymers
ー etc. In addition, the use of colloidal silicon oxide
It can also be used. In addition, it is added to improve the physical properties of the film.
As latex, acrylic ester, vinyl ester
Examples of copolymers of ethylene and other monomers having ethylene groups
You can Glycerin as a gelatin plasticizer,
Glycolic compounds, etc. can be mentioned as a thickening agent.
Styrene-sodium maleate copolymer, alkyl vinyl
Examples thereof include a nyl ether-maleic acid copolymer. In the silver halide color photographic light-sensitive material of the present invention, milk
To prepare coating agents and other hydrophilic colloid layer coating solutions
The hydrophilic colloid used is gelatin, a derivative gel
A graft polymer of tin, gelatin and other polymers,
Proteins such as rubumin and casein, hydroxyethyl cells
Cellulose such as sucrose derivatives and carboxymethyl cellulose
Glucose derivatives, starch derivatives, polyvinyl alcohol, poly
Vinylyl imidazole, polyacrylamide etc. are single
Or any of synthetic hydrophilic polymers such as copolymers
To be done. As a support of the silver halide color photographic light-sensitive material of the present invention
For example, glass plate, cellulose acetate, cellulose
Such as nitrite or polyethylene terephthalate
Polyester film, polyamide film, polycarbonate
Bonate film, polystyrene film, etc.
In addition, conventional reflective supports (eg baryta paper, polyester
It is equipped with ethylene coated paper, polypropylene synthetic paper and a reflective layer.
Or a transparent support with a reflector),
These supports are appropriately selected according to the intended use of the light-sensitive material.
It Silver halide emulsion layer used in the present invention and its
Dick ping coating, air coating
Doctor coating, curtain coating, hopper coating, etc.
A coating method can be used. U.S. Pat.No. 2,761,
Two or more layers by the method described in No. 791, No. 2,941,893
An application method can also be used. Having a core / shell type silver halide emulsion according to the present invention
After exposure, the photosensitive material is developed by a known method usually used.
Can be processed. Black and white developers are hydroxybenzenes, aminopheno
Alkaline-soluble, including developing agents such as
Liquid, other alkali metal sulfites, carbonates,
Can contain bisulfite, bromide, iodide, etc.
It Further, it is usually used when color-processing the light-sensitive material.
Color development can be performed by the color development method described above. Inversion method
Then first develop with a black and white negative developer, then apply white exposure.
Or in a bath containing a fog agent,
The color is developed with an alkaline developer containing a color developing agent.
There is no particular limitation on the processing method, any processing method
Can be applied, for example, as a typical one,
After color development, bleach-fix processing is performed.
Bleach after washing or stabilizing treatment or after color development
And fixing are separated, and if necessary, washed with water and stabilized.
A method of performing processing can be applied. Color developing solutions are generally alkaline water containing a color developing agent.
Consisting of a solution. Color developing agent is a known primary aromatic amine
Developers such as phenylenediamines (eg 4-amidamine
No-N, N-diethylaniline, 3-methyl-4-amino
-N, N-diethylaniline, 4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylanili
3-methyl-4-amino-N-ethyl-N-β-me
Tansulfamidoethylaniline, 4-amino-3-me
Tile-N-ethyl-N-β-methoxyethylaniline,
Etc.) can be used. In addition to this, written by L.F.A.Mason
 Photographic Processing Chemistry (ph
otographic Processing Chemistry) Focal Pre
(Focal Press), 1966), pages 226-229, US
No. 2,193,015, 2,592,364, JP-A-48-64933
Any of those described may be used. Other color developers include pH buffers, development inhibitors, and fog.
Inhibitors and the like can be included. If necessary, hard
Water softener, preservative, organic solvent, development accelerator, dye forming agent
Pullers, competitive couplers, foggants, auxiliary developers, viscosity
Giving agent, polycarboxylic acid chelating agent, antioxidant, etc.
May be included. The photographic emulsion layer after color development is usually bleached. bleaching
Alternatively, the bleach-fixing solution may be used in U.S. Pat.
41,966, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 45-8836, etc.
Bleach accelerators listed, thiolation as described in JP-A-53-65732.
In addition to the compound, various additives can be added. In the present invention, the organic acid ferric acid complex salt and thiol are used after color development.
Bleach-fixing treatment with a bleach-fixing solution containing sulfate as the main component
However, it is preferable that a bleaching accelerator is added to the bleach-fixing solution.
Be done. The bleach-fixing solution contains a ferric iron complex salt of an organic acid as a bleaching agent.
(Hereinafter referred to as ferric organic acid complex salt of the present invention)
It The molecular weight of the organic acid is preferably 300 or more. The organic acid for forming the ferric acid complex salt of the organic acid of the present invention is as follows.
The representative ones are listed below. (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 orthohydroxyphenylmethy
Renphosphonic acid (MW = 432.31) (15) Ethylenediaminetetramethylenephosphonic acid (MW = 43
6.13) The ferric organic acid complex salt of the present invention is not limited to these,
Any one of these can be selected and used.
If necessary, use two or more types in combination.
I can do it. The organic acid ferric acid complex salt of the present invention is a free acid (hydrogen salt),
Alkali gold such as sodium salt, potassium salt, lithium salt
Group salt, ammonium salt, or water-soluble amine salt
Used as triethanolamine, for example, but
Or potassium, sodium and ammonium salts
used. At least one of these ferric complex salts should be used.
However, two or more kinds may be used in combination. Its use
The amount of silver can be selected arbitrarily, and
And the composition of silver halide. That is, it is preferable to use 0.01 mol or more per 1 liquid used.
And more preferably 0.05 to 1.0 mol. Na
In the replenisher, the solubility and
It is desirable to concentrate it on the skin and use it as a replenisher.
Yes. The bleach-fixing solution of the present invention is preferably used at pH 2.0 to 10.0.
More preferably, more preferably pH 3.0-9.5, most preferably,
Used at pH 4.0-9.0. Use at a processing temperature of 80 ° C or lower
Is desirable, more preferably below 55 ℃, most desirable
It is preferably used at 45 ° C or lower with reduced evaporation. Bleach-fix
The treatment time is preferably 8 minutes or less, more preferably 6 minutes or less.
It is within. The bleach-fixing solution of the present invention is used as a bleaching agent as described above.
Including various addition phases with ferric complex organic acid salt
You can As an additive that contributes to bleach-fixability,
Lucari halide or ammonium halide, eg odor
Potassium bromide, sodium bromide, sodium chloride,
Ammonium, ammonium iodide, sodium iodide, iodide
It is desirable to contain potassium or the like. Also Trieta
Solubilizing agents such as nolamine, acetylacetone, phospho
Nocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxyca
Rubonic acid, polycarboxylic acid, alkylamines, polyester
It is known to be added to general-purpose bleaching solutions such as ethylene oxide.
What is mentioned can be added suitably. As a silver halide fixing agent contained in the bleach-fixing solution of the present invention
Is a silver halide used in ordinary fixing processing.
Compounds that react with water to form water-soluble complex salts, such as thiol
Potassium sulfate, sodium thiosulfate, ammonium thiosulfate
Thiosulfates such as um are used. These fixing agents are 5 g / l or more, preferably 50 g / l or more,
More preferably, it can be used in an amount within the range that can dissolve 70 g / l or more.
It The bleach-fixing solution of the present invention contains boric acid, borax, and sodium hydroxide.
Um, potassium hydroxide, sodium carbonate, potassium carbonate
Sodium, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
Thorium, ammonium hydroxide and other various pH buffering agents
May be contained alone or in combination of two or more
Absent. Furthermore, various fluorescent whitening agents, antifoaming agents or
It can also contain a bactericide. Also hydroxyl
Amine, hydrazine, sulfite, isomeric bisulfite, al
Preservatives such as bisulfite adducts of dehydration and ketone compounds,
Other additives, methanol, dimethylformamide,
Appropriately contain organic solvent such as dimethyl sulfoxide
be able to. See also Japanese Patent Application No. 50-51803
Such as a polymer or copolymer having a vinylpyrrolidone nucleus
It is desirable to add. Bleaching that is added to the bleach-fixing solution of the present invention to promote bleach-fixability
The accelerator is represented by the above general formulas [I] to [VII] and [VII] '.
However, typical examples thereof are as follows.
You can list things, but not limited to
Absent. [Exemplified compound] (II-28) H₂N-CSNHNHCS-NH₂  (II-34) H₂N-CSNH (CH₂)₂NHCS-NH₂ (II-35) H₂N-CSNH (CH₂)_FourNHCS-NH₂ (II-36) H₂N-CSNH (CH₂)_FiveNHCS-NH₂  (III-1) H₂N-CH₂CH₂-SH (III-5) HOOC ・ CH₂CH₂・ SH (VII-3) SCH₂CH₂NHCH₂CH₂CH₂SO₃H)₂  (VII-17) HSCH₂CH₂NHCH₂CH₂OH (VII'-2) N (CH₂CH₂OH)₃  (VII'-5) (HOCH₂CH₂CH₂)₂NCH₂CH₂N (CH₂CH₂CH₂O
H)₂  In the processing method of the present invention, the bleaching of the present invention is carried out immediately after color development.
Fixing is the preferred processing method, but color development
After this, after washing or rinsing or stopping, etc.
Bright bleach-fix processing may be performed. Most preferably the above
As described above, after pre-fixing processing is performed after color development,
The white fixing process is performed. In this case, the pre-fixing process is performed.
May contain the bleaching accelerator of the present invention. The bleach-fixing process of the present invention can be performed stably without washing with water.
You can do it, or wash it with water and then stabilize it.
Yes. In addition to the above steps, hardening, neutralization, black and white development, reversal,
Various auxiliary processes such as washing with water are added as needed.
May be. Representative specific examples of preferable processing methods will be given.
And the following steps are included. (1) Color development → bleach-fixing → washing with water (2) Color developing → bleach-fixing → washing with a small amount of water → washing with water (3) Color developing → bleach-fixing → washing → stable (4) Color developing → bleach-fixing → stable (5) Color developing → Bleach-fixing → 1st stability → 2nd stability (6) Color development → Washing (or stabilizing) → Bleach-fixing → Washing
(Or stable) (7) Color development → pre-fixing → bleach-fixing → washing with water (8) Color development → pre-fixing → bleach-fixing → stable (9) Color development → pre-fixing → bleach-fixing → 1st stability → 2nd stability
Constant (10) Color development → Stop → Bleach fixing → Washing → Stable Even among these processing steps, the effect of the present invention becomes more remarkable.
Because it appears, (3), (4), (5), (8) and
The treatment step (9) is more preferably used in the present invention.
It And most preferably (4), (5), (8) and
And (9) processing step. Various inorganic metal salts are added to the bleach-fixing solution of the present invention.
It is preferable. These inorganic metal salts are various chelate
It is also preferable to add the metal complex salt after forming it with the agent.
It is a new method. The bleach-fixing solution of the present invention contains a chelating agent other than the present invention and / or
May add its ferric complex salt. However, the book
The ferric iron complex salt outside the invention is different from the organic acid ferric iron complex salt of the present invention.
It is preferably used at 0.45 mol% or less. The pre-fixing solution may contain the bleaching accelerator of the present invention.
Preferred is as described above, at this time bleach-fixing
The person who most preferably contains a bleaching accelerator in the solution
Is the law. However, only one of them should be included.
It may be ok. When a bleaching accelerator is added only to the pre-fixing solution
The bleaching accelerator is a silver halide color copy from the prefix solution.
Brought to the bleach-fixing solution by a true light-sensitive material and exerts its effect
Will be done. In the bleach-fix solution, the iron complex salt generated in the bleach-fix solution
Oxidizing treatment may be applied to convert the reductant back to the oxidant
Although preferable, the oxidation treatment is, for example, an air oxidation treatment process.
Is used. What is the air oxidation process here?
Forced air bubbles in the processing solution in the bleach tank and bleach-fix tank
The forced oxidation process, in which the oxidation treatment is carried out by bringing them into contact with each other, is specified.
However, it also includes the fact that the liquid surface is naturally oxidized by contact with air.
However, this method is usually called
The air sent from a device such as a lesser has an oxidizing effect.
Like air distributor to increase the rate
A diffuser with fine holes allows the air to be as small as possible.
Use a small diameter to increase the contact area with the liquid, and
Oxidized by contact between the bubbles sent into the solution and the processing solution
Is preferable because the oxidation efficiency is high. This aeration is mainly performed in the processing tank.
However, it may be done in a batch in another tank, or
By the auxiliary tank for aeration attached to the side
You can go. Especially the regeneration of the bleaching solution and the bleach-fixing solution
When it is carried out, it is preferably carried out outside the tank liquid. Book
In the invention, it is usually called over-aeration
You don't have to think about it, so you can
May be performed, and a strong aeration is intermittent
It may be performed by any method and can be performed by any method. However
The smaller the air bubble diameter is, the better the efficiency.
It is preferable that you can prevent it from mixing with other liquids by splashing etc.
It can be said to be a good method. In the present invention, when the automatic processing machine is stopped
Perform aeration and stop aeration during processing
The method described above is also a preferable method. Also the processing is processed
The liquid may be introduced to the outside of the tank and separately performed. The above
The allocations are JP-A-49-55336, 51-9831, and 54-
Shower method and spray method described in Japanese Patent No. 95234
And jet spraying method can be used together.
The method described in Patent (OLS) 2,113,651 can also be used. [Examples] The present invention will be described in detail below with reference to Examples.
However, the embodiments of the present invention are not limited. Example 1 The silver halide emulsions shown in Table 1 were gold-sensitized and sulfur-sensitized.
The sensitizing dye exemplified compound (VIII-12) and [VIII
-16) was added to each 100mg / 1mol AgX, magenta coupler
Of the exemplified compounds M-25 and M-1 in the same amount as tricresylphos
Dispersion that is dissolved in fate and protected and dispersed by a conventional method
Add the solution to 0.3 mol of coupler per mol of AgX.
It was Furthermore, 4-hydroxy-6-methyl-1, as a stabilizer,
3,3a, 7-Tetrazaindene, 1-fu as an antifoggant
Phenyl-5-mercaptotetrazole and physical development inhibition
Adding poly-N-vinylpyrrolidone as an agent
It was applied on the above-mentioned cellulose acetate film. In addition
Add a Latin hardener to adjust the film swelling speed T1 / 2 to 8-14 seconds.
Arranged Binder swelling speed T1 / 2 is known in the art
It can be measured according to any arbitrary method, such as
Photographic services by A. Green et al.
Yence and Engineering (Phot.Sci.En
g.), Volume 19, Issue 2, pages 124-129
Can be measured by using a
Maximum reached when processed with color developer at 30 ℃ for 3 minutes 15 seconds
90% of the swollen film thickness is taken as the saturated film thickness, and this half of the film thickness is reached
It is defined as the time to do. Applying silver halide for silver halide color photographic light-sensitive material
The hydrophilic binder used to do this is usually gelatin.
However, in some cases high molecular weight polymers are used,
The swelling speed T1 / 2 must be less than 25 seconds.Non-wedge exposure of the above samples (A) to (G) by 32 CMS by a conventional method.
And developed with the following color developer to develop the maximum density of developed silver.
By measuring the ratio of the coated silver amount and the sensitivity of the sample (A).
The relative sensitivity of 100 is shown in Table 1. Processing process (38 ℃) Color development 3 minutes 15 seconds Bleach-fixing (1st bath) 2 minutes 〃 (2nd bath) 2 to 30 minutes Washing alternative stabilizer (1st bath) 50 seconds 〃 (2nd bath) 50 seconds Stable 40 seconds Drying 1 minute 30 seconds The formulation of each treatment liquid in each treatment step is as follows. : Color developer: Potassium carbonate 30g Sodium sulfite 2.0g Hydroxyamine sulfate 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) 1.0 g Magnesium chloride 0.3 g Hydroxyethyliminodiacetic acid 3.0 g Potassium bromide 1.2 g Sodium hydroxide 3.4 g N-ethylene-N-β-hydroxyethyl-3-methyl
-4-Aminoaniline hydrochloride 4.6g Add water to make 1 and adjust to pH 10.1 with sodium hydroxide.
did. : Bleach-fixing solution: Diethylenetriamine pentaacetic acid ferric ammonium salt 150g Hydroxyethyliminodiacetic acid 20g Ammonium thiosulfate 200g Ammonium sulfite 10g Ammonia water (28%) 20ml Adjust to 1 with water and adjust the pH to 7.6 with acetic acid and ammonia water.
It was : Stabilizing solution for washing with water: 5-chloro-2-methyl-4-isothiazoline-3-o
0.01 g 2-Methyl-4-isothiazolin-3-one 0.01 g Ethylene glycol 2.0 g Make to 1 with water. : Stabilizer: Formalin (37% aqueous solution) 3 ml Conidax (Konishi Roku Photo Co., Ltd.) 7 ml Add water to finish to 1. In the processing step, the bleach-fix solution was subjected to iodination shown in Table-2.
The amount of potassium is made to exist in each of the first tank and the second tank, and
Addition of bleach-fixing end time and 2 minutes of the first tank is shown in Table-2.
It was For comparison, the desilvering time of the one-bath bleach-fixing process is shown.
It is also shown in 2.As is clear from Table-2, the test which is the subject photosensitive material of the present invention
The effects of the present invention are obvious in the materials (D) to (G). Next, change the sensitizing dye to the following sensitizing dye A and perform the same experiment
Was repeated, but in any case of the two-bath treatment of the present invention,
However, the results were inferior to those of Table-2. Sensitizing dye AExample 2 Using the sample (E) of the above Example 1 and carrying out the above-mentioned treatment steps
And the processing solutions other than the bleach-fix solution have the same composition,
Iodide according to the present invention as a composition for landing, as a bleaching agent
The combined effect of organic acid iron complex salt and bleaching accelerator was examined. That
The composition conditions are shown in Table-3, and the same treatment was applied to the bath treatment in the first tank.
The total desilvering time including the bleach-fixing time of 2 minutes is listed. As is clear from Table 3, the desilvering promoters of the exemplified compounds
When added, is the desilvering time shorter than the results in Table-2?
In addition, the desilvering promoter according to the present invention represented by the above general formula is extremely
It can be seen that a favorable effect is exhibited. Further, in the present invention, the organic acid contained in the bleach-fixing solution
A ferric salt is a diethyl ether whose free acid has a molecular weight of 300 or more.
Ethylenediamine with less than 300
It turns out that it is preferable as compared with tetraacetic acid. For bleaching accelerators, in addition to those shown in Table-3, I-1
4, I-15, I-16, I-17, I-28, II-85, II-10
0, II-145, II-148, II-152, II-157, II-158, II
I-2, III-3, III-4, IIII-6, III-33, IV-
Completely the same treatment was carried out using 1, VI-11 and V-70.
However, the same effect as II-70 in Table 3 was shown. Example 3 In the processing step and processing solution of Example 1, a bleach-fix solution was used.
Bleaching accelerator exemplified compound V-71 in 1.0 g / l, potassium iodide
About 1st tank 1.0g / l, 2nd tank 0.1g / l, bleach diet
Instead of rentriaminepentaacetic acid, the organic acids listed in Table 4
The same procedure as in Example 1 was conducted using the sample (E) using a diiron complex salt.
And the total time required for desilvering was measured.
It was As is clear from Table-4, the present invention provides organic acid ferric complex salts.
The molecular weight of the free acid is preferably 300 or more.Example 5 A multilayer color light-sensitive material was prepared as described below, and was applied to the sample.
Ming processing method using automatic processor (Konishi Rokusha Kogyo NP
-34 modified machine), and the bleach-fix replenisher amount
The effect of the present invention is obtained by continuously treating the volume until it reaches three times the total capacity of the tank.
I observed. [Preparation of multilayer color light-sensitive material] Support; Cellulose triacetate film First layer; Antihalation layer Gelatin layer containing black colloidal silver Second layer; Intermediate layer (gelatin layer) Third layer; First red-sensitive emulsion layer Core below / Shell emulsion A: Coating silver amount: 1.6g / m² Sensitizing dye I (Ex. VIII-2) ... 6 × 10^-FiveMol / Ag mol Sensitizing dye II (Ex. VIII-16) ...... 1.5 × 10^-FiveMol / Ag mol Cyan coupler (exemplary C-1): 0.044 mol / Ag mol Fourth layer: second red-sensitive emulsion layer Core / shell emulsion B: coating silver amount: 2.0 g / m² Sensitizing dye I (Ex. VIII-2) ... 3.5 × 10^-FiveMol / Ag mol Sensitizing dye II (Ex. VIII-16) …… 1.0 × 10^-FiveMol / Ag mol Cyan coupler (Ex. C-28) ...... 0.020 mol / Ag mol Fifth layer; intermediate layer Same as second layer Sixth layer; first green-sensitive emulsion layer Core / shell emulsion A: Coated silver Amount 1.8g / m² Sensitizing dye III (Ex. VIII-12) …… 3.3 × 10^-FiveMol / Ag mol Sensitizing dye IV (Ex. VIII-20) …… 1.0 × 10^-FiveMol / Ag mol Magenta coupler (exemplary M-1) ...... 0.044 mol / Ag mol 7th layer; second green-sensitive emulsion layer Core / shell emulsion B ...... Coating silver amount 1.8g / m² Sensitizing dye III (Ex. VIII-12) ... 2.65 × 10^-FiveMol / Ag mol Sensitizing dye IV (Ex. VIII-20) ...... 0.89 × 10^-FiveMol / Ag mol Magenta coupler (exemplary M-25) ...... 0.02 mol / Ag mol Eighth layer; Yellow filter layer Gelatin layer containing yellow colloidal silver Ninth layer; First blue-sensitive emulsion layer Core / shell emulsion A below … Amount of coated silver 1.4g / m² Sensitizing dye V (below) …… 2.5 × 10^-FiveMol / Ag mol Yellow coupler Y (below) ...... 0.25 mol / Ag mol 10th layer; 2nd blue-sensitive emulsion layer Core / shell emulsion A ...... Coating silver amount 1.4g / m² Sensitizing dye V (below) …… 2.5 × 10^-FiveMol / Ag mol Yellow coupler Y (below) ...... 0.06 mol / Ag mol 11th layer; 1st protective layer Gelatin layer in which UV absorber is emulsified and dispersed 12th layer; 2nd protective layer Trimethylmethacrylate particles (diameter 1.5 μm) including
Gelatin layer In addition to the above composition, a gelatin hardener and a surface active agent are added to each layer.
A sex agent was added. The film swelling speed T1 / 2 was adjusted to 9 seconds.・ Core / Shell Emulsion A 5 mol% silver iodide, silver iodobromide, shell thickness 0.01 μm, grains
Diameter 0.50 μm Core / shell emulsion B 7 mol% silver iodide silver iodobromide and shell thickness 0.02 μm
1.0 μm ・ Sensitizing dye V・ Yellow coupler Y[Development processing of sample light-sensitive material]: processing step; in the processing step of Example 1, bleach-fixing (second bath) was performed for 2 minutes.
Stable with bleach-fixing bath and washing with water
The chemical bath was based on a two-stage retrograde overflow system. Other than the above
This was copied as in Example 1. : Treatment liquid prescription and amount of replenishing liquid; Prescription of treatment mother liquor (tank liquid) in each treatment bath was carried out in Example 1
The same for each treatment liquid formulation. However, the bleach-fix solution
Add potassium iodide as follows according to the purpose of Ming
There is. The replenisher of each processing solution and the prescription of the bleach-fixing mother liquor are as follows.
Is. Color development replenisher; replenishment rate 15 ml / dm² Potassium carbonate 40g Sodium hydrogen carbonate 3g Potassium sulfite 7g Potassium bromide 0.9g Hydroxylamine sulfate 3.1g 4-Amino-3-methyl-N-ethyl-N- (β-hydride
Roxylethyl) aniline sulfate 6.0 g Nitrilotriacetic acid trisodium salt 3.0 g Potassium hydroxide 2.0 g Add water to make 1 and add potassium hydroxide or 20% sulfuric acid.
Adjust to pH 10.12 using. Bleach-fixing replenisher; replenishment rate 10 ml / dm² Bleach-fixing solution of Example 1 1 Exemplified compound V-71 1.0 g Bleach-fixing first tank mother liquor; Bleach-fixing solution of Example 1 1 Exemplified compound V-71 1.0 g Potassium iodide 1.0 g Bleach-fixing second tank mother liquor; Implementation Bleach-fixing solution of Example 1 1 V-71 1.0 g Potassium iodide 0.1 g Washing substitute stable replenisher; Replenishment rate 10 ml / dm² The same stable replenisher as the water-replacement stabilizer of Example 1; replenishment rate 10 ml / dm² The stabilizing solution of Example 1 was subjected to the same continuous treatment as above, and as a result, 32 CMS
The amount of residual silver in the maximum density part of the sample subjected to wedge exposure is
From a practical point of view, it was zero and the result was extremely good. still
The amount of developed silver before desilvering was 20 to 25% of the coated silver amount. Also, the mother liquor of the first and second tanks for bleach-fixing after the completion of continuous processing
The contents of iodide in potassium iodide are 1.0 g / l and 0.2 g / l, respectively.
Met. In addition, the iodide was removed from the bleach-fixing solution and the replenishing solution to obtain a single tank.
As a result of the same continuous treatment in (one bath) treatment, bleach-fixing 4
10 mg / dm in minutes²Residual silver is present, and zero residual silver
It took 13 minutes to bleach and fix. Further, the light-sensitive material sample that has been subjected to the processing of the present invention is
(Bath) compared to the treated sample, no leuco dyeing occurred,
It also gives good results for image preservation and stain.
There was no loss of sensitivity or deterioration of graininess.

Claims (10)

[Claims] 1. In the processing of a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer containing a core / shell emulsion containing 3.5 mol% or more of silver iodide, exposure and color development are carried out. After that, the developed silver amount in the maximum density portion of the light-sensitive material was adjusted to 50% or less of the coated silver amount, and then at least two tanks were prepared using a bleach-fixing solution containing an organic acid ferric salt and thiosulfate as main components. When the bleach-fixing bath treatment consisting of the above bleach-fixing tank is performed, the iodide concentration in the bleach-fixing solution in the final bleach-fixing tank is adjusted to 50% or less of the iodide concentration in the bleach-fixing solution in the first tank. A method of processing a silver halide photographic light-sensitive material, which is characterized by holding the same. 2. The bleach-fixing solution is represented by the following general formulas [I] to [VI.
I] and [VII ′] containing a compound selected from
A silver halide mosquito according to claim 1, characterized in that
Method for processing photographic light-sensitive material.General formula (VII)[In the above general formula, Q is a heterocycle containing at least one N atom.
(At least one 5- or 6-membered unsaturated ring is condensed to this
The atomic groups necessary to form
IsOr n₁Valent heterocyclic residue (less 5 to 6 membered unsaturated ring
(Including one condensed to this), and B is
Represents an alkylene group having 1 to 6 carbon atoms, M is a divalent metal
Represents an atom, and X and X ″ represent ═S, ═O or ═NR ″,
R ″ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Chloroalkyl group, aryl group, heterocyclic residue (5- or 6-membered
Also having at least one unsaturated ring fused to
Or N- or CH-.
Represents, Z is hydrogen atom, alkali metal atom, ammonium
Group, amino group, nitrogen-containing heterocyclic residue orAnd Z'represents Z or an alkyl group, R¹Is hydrogen
Child, alkyl group having 1 to 6 carbon atoms, cycloalkyl group,
Aryl group, heterocyclic residue (5- to 6-membered unsaturated ring is few
At least one condensed with this) or
R represents the², R³, R^Four, R^Five, R and R'are hydrogen
Child, alkyl group having 1 to 6 carbon atoms, hydroxy group, carbo
Xyl group, amino group, acyl group having 1 to 3 carbon atoms, aryl
Represents a group or an alkenyl group. However, R^FourAnd R^FiveIs -B-
SZ may be represented and R, R ', R²And R³, R^FourAnd R^FiveHaso
Heterocyclic residues (5- to 6-membered unsaturation)
Including at least one ring fused thereto)
You may form. R⁶, R⁷Are eachRepresents R⁹Is an alkyl group or-(CH₂) n₈SO₃ Represents (but
R⁸But- (CH₂) n₈SO₃ When, 1 represents 0 or 1. )
G Is anion, m₁Through m_FourAnd n₁Through n₈Are each
An integer from 1 to 6, m_FiveRepresents an integer of 0 to 6. R⁸Is hydrogen
Child, alkali metal atom,Or represents an alkyl group. However, Q'is synonymous with the above Q.
It D is a mere bond, an alkylene group having 1 to 8 carbon atoms
Alternatively, it represents a vinylene group, and q represents an integer of 1 to 10. Compound
Several D's may be the same or different and form with a sulfur atom.
The ring formed may be further condensed with a 5- or 6-membered unsaturated ring.
Yes. X'is -COOM ', -OH, -SO₃M ′, -CONH₂, -SO₂N
H₂, -NH₂, -SH, -CN, -CO₂R¹⁶, -SO₂R¹⁶, -OR¹⁶, -NR
¹⁶R¹⁷, -SR¹⁶, -SO₃R¹⁶, -NHCOR¹⁶, -NHSO₂R¹⁶, -OCOR
¹⁶Or-SO₂R¹⁶And Y'isOr represents a hydrogen atom, and m and n are each an integer of 1 to 10.
Represents R¹¹, R¹², R¹⁴, R¹⁵, R¹⁷And R¹⁸Is a hydrogen atom, lower
An alkyl group, an acyl group orRepresents R¹⁶Represents a lower alkyl group. R¹⁹Is-NR
²⁰R^{twenty one}, -OR^{twenty two}Or-SR^{twenty two}Represents R²⁰And R^{twenty one}Is a hydrogen atom
Or a lower alkyl group, R^{twenty two}Is R¹⁸And connect the ring to
Represents the atomic groups necessary to form. R²⁰Or R^{twenty one}And R¹⁸Is
They may be linked to form a ring. M'is a hydrogen atom or cut
Indicates ON. In addition, it is represented by the above general formulas [I] to [V].
The compounds include enol compounds and salts thereof. ] General formula [VII ′][In the above general formula, Ar is an aromatic linking group, B¹And B²Is it
Each represents a lower alkylene group. R^{twenty three}, R^{twenty four}, R^{twenty five}And R²⁶Is
Each represents a hydroxy-substituted lower alkyl group. G'is
Anions, x and y are integers of 0 or 1, and z is
Represents an integer of 0, 1 or 2. ] 3. A silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the total silver coating amount of the silver halide color photographic light-sensitive material is 35 mg / dm ² or more. Processing method. 4. The silver halide color photographic light-sensitive material is below.
Containing a sensitizing dye represented by the general formula [VIII]
Claims characterized in any one of claims 1 to 3.
Method for processing silver halide color photographic light-sensitive material. General formula
[VIII]Where Z₁And Z₂Is a benzene ring fused to a heterocycle
Alternatively, it represents an atomic group necessary for forming a naphthalene ring.
The heterocyclic nucleus formed may be substituted with a substituent. R₁
And R₂Is an alkyl group, an alkenyl group or an aryl, respectively.
R group, R₃Is a hydrogen atom or an alkyl having 1 to 3 carbon atoms
Represents a group. X₁ Represents an anion, p represents 0 or 1.
You Y₁And Y₂Is oxygen atom, sulfur atom, selenium atom, nitrogen
Represents an atom and a terium atom. 5. The iodide concentration in the bleach-fixing solution in the final tank of the bleach-fixing tank is set to 30 times the iodide concentration in the bleach-fixing solution in the first tank.
% Or less, the method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 4. 6. The bleach-fixing solution of the first tank of the bleach-fixing tank has an iodide concentration of 0.002 to 0.03 mol / l. Method for processing silver halide color photographic light-sensitive material. 7. In the bleach-fix bath treatment, a bleach-fix replenisher is placed in a final tank to prevent overflow of the bleach-fix bath in a direction opposite to the traveling direction of the silver halide color photographic light-sensitive material to be treated. 7. A processing method of a silver halide photographic light-sensitive material according to any one of claims 1 to 6, characterized in that a multi-stage retrograde overflow system is used in which the solution is sequentially introduced into the front tank and outflowed from the first tank. 8. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the bleach-fixing bath treatment comprises two baths. 9. A silver halide color photograph according to any one of claims 1 to 8, wherein the free acid constituting the ferric organic acid salt has a molecular weight of 300 or more. Method of processing photosensitive material. 10. A silver halide color photograph according to any one of claims 2 to 9, wherein the compounds represented by the general formulas [I] to [VII] are the following compounds. Method of processing photosensitive material. Or