JPS6147959A - Treatment of silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To bleach quickly a high-sensitivity color photosensitive material by subjecting the core-shell type photosensitive material contg. silver halide to an exposing and developing process then processing the material with a bleaching soln. contg. an org. acid ferric complex salt. CONSTITUTION:The photosensitive material of the core-shell type is manufactured by forming the core of the silver halide contg. silver iodide and forming the shell of silver bromide, silver chlorobromide, etc. thereon to 0.01-0.5mum thickness. The bleaching agent contg. the org. acid ferric complex salt, for example, diethylene triamine pentaacetic acid ferric complex salt, diethylene triamine pentamethylene phosphonic acid ferric salt, etc. is prepd. as the bleaning agent. The photosensitive material is developed after imagewise exposing and is bleached by such bleaching agent. Since the core-shell type photosensitive material having high sensitivity is processed by the above-mentioned bleaching agent, the quick bleaching of the developed silver is made possible. The simultaneous and faster cleaning and fixing of the photosensitive material are made possible by adding an ammonium salt, etc. to the bleaching soln. to prepare the bleach-fix bath.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing silver halide color photographic materials having rapid silver bleaching ability.

[Prior Art] Generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material, after the color development step, there is a step of treating the produced metallic silver with a processing solution having bleaching ability. is provided.

Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, a step of fixing the silver halide with a fixing agent is usually added next to the bleaching step, but with a bleach-fixing solution, bleaching and fixing are performed in one step.

Inorganic oxidizing agents such as red blood salts and dichromates are widely used as oxidizing agents for bleaching image silver in processing solutions that have bleaching ability in processing silver halide color photographic light-sensitive materials. .

However, some serious drawbacks have been pointed out to the bleaching solutions containing these inorganic oxidizing agents. Although it is relatively good, it has undesirable properties in terms of pollution prevention, as it may decompose when exposed to light and generate cyanide ions and hexavalent chromium ions that are harmful to the human body. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers (fixing agents) such as thiosulfates in the same processing solution, and these agents are not used in bleach-fixing baths. It is almost impossible to use saponifying agents;
This makes it difficult to achieve the goal of speeding up and simplifying processing. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment.

On the other hand, gold-Fi of organic acids such as aminopolycarboxylic acid gold-B complex salts have been proposed as a method that has few pollution problems and meets the requirements of speeding up and simplifying treatment, and being able to reuse waste liquid.
E&! Processing solutions that use salt as an oxidizing agent have come into use. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so they have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow. 0 For example, ethylenediaminetetraacetate iron <m) complex salt, which is considered to have a strong bleaching edge among the aminopolycarbonate complex salts, has been put into practical use as a bleach solution and bleach-fix solution in some places, but High-sensitivity silver halide color photographic materials based on silver and silver iodobromide emulsions, especially color papers for photography containing silver iodide as silver halide, color negative films for photography, and color reversal films with bleaching blades. is insufficient, and even after long-term processing, traces of image silver remain, resulting in poor desilvering properties. This tendency is particularly noticeable in bleach-fix solutions in which oxidizing agents and thiosulfates and sulfites coexist because the redox potential decreases.

Furthermore, in addition to the above-mentioned high-sensitivity silver iodide emulsions, core-shell emulsions have recently been developed as silver halide emulsions that are highly sensitive, have fine grains, and utilize silver effectively to meet the requirements for resource conservation. . This emulsion is a monodisperse core-shell emulsion made by using a preceding silver halide emulsion as a crystal nucleus, successively layering subsequent precipitates on top of this, and intentionally controlling the composition or environment of each precipitate. Among these, the core-shell type high-sensitivity emulsion containing silver iodide in the core has been found to have a high covering power for developed silver and to have extremely favorable characteristics in terms of photographic performance. However, as a result of studies conducted by the present inventors, when this emulsion is applied to color photographic light-sensitive materials, the bleaching performance of the developed silver is extremely poor with conventional bleaching solutions and bleach-fixing solutions, and the developed silver of general silver halide emulsions has a very poor bleaching performance. It was found that it has properties that make it less susceptible to bleaching.

That is, developed silver of a photographic silver halide emulsion containing 0.1 mol % or more of silver iodide, especially a core-shell emulsion, which contains silver iodide in the core and has a shell thickness of 0.5 µm. Although the developed silver of the following silver halide grains has excellent sensitivity, granularity, covering power, etc., in color photographic light-sensitive materials that require bleaching, the form of the developed silver is different from conventional ones, so bleaching is required. It has been found that it is particularly difficult to use bleaching solutions and bleach-fix solutions using conventionally known ethylenediamine ferric complex salts and nitrilotriacetic acid ferric complex salts as bleaching agents. Similarly, as an emulsion to improve the conventional drawbacks, JP-A-58-11
No. 3930, No. 58-113934, No. 58-127
Techniques using tabular silver halide grains have been developed, such as those described in No. 921 and No. 58-108532.

With this tabular grain technology, even if the number of photons captured by silver halide grains increases, the amount of silver used does not increase, and image quality does not deteriorate. Developed silver formed by development with a phenylenediamine color developing agent has the disadvantage of poor sheet bleaching properties. Therefore, there is a strong desire for a processing solution that can quickly bleach or bleach-fix color photographic materials comprising core-shell emulsions and/or tabular silver halide emulsions, which are excellent emulsions such as those mentioned above.

[Problems to be Solved by the Invention] First, the present invention provides an excellent method for bleaching or bleach-fixing high-sensitivity fine-grain type high-sensitivity silver halide color photographic materials that can achieve both resource conservation and ultra-high sensitivity. The technical issue is to provide a processing method, and the second is to provide a specific treatment method! acid second
A technical object of the present invention is to provide a processing method using a bleach solution or a bleach-fix solution that enables rapid processing of high-sensitivity color photographic materials by using iron complex salts.

[) Composition of A Ming As a result of intensive research, the present inventor found that a core consisting essentially of silver halide containing silver iodide, and silver bromide, silver chloride, silver chlorobromide, or silver iodobromide, or A silver halide color photographic photosensitive material comprising tabular silver halide grains containing silver halide grains and/or silver iodide and a shell consisting essentially of a mixture of and having a thickness of 0.01 to 0.57 zm. After imagewise exposure, the material is developed, and p) I of at least one organic acid ferric complex salt (A) selected from the following ferric complex salt group or the following standard solution of an organic acid ferric complex salt is used as a bleaching agent. is 5
．． By treating with a treatment solution having bleaching ability containing at least one organic acid ferric complex salt (B) having a redox potential difference within 100 mV between 0 and 8.0, the above-mentioned technical I discovered that the problem (purpose) could be solved.

[Organic acid ferric chain kM (A)] (1) Diethylenetriaminepentaacetic acid ferric complex salt (2) Diethylenetriamine triphosphate w42 iron complex salt (3) Cyclohexanediaminetetraacetic acid ferric complex salt (0 cyclohexanediaminetetraphosphorus #t52 iron Complex salt (5) Triethylenetetraminehexaacetic acid WI12 iron complex salt (6) Triethylenetetramine hexaphosphate ferric complex salt (7) Glycol ether diamine tetraacetic acid ferric complex salt (8) Glycol ether diamine tetraphosphate ferric complex salt (11) ) 1.2-Diaminopropanetetraacetic acid ferric complex salt (10) 1.2-diaminopropanetetraacetic acid ferric complex salt (
11) Ferric methyliminodiacetic acid complex salt (12) Ferric methyliminodiaphosphate complex salt [Reference solution of ferric organic acid complex salt of an organic acid such as aminopolycarboxylic acid for redox potential measurement] Ferric chloride 0.23M aminopolycarboxylic acid Organic acids such as acids 0.305M thiogm ammonium 1.0Mi ammonium sulfate
'JJM p)I using 0.1M ammonia water and acetic acid, and measure the redox potential.

The present inventor has developed a legalized silver core-shell emulsion and/or a legalized silver tabular silver halide emulsion that produces developed silver that is difficult to bleach when treated with a processing solution having bleaching ability containing an ethylenediaminetetraacetic acid ferric complex salt. (hereinafter referred to as the emulsion of the present invention), it was found that the present invention takes advantage of the characteristics of an excellent core-shell emulsion that can maximize the silver utilization effect and obtain a high-sensitivity fine-grain emulsion. However, we have discovered that it is possible to improve the bleaching properties of developed silver, which is its biggest drawback.

Furthermore, the present inventor found that although there is no significant difference in the butyricating power of various well-known organic ferric complex salts compared to the developed silver of conventional emulsions, surprisingly, the emulsion of the present invention has a In the case of developed silver, it has been discovered that when the unique organic acid ferric complex salt according to the present invention is used as a bleaching agent, processing can be carried out in an extremely short time.

In a preferred embodiment of the present invention, the processing solution having bleaching ability is a bleach-fixing solution, and the surface tension of the processing solution having bleaching ability is 55 dyne/C11 or less. We have found a way to achieve the purpose of the invention more effectively.

In the present invention, processing with a processing solution having bleaching ability means
This means processing with a bleach solution or a -bath bleach-fix solution, but the effect of the present invention is better achieved when a -bath bleach-fix treatment is performed. The following explanation will mainly be made regarding this one-bath bleach-fixing process.

The bleach-fix solution of the present invention contains an organic acid ferric complex salt (A) or (B) as a bleaching agent.

As the organic acid ferric complex salt (A), one type can be arbitrarily selected from among the above 12a, and two or more types can also be used in combination as necessary.

Among the above 12 kinds of compounds of the organic acid 12-iron complex salt (A), the following are particularly preferable.

(I) diethylenetriaminepentavinegar ugly ferric complex salt (II
) Cyclohexanediaminetetraacetic acid ferric complex salt (■) Triethylenetetramine hexaacetic acid ferric complex salt Organic acid ferric complex salt (B) is a group of multiple organic acid ferric complex salts regulated by redox potential, One type can be arbitrarily selected from these and used, and two or more types can also be used in combination as necessary.

In the present invention, the oxidation-reduction potential of a reference solution of an organic acid ferric complex salt such as aminopolycarbonate is measured using a platinum electrode at 25°C using an ordinary PH meter, and the reference electrode is calomel. This was measured using an electrode.

Regarding the relationship between pi and potential of organic acid ferric complex salts such as aminopolycarbonate, data for the ferric complex salt alone is known. However, when measured with the bleach quantitative standard solution of the present invention, there is a wide range of This was a surprising discovery, as it was completely unknown that only organic acids such as aminopolycarboxylic acids, which have a small difference in redox potential across the PH region, exhibit the favorable effects of the present invention.

Specific examples of organic acid complex salts such as aminopolycarboxylic acids having a redox potential within the scope of the present invention include, but are not limited to, the following.

(1) Ferric diethylenetriaminepentaacetic acid complex salt (2) Ferric diethylenetriaminepentaphosphate complex salt (3) Ferric cyclohexanediaminetetraacetic acid complex salt (4) Ferric cyclohexanediaminetetraphosphate rust salt (5) Ferric salt of cyclohexanediaminetetraphosphate Ethylenetetraminehexaphosphate ferric complex salt (6) Triethylenetetraminehexaphosphate ferric rust salt The ferric complex salt of an organic acid according to the present invention is a free m(hydrogen salt), sodium salt, potassium salt, Alkali metal salts such as thium salts, ammonium salts, or water-soluble amine salts such as triethanolamine salts are used, but potassium salts, sodium salts, and ammonium salts are preferably used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but in general, its concentration is lower than that of other 7-minoboricarboxylate salts because of its high oxidizing power. For example, it can be used in an amount of 0.01 mol or more per working solution 14Q, preferably 0.05 to 0.6 mol. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

The treatment liquid having bleaching ability of the present invention has a surface tension of 55d7n.
It is preferably less than e/am, more preferably 5
0d7ne/am or less, most preferably 40dyne/am
ctrr or less.

The surface tension of the treatment liquid with bleaching ability used in the treatment of the present invention is determined from "Analysis and Testing Methods of Surfactants" (co-authored by Fumio Kitahara, Shigeo Hayano, and Betsu Hara, published March 1, 1382, ■Kodansha In the present invention, the value of surface tension is measured by a general measuring method at 20°C.

In the present invention, any method may be used to reduce the surface tension of the processing liquid having bleaching ability to 55 dyne/cm or less, and any method may be used, but surfactants are preferably used. These surfactants that lower the surface tension of processing solutions having bleaching ability to 55 dyne/cm or less may be added to the tank solution from the replenisher solution, or may be added from the prebath by being attached to the photosensitive material. Furthermore, the surfactant may be contained in the light-sensitive material and dissolved and added to the processing solution having bleaching ability of the present invention.

Among the surfactants of the present invention, compounds represented by the following general formulas (1) to (0) are preferably used from the viewpoint of achieving the desired effects of the present invention.

General formula (1) % formula % In the formula, one of R1 and R2 is a hydrogen atom, and the other is a formula -
S03M (M represents a hydrogen atom or a -valent cation,
), Al represents an oxygen atom or a group represented by the formula -N
R3 represents a group represented by Rs - (Rs represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms);
and R4 each represent an alkyl group having 4 to 1B carbon atoms;

The alkyl group represented by R3, R4 or Rs may be substituted with a fluorine atom.

General formula (2) % formula % In the formula, Az is a monovalent organic group, for example, a carbon atom number of 6 to 2
0, preferably 6 to 12 alkyl groups (for example, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.), or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms. The substituent is preferably an alkyl group having 3 to 12 carbon atoms (eg, propyl).

butylpentyl, -hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, etc., and the aryl group includes phenyl, tolyl, xynyl, biphenyl or naphthyl, preferably phenyl. or tolyl group. The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta, and para positions, B represents ethylene oxide or propylene oxide, 1m represents an integer from 4 to 50, xl is a hydrogen atom, SO3Y or PO3Y z shows,
Y, Y2 are hydrogen atoms, alkali metal atoms (, Na
, K or Li) or ammonium ion.

General formula (3) In the formula, Rs, Rv, Ra and R9 each represent a hydrogen atom, an alkyl group, or a phenyl group, but Rs, Ry, Ra
and the total number of carbon atoms of Ri is 3 to 50. x2 represents an anion such as a halogen atom, a hydroxyl group, a sulfuric acid group, a carbonic acid group, a nitric acid group, an acetic acid group, and a p-1-luenesulfonic acid group.

General formula (0 In the formula, Ru, Ru, Ru, and RL3 each represent a hydrogen atom or an alkyl group, and K has the same meaning as in general formula (1).! I and P are each O or an integer of 1-4. It is a value that satisfies 1≦n+p≦8.

The bleaching solution and bleach-fixing solution of the present invention are as follows: p) 10.2 to 9
．． 5, preferably 4 to 8, more preferably 5
．． 5 to 8.5. The treatment temperature is used at 80° C. or lower, preferably 55° C. or lower, most preferably 45° C. or lower to suppress evaporation.

The treatment time is preferably within 8 minutes, more preferably within 6 minutes.

The bleaching solution according to the present invention can contain various additives in addition to the organic acid ferric complex salt as a bleaching agent as described above. As additives, it is particularly desirable to include alkali halides or ammonium/X-ray inhibitors such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. Borate, oxalate, acetate, carbonate,
P)I buffers such as phosphates, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkyl heptamines, polyethylene oxides, etc. Those known to be added to ordinary bleaching solutions can be added as appropriate.

The bleach-fix solution according to the present invention includes a bleach-fix solution containing a small amount of a halogen compound such as potassium bromide,
Or, conversely, a bleach-fix solution with a composition containing a large amount of a halogen compound such as potassium bromide or ammonium bromide, or a special composition containing a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide. A bleach-fix solution or the like can also be used.

In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. can also be used.

The silver halide fixing agent to be included in the bleach-fixing solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex, such as potassium thiosulfate, thiosulfate, etc., which is used in ordinary fixing processes. Representative examples include sodium, thiosulfate such as ammonium thiosulfate, thiocyanate such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thiourea, thioether, high concentration bromide, iodide, etc. .

These fixing agents are 5g/1 or more, preferably 50g/1
1 or more, preferably ? It can be used in an amount that can dissolve Og/JL or more.

Note that the bleach-fixing solution according to the present invention includes boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, linalum carbonate 1 bicarbonate potassium bicarbonate, acetic acid, acetic acid. pH consisting of various salts such as sodium and ammonium hydroxide
Buffers may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or antifoaming agents can be contained. Also, preservatives such as droxyamine, hydrazine, sulfites, isomeric bisulfites, bitonite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphorus, oxycarboxylic acid, polyester, etc. Organic chelating agents such as carboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids, stabilizers such as nitro alcohol, nitric acid groups, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, An organic solvent such as dimethylformamide or dimethyl sulfoxide can be appropriately contained.

In the processing method of the present invention, the most preferable processing method is to bleach or bleach-fix immediately after color development, but after performing treatments such as washing, rinsing, or stopping immediately after color development,
Bleaching or bleach-fixing may be performed, or a prebath containing a bleach accelerator may be used as a processing solution prior to bleaching or bleach-fixing.

After bleaching and fixing (or bleach-fixing), stabilization processing can be performed without washing with water, or washing with water and stabilization processing can be performed after that.In addition to 0 or more steps, hardening, neutralization, black and white development 1
Typical examples of preferred processing methods include the following steps, in which known auxiliary steps such as inversion and washing with a small amount of water may be added as necessary.

(1) Color development → bleach fixing → water washing (2) color development → bleach fixing → small amount of water washing → water washing (3) color development → bleach fixing → water washing → stable (4) color development → bleach fixing → stable (5) color development → Bleach fixing → 1st stability → 2nd stability (6)
Color development → washing with water (or stable) → bleach-fixing → washing with water (or stable) (7) Color development → stop - 1'7! White fixation → washing with water (or stabilization) (8) Color development → bleaching - washing with water fixation → washing with water → stabilization (
8) Color development → bleaching → fixing, washing with water → stable (lO) color development → bleaching → fixing → first stable pass, second stable (11) color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stable (12) ) Color development → washing with a small amount of water → bleaching → washing with a small amount of water → fixing →
Wash with a small amount of water → Wash with water → Stabilize (13) Stop color development → Bleach → Wash with a small amount of water → Fixation level 1
Washing with water → stable (10 black and white development → washing with water (or stable) → reversal color development →
Bleaching → fixation, washing with water (or omission) → stabilization (15) pre-dural mater →
Neutralization → black and white development toge stop toge toge color development → bleaching → regular cleaning → washing with water (
(or omitted) → Stability Among these treatment steps, one of the effects of the present invention is more noticeable, so (1), (2), (3), (4), (
The processing steps having the bleach-fixing steps of 5), (13) and (7) are more preferably used in the present invention.

It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention. It is also preferable to add these inorganic metal salts after forming them into metal complex salts together with various chelating agents.

It is preferable to add a chelating agent and/or a ferric complex salt thereof other than the present invention to the bleach-fixing solution of the present invention. It is preferable to use it in an amount of 0.45 mol% or less when expressed as mol%.

Regarding the core-shell emulsion used in the present invention, JP-A No. 57
As described in detail in No. 154232, a preferred color photographic light-sensitive material has a silver halide composition of 0 silver iodobromide.
．． The silver halide contains 1 to 20 mol%, preferably 0.5 to 10 mol%, and the shell is composed of silver bromide, silver chloride, silver iodobromide, or silver chlorobromide.

Particularly preferably, the shell is a silver halide emulsion comprising silver bromide. Further, in the present invention, the core is made of monodisperse silver halide grains, and the thickness of the shell is 0.01 to 0.
．． A preferable effect can be achieved by setting the thickness to 5 μm.

The silver halide color photographic light-sensitive material of the present invention is characterized by being made of silver halide grains containing silver iodide, and in particular, using silver halide grains containing silver iodide as a core, By hiding the core of silver halide grains made of silver bromide or silver iodobromide using a shell having the above-mentioned specific thickness, the ability of silver halide grains containing silver iodide to be highly sensitive can be utilized. , and conceals the disadvantageous properties of the particles. More specifically, the core is made of silver halide containing silver iodide, and the thickness range necessary to effectively exhibit only the desirable properties of this core and to shield undesirable behavior is strictly regulated. The purpose is to provide a shell to the core. The method of covering the core with a shell that has the necessary minimum absolute thickness to effectively utilize its properties can be used to change the purpose, and therefore to change the materials of the core and shell, for example, to improve or increase the shelf life. It is extremely advantageous in that it can be used for purposes such as improving the dye-sensitive adsorption rate.

The silver iodide content in the silver halide grains (core) serving as the matrix ranges from 0.1 to 20 mol% solid solution to mixed crystal, but is preferably 0.5 to 10 mol%. . The silver iodide contained within the core may be distributed unevenly or uniformly, but uniform distribution is preferred.

The silver halide emulsion of the present invention having silver halide grains having a shell of a specific thickness can be produced by coating the core with silver halide grains contained in a monodisperse emulsion with a shell. . In addition, when the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 10 mol % or less.

To make the core a monodisperse silver halide grain.

Particles of a desired size can be obtained by the double jet method while keeping PAg constant. Furthermore, the production of highly monodisperse silver halide emulsions was disclosed in Japanese Patent Application Laid-Open No. 54-48521.
The method described in this issue can be applied. A preferred embodiment of this method is a method in which an aqueous potassium-gelatin solution and an aqueous ammonium silver nitrate solution are added to an aqueous gelatin solution containing silver halide seed particles while changing the addition rate as 1321 times the time. It is manufactured by At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, pH, pag, temperature, etc.

Since the particle size distribution of a monodisperse emulsion is almost a normal distribution, the standard deviation can be easily determined. From this, if we define the relation x too = width of distribution (%) by the average particle size, the width of distribution that can meaningfully control the absolute thickness of the coating is monodisperse of 20% or less. It is preferable that there is a value of 10, more preferably 10
% or less.

Next, the thickness of the shell covering the core must be such that it does not hide the favorable qualities of the core, and on the contrary, it must be thick enough to hide the unfavorable qualities of the core, i.e.
The thickness is limited to a narrow range defined by such upper and lower limits. Such a shell can be formed by depositing a soluble halide solution and a soluble silver solution onto a monodisperse core by double jetting.

For example, an average grain size of 1 μm containing 2 mol% silver iodide in the core
According to experiments using monodisperse silver halide grains of 0.2 mol % silver iodobromide as a shell and varying the coating thickness, 1, for example, when a shell with a thickness of 0.85 μm was made, this method The monodisperse silver halide grains obtained by the method had low covering power. This was treated with a physically developing processing solution containing a solvent that dissolves silver halide, and when observed under a scanning electron microscope, it was found that no developed silver filaments were present. This suggests that the optical density and even the covering power are reduced. Therefore, considering the filament form of developed silver, we thinned the thickness of the silver bromide shell on the surface while changing the average grain size of the core. The thickness is 0.5 l or less (preferably 0.
．． 27 tm or less), a large number of good developed silver filaments were produced, sufficient optical density was produced, and the quality of the core for high sensitivity was not impaired.

On the other hand, if the thickness of the shell is too thin, parts of the core material containing silver iodide will be exposed, and the effect of covering the surface with the shell, that is, the chemical sensitization effect, rapid development, fixing properties, etc. will be lost. be exposed. Its thickness limit is 0.1 μm.

Further confirmed by a highly monodisperse core with a distribution width of 10% or less, the preferred shell thickness is 0.01 to 0.08 g.
m, and the most preferable thickness is 0.03 p, rx or less.

The above-mentioned development silver filaments are sufficiently generated to improve the optical density, the high-sensitivity properties of the core are utilized to produce a sensitizing effect, and rapid development and fixing properties are achieved due to the high This is due to the synergistic effect between the shell whose thickness is regulated as described above by the dispersible core and the silver halide composition of the core and shell, so if the thickness regulation of the shell can be satisfied, the shell is constituted. As the silver halide, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used. Among them, silver bromide, silver iodobromide, or a mixture thereof is preferred from the viewpoint of core compatibility, performance stability, storage stability, etc.

The light-sensitive silver halide emulsion used in the present invention is prepared by forming a core and shell silver halide precipitate.

Doping may be performed with various metal salts or metal complex salts during or after grain growth.For example, metal salts or complex salts such as gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper, etc., and combinations thereof are applied. can.

In addition, excess halogen compounds generated during the preparation of the emulsion of the present invention, salts such as nitrates and ammonium, and compounds that are duplicated or become unnecessary may be removed. ,
A dialysis method, a coagulation precipitation S method, or the like can be used as appropriate.

Furthermore, the emulsion of the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin or the like, either alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There is no particular restriction on the method for optically sensitizing the emulsion of the present invention. For example, cyan dyes such as zeromethine dyes, monomethine dyes, trimethine dyes, Alternatively, optical sensitization can be carried out using an optical sensitizer such as a merocyan dye alone or in combination (for example, superchromatic sensitization). These technologies are described in U.S. patents 2 and 8.
No. 88,545, No. 2,912.32i3, No. 3,3
No. 97,080, No. 3,815.635, No. 3,82
No. 8,984, British Patent No. 1,195,302, No. 1,
No. 242,588, No. 1,293,882, West German Patent (OL S) No. 2,030,328, IEil
No. 2,121,780, Special Publication No. 43-4936, No. 4
4-14030 etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

In forming the silver halide grains contained in the silver halide emulsion used in the present invention, a silver halide emulsion in which the core grains are monodisperse silver halide grains is used, and the core grains have shells. By coating a monodisperse silver halide emulsion with a substantially uniform shell thickness, a monodisperse silver halide emulsion can be used with its grain size distribution unchanged. Alternatively, two or more types of monodisperse emulsions having different average grain sizes may be blended at any time after grain formation to obtain a predetermined gradation for use.

Thu) The silver halide emulsion used in A-Ming is contained in the emulsion at a proportion equal to or higher than that of an emulsion obtained by coating a shell on a monodisperse core with a distribution width of 20% or less. It is desirable that the silver halide grains of the present invention be included in all silver halide grains, but silver halide grains other than the present invention may also be included as long as they do not impede the effects of the present invention. The silver halide may be of core-shell type or may be of a type other than core-shell, and may be monodispersed or polydispersed. In the silver halide emulsion used in the present invention, the emulsion contains It is preferable that at least 65% by weight of the silver halide grains contained be the silver halide grains of the present invention, and it is desirable that almost all of them be the silver halide grains of the present invention.

The present invention includes the case where the silver halide emulsion is an emulsion containing tabular silver halide grains containing silver iodide. That is, in the emulsion of the present invention used in the silver halide emulsion layer of the present invention, the silver halide grains are (1) the above-mentioned silver iodide-containing core-shell grains, and (2) are legalized silver tabular silver halide grains. (The legalized silver tabular silver halide grains may be of a core-shell type or of other types.); ■It is a mixture of the above ■ and ■. Even if it is an embodiment, it is included in the present invention.

The legalized silver tabular silver halide grains will be explained below.

The tabular silver halide grains preferably have a grain size of 5 times or more the grain thickness.
8-127921 and 58-108532, etc., and in the present invention, from the viewpoint of effects on color staining and image quality, the particle diameter is 5% of the particle thickness. more than twice, preferably 5 to 100 times,
It is particularly preferable to use a particle size of 7 to 30 times, more preferably a particle size of 0.3 μm or more, and 0.5 to 8 μm.
Those of p, , m are particularly preferably used. When these tabular silver halide grains are contained at least 50% in at least one silver halide emulsion, the desired effects of the present invention are more preferably exhibited, and almost all of them are the above-mentioned tabular silver halide grains. In some cases, particularly favorable effects can be achieved.

It is particularly useful when the tabular silver halide grains are core-shell grains. In the case of core-shell particles, it is preferable that the requirements described above for the core-shell are also satisfied.

In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore "thickness" in the present invention is expressed as the distance between the two parallel surfaces constituting the tabular silver halide grain.

The halogen composition of the tabular silver halide grains is preferably silver bromide and silver iodobromide.

In particular, silver iodobromide having a silver iodide content of 0 to 10 mol% is preferred.

Next, a method for producing tabular silver halide grains will be described.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, seed crystals containing tabular silver halide grains of 40% or more by weight are formed in an atmosphere with a relatively high pag value of par 1.3 or less, and a silver and halogen solution is grown while maintaining the par value at the same level. It can be obtained by growing seed crystals while simultaneously adding them.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc. By using a silver halide solvent as necessary during production of silver grains, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The amount of silver halide solvent to be used is the anti-E solution IX1G-3 to 1. Off
The amount of I is preferably 10% by weight.

For example, as the amount of silver halide solvent used increases, the silver halide grain size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of silver halide grains to increase with the amount of silver halide solvent used.

Examples of the silver halide solvent used include ammonia, thioethers, and thioureas. Regarding thioethers, reference may be made to US Pat. Nos. 3,271.157, 3,790.387, and 3,574,828.

It is added to accelerate grain growth during production of the tabular silver halide grains of the present invention. Silver salt solution (e.g. AgN0i
A method of increasing the addition rate, amount, and concentration of the aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used.

These methods are described, for example, in British Patent 1, 335.
No. 925, U.S. Pat. No. 3,872,900, U.S. Patent No. 3,85
No. 0,757, No. 4,242,445, Japanese Unexamined Patent Publication No. 1983-
Reference can be made to the descriptions in No. 142329, No. 55-158124, and the like.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary. Regarding the chemical sensitization method, the description of the sensitization method explained for the core shell can be referred to, but from the viewpoint of silver saving in particular, the tabular silver halide grains of the present invention may be gold sensitized, sulfur VL sensitized, or It is preferable to use them together.

In the layer containing the tabular silver halide grains of the present invention,
It is preferable that the tabular silver halide grains are present in a weight ratio of 40% or more, particularly 60% or more, based on all the silver halide grains in the layer.

The thickness of the layer containing tabular silver halide grains is 0.5e
m ~5. Ogm, special D1.07zm ~33-0x
It is preferable that there is a

Also, coating ff1 (on one side) of tabular silver halide grains is 0.5 g/rn'' to 8 g/m'', especially Ig
/m” to 4 g/m” is preferable.

Other components of the layer containing tabular silver halide grains of the present invention 1 For example, a binder, a hardening agent, an antifoggant, a silver halide stabilizer, a surfactant, a spectral sensitizing dye, a dye, and an ultraviolet absorber. There are no particular restrictions on, for example,
Re5earch Disclosure Volume 17S, 2
Reference may be made to the description on pages 2-2B (December 1978).

Next, the structure of the silver halide emulsion layer (hereinafter referred to as upper silver halide emulsion layer) which is present outside (on the surface side) of the layer containing tabular silver halide grains of the present invention will be described.

The silver halide grains used in the upper silver halide emulsion layer are preferably high-sensitivity silver halide grains used in ordinary direct X-ray films.

The shape of the silver halide grains is preferably spherical, polyhedral, or a mixture of two or more of these, and the average grain size is preferably 0.5 μJ1 to a river layer.
If necessary, it can be grown using a solvent such as ammonia, 1,000-onythyl, thiourea, etc.

The silver halide grains must be highly sensitive by a gold sensitization method, a sensitization method using other metals, a reduction sensitization method, a sulfur sensitization method, or a sensitization method using a combination of two or more of these. is preferred.

The other compositions of the upper emulsion layer are not particularly limited as in the case of the calendar containing tabular silver halide grains, and the above-mentioned Re
The description in Volume 178 of 5earch Disclosure may be referred to.

It is also preferable that the emulsion of the present invention contains epitaxially bonded silver halide grains as described in JP-A-53-103725 and the like.

The emulsion of the present invention may contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds, etc. Hardening agents such as aldehyde-based, aziridine-based, inoxazole-based, vinyl sulfone-based, 7-acryloyl-based, albodiimide-based, maleimide-based, methanesulfonate-based, triazine-based, etc.; benzyl alcohol, polyoxyethylene-based compounds, etc. Development accelerator; chroman type,
Examples include Claman-based, bisphenol-based, and phosphite-based image stabilizers; lubricants such as waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. In particular, it is preferable that these surfactants are eluted into a processing solution having bleaching ability. Effective antistatic agents include diacetylcellulose, styrene perfluoroalkylrhydium maleii) co-ffi polymer, and alkali salts of styrene-maleic anhydride copolymers and p-7 minobenzenesulfonic acid tono-reactants. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

Supports for light-sensitive materials made using the emulsion of the present invention prepared as described above include, for example, baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, glass,
There are cellulose acetate, cellulose nitrate, polyvinyl acecool, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc., and these supports are appropriately selected depending on the purpose of use of each silver halide color photographic light-sensitive material. .

In order to apply the emulsion of the present invention to color light-sensitive materials, the emulsion of the present invention is color-sensitized and adjusted to red sensitivity, green sensitivity, and blue sensitivity, and contains cyan, magenta, and yellow couplers in combination. The methods and materials used for photosensitive materials may be used.

The silver halide color photographic light-sensitive material to which the processing solution having bleaching ability of the present invention can be applied is an internal development method (U.S. Pat. No. 2,378,679,
2,801,171), as well as an external development method in which a coloring agent is contained in the developer (see U.S. Pat. No. 2,252,
No. 718, No. 2,592,243, No. 2,58Q, 9
For example, the cyan coloring agent is based on a naphthol or phenol structure, and by coupling it can be formed with indoaniline. Those that form pigments, magenta coloring agents include those having a 5-pyrazolone ring having an active methylene group as a skeleton structure, and yellow coloring agents include benzoylacedoanilide and pivalylacetanilide having active methylene chains. Those having an acylacedoanilide structure, such as those having a substituent at the coupling position, or those having a substituent at the coupling position can be used. In this way, the so-called 2 color formers
Both equivalent type couplers and 4-equivalent type couplers can be applied.

The black-and-white developer that can be used in the processing of the present invention is a commonly known black-and-white VGL developer used in the processing of color photographic materials, or a developer used in the processing of black-and-white photographic materials. Various additives added to the black and white developer can be contained.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and I\hydroquinone;
Preservatives such as sulphites, accelerators consisting of 71 recalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc.
Surface overdevelopment consisting of organic or organic inhibitors such as potassium bromide, 2-methylenebenzimidazole, and methylbenzthiazole, water softeners such as poly1nonate, and trace amounts of iodide and mercapto compounds. Inhibitors and the like can be mentioned.

The aromatic primary amine color developing agent used in the color developer used before processing with the processing solution having bleaching ability of the present invention is a known color developing agent that is widely used in various color photographic processes. Includes: These developers often include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used in concentrations of about 0.1 g to about 30 g per color developer lft, more preferably about 1 g to about 15 g per batch.

Examples of amine phenol developers include 0-7 minophenol, p-7 minophenol, and 5-amino-2-
Oxytoluene, 2-7 minnow 3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.

A particularly useful aromatic primary amine color developer is N.

It is an N-dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted.Among these, a particularly useful compound is N,N-diethyl-P- Phenylenediamine hydrochloride, tomethyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2=amino-5-(N-ethyl-N-dodecylamino)-toluene, toethyl-N-β -Methanesulfonamidoethyl-3-methyl-4-7mi/aniline sulfur salt, N
-Ethyroot β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N,N-diethylaniline, 4
-Aminot(2-methoxyethyl)-N-ethyl-3
-Methylaniline-p-toluenesulfonate and the like.

The paraphenylenediamine color developing agent is preferably mixed into the bleach-fix solution of the present invention.

The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention includes, in addition to the above-mentioned aromatic primary amine color developing agent, various kinds of color developing solutions that are usually added to the color developing solution. Ingredients such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal ocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, 1- A water softener and a thickening agent such as hydroxyethylene-1,1-diphosphonic acid may optionally be included. The pH of this color developer is 1, usually 7 or higher, and most commonly about 10 to 7.
It is about 13.

The bleaching solution and bleach-fixing solution according to the present invention include color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies,
It can be applied to silver halide color photographic materials using the emulsion of the present invention, such as color reversal films for TVs and reversal color papers, but especially when the total coated silver amount is 20 mg/
It is most suitable for processing high-sensitivity color photographic materials with drn' or higher.

[Examples] Hereinafter, the present invention will be explained in detail by way of Examples, but the embodiments of the present invention are not limited thereto.Comparative examples will be explained first.

Comparative Example 1 [Manufacture of emulsion] Average grain size 1 consisting of silver iodobromide containing 1.5 mol% of iodide
．． 2 m of the following four types of monodisperse cubic emulsions A, B, C,
D, E, and monodisperse cubic emulsion F consisting of pure silver bromide with an average grain size of 1.2 ILm were each subjected to gold sensitization and sulfur sensitization,
After aging, 4-hydroxy-6-methyl-1,3,3
a,? - After adding tetrazaindene, the amount of silver is 50 mg
/100 crn' emulsions A to F below were prepared.

(Emulsion A) Silver bromide shell (thickness 0.3 JLta
) Silver iodobromide (emulsion B) Silver bromide shell (thickness 0.05 JJ, I
O) Silver iodobromide (emulsion C) Silver bromide shell (thickness 0.017za+
) Silver iodobromide (emulsion D) Silver iodobromide (emulsion E) with a silver bromide shell (thickness 0.41 Lm) Silver iodobromide without a silver bromide shell (emulsion F)
Six types of samples (1) were prepared using each of the pure silver bromide non-layered emulsions A to F.
~(6) was made.

[Manufacture of photosensitive material] Anhydro-3,3-di(3-
Sulfoproyl/l/focyanine hydroxide (dye p-1) 28
5+++ g/1 mol Agx, anthro-o-3.3-di(3-sulfoproloxide (dye p-2) 38.5+
og/1 mol AgX and anhydro-1,3-diethyl-3-(3-sulfopropyl)-5-trichloromethyl-4,5-benzobenzimidazolothiacarboxyanine hydroxide (dye p-3) 11G+g/1
Optical sensitization was performed using molar AgX. This photographic emulsion contains 2-(α, α, β, β, γ, γ) as a cyan coupler.
, δ, δ-octafluorohexanamide)-5-[2
-(2,4-di-t-amylphenoxy)hexanamide]phenol is dissolved in tricresyl phosphate,
AgX 1
The amount of coupler per mole was 0.3 mole. Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1.3
,3a,? -tetrazaindene, with addition of poly-N-vinylpyrrolidone and a fog inhibitor as a physical development inhibitor,
A photosensitive material was obtained by coating on a polyethylene terephthalate film.

[Development Treatment] After the above photosensitive material was exposed to light in a conventional manner, the following development treatment was performed.

Color development for 3 minutes and 15 seconds, bleaching for 1 to 20 minutes, washing with water for 2 minutes, and stabilization for 1 minute are carried out in sequence, followed by drying.

Note that each treatment was performed at 37.8°C, and each treatment liquid was prepared according to the following formulation.

[Color developer] Potassium carbonate 30.0g subf
! Sodium acid 2.0g Hydroxyamine sulfate 2.0g Potassium bromide
1.2g sodium hydroxide
3.4 g N-ethylene-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.6 g water was added to make 1 fL, and the pH was adjusted to 10.1 with sodium hydroxide.

[Bleach-fix solution] Ethylenediaminetetraacetic acid diammonium salt ?・5g ethylenediaminetetraacetic acid iron (m) Ammonium salt 100.0g ammonium bromide 250.0g ammonium fcite (50% solution) lO, 0g ammonium thiosulfate (70% solution) 90.0g Add water to make 11, water The pH was adjusted to 8.2 with ammonium oxide.

[Stabilizing solution] Formalin (35% aqueous solution) 7.0+1j
LCs HuGO-(11;Hz GHz O)u H
1. Add o+fL water to make 11.

The results are shown in Table 1. Sensitivity is expressed as relative sensitivity with the sensitivity of sample (2) as 100. In the table, S stands for sensitivity, Fog stands for fog density, and DAg stands for covering power.

In addition, a processing step in which the silver was not bleached was separately provided, and the amount of developed silver was determined by fluorescent X-ray analysis.

Table 1 Standard deviation Width of distribution C = -X As is clear from the results with an average particle size of 100 or more, samples (1), (2), and (3) that violate the conditions of the present invention are used as photosensitive materials. Even if conventional bleaching agents are used, other samples (4), (5) and Moreover, the results in Table 1 suggest that there is an optimum shell thickness. turns out to be extremely bad.

Example 1 The bleach-fix solution of Comparative Example 1 was replaced with the following bleach-fix solution.

[Bleach-fix solution] Iron diethylenetriaminepentaacetate (m) Ammonium 1M 150. Og Ammonium ethylenediaminetetraacetate 3.0g Ammonium thiosulfate (70% aqueous solution) 90.0g Ammonium sulfite (50% aqueous solution) lO, 0g Ammonium bromide 200.0g Add water to make 11, and add ammonium hydroxide.

The pH was adjusted to 13.2.

The bleaching time was run from 1 to 20 minutes at 1 minute intervals and the completion time was measured. The results are shown in Table 2.

Table 2 The results in Table 2 also show that the color photographic material using the silver halide emulsion according to the present invention has a greatly improved desilvering property by the bleaching solution according to the present invention.

Example 2 The photosensitive material of Sample (2) in Example 1 was treated in the same manner as in Example 1, except that the compounds shown in Table 3 below were used in place of diethylenetriaminepentaacetic acid ammonium salt diethylenetriaminepentaacetate. The results are shown in Table 3.

As is clear from the above table, when the bleaching agent of the present invention is used, it is found that the bleaching properties are very excellent.

Example 3 A similar experiment was carried out in Example 1 except that the bleach-fix solution was replaced with the following bleach and fix solutions during the processing steps. The results are shown in Table 4.

[Bleach solution (A)] Ethylenediaminetetraacetic acid ferric complex salt (ammonium salt) 150.0g Hydroxyethylethylenediaminetriacetic acid #5.0g Ammonium bromide 150.0g Add water to make 11, aqueous ammonia (28% aqueous solution) ) to adjust the pH to 8.2.

[Bleach solution (B)] Diethylenetriamine iron pentaacetate CI [I] ammonium 1M150, Ogk base ethylenediaminetetravinegar 20.0g ammonium bromide 3.0g Add water to make tU, ammonia water (28% aqueous solution) The pH was adjusted to 8.2.

[Fixer 1 Ammonium sulfite (50% solution) 10.0g
Ammonium thiosulfate (70% solution) IIO,0
g Add water to bring the pH to 11, and adjust the pH to 8 with ammonium hydroxide.
, adjusted to 2.

From the results shown in Table 4, it can be seen that the desilvering properties of color photographic materials using the silver halide emulsion according to the present invention are greatly improved by the bleaching solution containing the bleaching agent of the present invention.

Example 4 A tabular silver halide emulsion was prepared with reference to JP-A-58-113934 (Example Emulsion 2.3.4), and the following photographic material was self-produced.

A multilayer color photosensitive material sample was prepared on a polyethylene terephthalate film support, each layer having the composition shown below.

First layer: Antihalation layer Black gelatin layer containing colloidal silver Second layer: Intermediate layer 2, Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone Third layer: First red-sensitive emulsion layer Silveride (silver iodide: 3.5 mol% Average grain size 0.3 color m
(monodispersed spherical particles)...Silver coating amount 0.8 g/rn' Silver iodobromide (silver iodide: 3 mol%) Average grain thickness 0.2 mm, average grain size 4.0 m tabular Particles)... Silver coating amount 0.8 g/m" Sensitizing dye... 6 x 10 moles per mole of silver Sensitizing dye ■... 1.5 x 10 moles cyan coupler per mole of silver ...0.044 mol per mol of silver 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide (Silver iodide: 7 mol %, average grain size 1.0 mm spherical grains) ...Silver Coating amount: 2.0 g/m'' Sensitizing dye: 3.5 x 10 moles per mole of silver Sensitizing dye: 1, OX 10 per mole of silver Molscian coupler: Silver 0.020 mol per mol 5th layer: Intermediate layer Same as 2nd layer 6th layer: 1st green-sensitive emulsion layer Silver iodobromide (Silver iodide = 4.2 mol% Average grain size 0.34μ
m spherical polydisperse emulsion) ... Silver coating amount 1.8 g/m'' Sensitizing dye ■ ... 3.3X to mole per mole of silver Sensitizing dye ■ ... per mole of silver te1, lX1o Mol magenta coupler eφ 2g per mole of silver 7th layer: 2nd green-sensitive emulsion layer Silver iodobromide (silver iodide = 4.2 mol% Average grain thickness 0.2
5 m, average grain size 8.0 lm tabular grains)...Silver coating amount 1.8 g/rn' sensitizing dye ■...2.85 x 10 mole sensitization per mole of silver Dye ■・Φ・0.89X 10 mole per mole of silver Magenta coupler...0.02 mole per mole of silver 8th layer: Yellow filter 1 layer Yellow colloidal silver in gelatin aqueous solution, 2,5 -G-t
- Gelatin layer containing an emulsified dispersion of octylhydroquinone 9th M: First blue-sensitive emulsion layer Silver iodobromide (Silver iodide: 5.8 mol% Average grain size 0.3 m)
(spherical particles) ... Silver coating amount: 1.5 g/m" Yellow coupler: 0.25 mol per 1 mol of silver 10th layer: 2nd blue-sensitive emulsion layer Silver iodobromide (Silver iodide: 8 mol% Average particle size 0.78 m
(spherical particles) - Number - Silver coating amount 1.21 g/m' Yellow coupler - 0.06 mol per 11 mol of e1 11th layer: 1st layer. Protective layer Silver iodobromide (Silver iodide: 1 mol% Average grain size 0.0 μm
)...Amount of silver coated: 0.5 g Gelatin layer 12 containing an emulsified dispersion of ultraviolet absorber:
Second protective layer Gelatin layer containing trimethyl methacrylate particles (diameter 1.5 μm) In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer.

Sensitized material: Anhydro 5,5-dichloro-3,3'
-di(γ-sulfopropyl)-8-ethyl-thiacarbocyanine and droxide/pyridium salt Sensitizing dye 44 dye m: anhydro-8-ethyl-5,5-dichloro-3.
3'-di(γ-sulfopropyl)oxacarbocyanine sodium salt sensitizing dye
[β-(γ-Sulfopropoxy)ethoxy])ethylimidazolocarbocyanine hydroxide sodium salt The sample prepared above was treated in the same manner as in Example 1. As a result, as in Example 1, it was confirmed that the effects of the present invention were significantly greater than those of conventional photographic materials.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent
Patent attorney Nobuaki Sakaguchi (and one other person) Procedural amendment (voluntary) August 17, 1982

Claims (1)

[Scope of Claims] (1) A core consisting essentially of silver halide containing silver iodide, and consisting essentially of silver bromide, silver chloride, silver chlorobromide or silver iodobromide, or a mixture thereof. The thickness is 0.01~
After imagewise exposure, a silver halide color photographic light-sensitive material containing silver halide grains consisting of shells having a diameter of 0.5 μm and/or tabular silver halide grains containing silver iodide was developed, and the following bleaching agent was used. Difference in redox potential between at least one organic acid ferric complex salt (A) selected from the diiron complex salt group or the following reference solution of an organic acid ferric complex salt when the pH thereof is between 5.0 and 9.0. 1. A method for processing a silver halide color photographic light-sensitive material, comprising processing with a processing solution having a bleaching ability and containing at least one organic acid ferric complex salt having a ferric complex salt of 100 mV or less. [Organic acid ferric complex salt (A)] (1) Diethylenetriaminepentaacetic acid ferric complex salt (2) Diethylenetriaminepentaphosphate ferric complex salt (3) Cyclohexanediaminetetraacetic acid ferric complex salt (4) Cyclohexanediaminetetraphosphate ferric complex salt Ferric complex salt (5) Ferric triethylenetetramine hexaacetic acid complex salt (6) Ferric triethylenetetramine hexaphosphate complex salt (7) Ferric glycol ether diamine tetraacetic acid complex salt (8) Ferric glycol ether diamine tetraphosphate Complex salt (9) 1,2-diaminopropanetetraacetic acid ferric complex salt (1
0) 1,2-diaminopropane tetraphosphate ferric complex salt (11
) Ferric methyliminodiacetic acid complex salt (12) Ferric methyliminodiaphosphate complex salt [Organic acid ferric complex salt standard solution for redox potential measurement] Ferric chloride 0.23M Organic acid 0.305M Ammonium thiosulfate 1.0M Ammonium sulfite The pH is adjusted using 0.1M ammonia water and acetic acid, and the redox potential is measured. (2) The surface tension of the processing liquid with bleaching ability is 55 dyne.
/cm or less
A method for processing a silver halide color photographic light-sensitive material as described in . (3) Claim 1, wherein the organic acid ferric complex salt is diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid ferric complex salt. Or the method for processing a silver halide color photographic light-sensitive material according to item 2. (4) The method for processing a silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the processing solution having bleaching ability is a bleach-fix solution. (5) A method for processing a silver halide color photographic light-sensitive material according to claim 4, characterized in that a one-bath bleach-fix treatment using a bleach-fix solution is carried out directly following the color development treatment.