JPH0562728B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials), and more specifically, the present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials), and more specifically, the present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials). The present invention also relates to a treatment method using a treatment liquid containing peroxide. [Prior Art] Conventionally, the following methods have been generally used to process color photosensitive materials. After the color photosensitive material is subjected to imagewise exposure, it is treated with a color developing solution containing an aromatic primary amine developing agent, whereby the silver halide is reduced to metallic silver, and the aromatic primary amine is It is oxidized and undergoes a coupling reaction with the coupler to produce a dye image. The metallic silver is oxidized to soluble silver halide by a bleaching agent (oxidizing agent) in a bleaching process. Thereafter, by treatment with a fixing solution (eg, thiosulfate, thiocyanate, etc.), the silver complex ions are converted into silver complex ions and removed from the photographic material, leaving only the color image. In addition to the basic steps of color development, bleaching, and fixing, the actual development process includes auxiliary steps for physical photographic image preservation and quality preservation. There is also a method of processing with a bleach-fix solution that performs bleaching and fixing steps in one bath. As bleaching agents used in the bleaching process, red blood salts, ferric chloride, aminopolycarboxylic acid-metal complex salts, and peroxides are generally used. Both red blood salt and ferric chloride are good bleaching agents because they have a strong bleaching power and a fast bleaching rate (oxidation rate). However, since bleaching solutions using red blood salt liberate cyan ions through photolysis and cause environmental pollution, it is necessary to detoxify the treated waste liquid. In addition, bleaching walls using ferric chloride has a PH
Since the oxidizing power is very low and the oxidizing power is extremely high, the processing machine equipment that contains it is easily corroded, and iron hydroxide is precipitated in the emulsion layer during the water washing process after bleaching, producing so-called stains. There are drawbacks. For this reason, a cleaning step using an organic chelating agent is required after the bleaching process, which is not suitable for the purpose of speedy processing and labor saving, and is also undesirable due to the risk of generating chlorine gas in terms of environmental pollution. It has been proposed to use an aminopolycarboxylic acid-metal complex salt as a bleaching agent that causes less environmental pollution than the red blood salt and ferric chloride. however,
The bleaching solution of the aminopolycarboxylic acid-metal complex salt has low oxidizing power and has insufficient bleaching power. For example, when bleaching a low-sensitivity color light-sensitive material that is mainly composed of a silver chlorobromide emulsion, it is possible to achieve the desired purpose, but if the material is mainly composed of silver chlorobromoiodide or silver iodobromide and the color When processing sensitized high-sensitivity color light-sensitive materials, especially color light-sensitive materials using high-silver emulsions, the bleaching effect may be insufficient and desilvering may be insufficient, or oxidation products of color developing agents and couplers may The dye produced by oxidative coupling remains in the state of a leuco dye, which is a reaction intermediate, even after bleaching, and the dye is not completely formed, resulting in so-called poor color recovery. In any case, bleaching agents (oxidizing agents) such as red blood salts, ferric chloride salts, or aminopolycarboxylic acid metal complex salts have problems such as environmental pollution due to the pollution burden of waste liquid, so the treated waste liquid is completely harmless. Measures and other measures must be taken to ensure that metal ion-free peroxides, specifically persulfate ions and/or hydrogen peroxide or compounds that release hydrogen peroxide, are recommended. preferable. Peroxide used as a bleaching agent decomposes into water and oxygen or sulfate, so it does not increase biological oxygen demand (BOD) or chemical oxygen demand (COD), which is advantageous in terms of pollution control. However, for example, persulfate ions have stronger oxidizing power than the red blood salts, ferric chloride, and metal complex salts of organic acids, and have a high redox potential, but their bleaching power against silver is weak, and bleaching takes an extremely long time. It takes.
For this reason, it is known that various bleach accelerators are used in combination, and these bleach accelerators can be added to a solution containing persulfate ions or to a prebath prior to a bleach bath, for example, U.S. Pat. No. 3,707,374; 3722020
No. 3893858, Special Publication No. 51-28227, Japanese Patent Publication No. 1973
-94927, 53-95631, 55-25064, same
No. 55-26506, Research Disclosure No. 15704 (May 1977)
A method using a bleaching accelerator such as a mercapto compound or a dimethyl carbamate compound described in JP-A-55-149944 and JP-A No. 58-8352
No. 58-95347, a method has been proposed in which an amino compound is incorporated into a sensitive material, and this technique improves the bleaching power and makes it possible to speed up the bleaching time. However, even with these accelerators,
Such a processing solution with bleaching ability using peroxide as a bleaching agent has a black colloidal silver antihalation layer and a silver halide layer containing 3 mol% or more of silver iodide as the closest layer. It has been found that in high-sensitivity photographic materials such as those having a large film thickness, desilvering defects rapidly occur when continuous processing is performed. Furthermore, there is a core-shell emulsion that has recently been developed as a silver halide emulsion that is a high-sensitivity emulsion containing silver iodide, has fine grains, and effectively utilizes silver to meet the requirements for resource conservation. It is a monodisperse core-shell emulsion that is produced by using a preceding silver halide emulsion as a crystal nucleus, successively layering subsequent precipitates thereon, 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 and/or shell has extremely favorable photographic performance, but when applied to color photosensitive materials, conventional bleach-fixing baths have It was found that the bleach-fixing properties of developed silver and silver halide were extremely poor. That is, developed silver of a photographic silver halide emulsion containing 3 mol% or more of silver iodide, especially a core-shell emulsion, containing silver iodide in the core and/or shell,
Developed silver made of silver halide grains with a shell thickness of 0.5 μm or less may have excellent sensitivity, granularity, covering power, etc., but in color photosensitive materials that require bleaching, the form of the developed silver is Because this is different from conventional bleaching properties, the bleaching properties are significantly lower, especially in bleaching solutions and bleach-fixing solutions that use conventionally known ferric complex salts of ethylenediaminetetraacetic acid and ferric nitrilotriacetic acid salts as bleaching agents. It turned out to be difficult. Similarly, as emulsions for improving conventional defects, JP-A-58-113930 and JP-A-58-113934,
Techniques using tabular halogenated grains have been developed, such as those described in Japanese Patent No. 58-127921 and Japanese Patent No. 58-108532. With this tabular silver halide grain technology, even if the number of photons captured by the silver halide grains increases, the amount of silver used does not increase and image quality does not deteriorate. However, even these tabular silver halide grains have the disadvantage that developed silver formed by development with a p-phenylenediamine color developing agent has poor silver bleaching properties. Therefore, it is possible to rapidly bleach-fix color light-sensitive materials that are core-shell emulsions and/or tabular silver halide emulsions containing silver iodide, which are the excellent emulsions mentioned above, and have an antihalation layer made of black colloidal silver. There is a strong desire for a processing solution that can [Object of the Invention] Accordingly, the first object of the present invention is to provide an excellent bleach-fixing method for highly sensitive silver iodide-containing color light-sensitive materials in the processing of color light-sensitive materials. A second object is to provide a method for processing color photosensitive materials that has a low risk of environmental pollution and meets the requirements for pollution prevention. [Structure of the Invention] As a result of extensive research, the present inventor has developed a photographic constituent layer comprising a black colloidal silver-containing antihalation layer and blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support. the layer closest to the antihalation layer of the silver halide emulsion layer contains 3 mol% or more of silver iodide, and the shell has a thickness of 0.5 μm.
A silver halide color photographic light-sensitive material containing the following core-shell silver halide grains and having a total thickness of photographic constituent layers of 20 μm or less is developed after imagewise exposure, and contains peroxide as a bleaching agent. When processing with a processing bath that has silver bleaching ability,
It has been found that the objects of the invention are achieved by adding from 0.05 to 50 g of at least one bleach accelerator to the treatment bath and/or the bath preceding the bath. Here, the photographic constituent layer refers to all the hydrophilic layers that are on the same side as the support surface coated with the black colloidal silver-containing antihalation layer of the present invention and at least three silver halide emulsion layers and that participate in image formation. In addition to the antihalation layer and the silver halide emulsion layer, for example, a subbing layer, an intermediate layer (a mere intermediate layer, a filter layer, an ultraviolet absorbing layer, etc.),
It includes a protective layer and the like. The most preferred embodiment of the present invention is at least one of the compounds represented by the general formulas [] to [].
The inventors have found that the objects of the present invention are more effectively achieved by adding the seeds to a pre-bleach bath prior to a bleaching-capable treatment bath containing peroxide. I found it. General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] In the above general formula, Q represents an atomic group necessary to form a heterocycle containing one or more N atoms (including those to which at least one 5- to 6-membered unsaturated ring is fused), A is

【formula】

【formula】

【formula】

[Formula] -SZ' or _n represents a monovalent heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused), and B is a residue having 1 to 6 carbon atoms. represents an alkylene group, M represents a divalent metal atom, X and
X′ represents =S, =O or =NR″, and R″ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (a 5- to 6-membered unsaturated group), and (including those with at least one saturated ring condensed thereto) or an amino group, and Y is

[expression] or

[Formula], Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or

[Formula], Z′ represents Z or an alkyl group, and R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (a 5- to 6-membered unaltered R ₂ , R ₃ ,
R ₄ , R ₅ and R' are each a hydrogen atom, carbon number 1 to 6
an alkyl group, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group,
Or represents an alkenyl group. However, R ₄ and R ₅ are −
B-SZ may also be represented, and R and R′, R ₂ and R ₃ ,
R ₄ and R ₅ may each be cyclized with each other to form a heterocyclic residue (including one in which at least one 5- to 6-membered unsaturated ring is fused thereto). R ₆ and R ₇ are each

【formula】

[Formula] or

[Formula], R ₉ is an alkyl group or -(CH ₂ ) n ₈ SO ₃ ○-
(however, when R ₈ is −(CH ₂ ) n ₈ SO ₃ ○−, l
represents 0 or 1. ) G○− is an anion, m ₁ or
m ₄ and n ₁ to n ₈ are each an integer of 1 to 6, m ₅
represents an integer from 0 to 6. _R8 is a hydrogen atom, an alkali metal atom,

[Formula] or represents an alkyl group. However, Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 carbon atoms, and q represents an integer of 1 to 10.
A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further condensed with a 5- to 6-membered unsaturated ring. Note that the compound represented by the above general formula includes enolized compounds and salts thereof. That is, the present inventor continuously processed a high-sensitivity fine-grain color light-sensitive material having black colloidal silver as an antihalation layer and at least three silver halide emulsion layers containing a silver iodide-containing emulsion adjacent to the black colloidal silver layer. We have focused on the phenomenon that the desilvering properties of silver sensitizers deteriorate significantly when using silver iodide, and as a result of intensive research, we have found that when processed with a processing solution containing peroxide and having bleaching ability, color sensitizers containing silver iodide to be processed are It has been discovered that when the photographic constituent layers of the material are thinned below a certain value, the bleach-fixing properties are significantly improved and desilvering defects are improved. Furthermore, this phenomenon is caused by the fact that when the thickness of the photographic constituent layer of a silver iodide-containing color light-sensitive material increases, significant desilvering failure occurs at the boundary between the black colloidal silver-containing antihalation layer and the silver iodide-containing silver halide emulsion layer. It was found that there was a significant increase in Furthermore, the present inventor has found that when a specific bleaching accelerator is added to a bleach-fixing solution containing peroxide as a bleaching agent, the film thickness of the photographic constituent layer including the colloidal silver-containing antihalation layer and the silver halide emulsion layer (gelatin film If the thickness (thickness) exceeds a certain value, a good bleaching accelerating effect cannot be obtained, but if the thickness of the photographic constituent layer (gelatin film thickness) of the color photosensitive material is below a certain value, the bleaching accelerating effect of the specific bleaching accelerator will be improved. We discovered the surprising fact that this significantly increases the According to a preferred embodiment of the present invention, the thickness of the photographic constituent layer of the color photographic light-sensitive material is 18 μm or less. It has been found that the object of the present invention can be achieved more effectively by this. Furthermore, as the most effective embodiment, the above-mentioned object of the present invention can be most effectively achieved by a processing method in which a fixing process is performed after a color development process and as a preprocessing step of a bleach-fixing process. I discovered that. Hereinafter, this fixing treatment will be referred to as a pre-fixing treatment or pre-fixing, and the processing liquid used in the pre-fixing treatment will be referred to as a pre-fixing treatment liquid or pre-fixing solution, or a pre-fixing treatment bath or a pre-fixing bath. The bleaching accelerator of the present invention is represented by the general formulas [] to [], and typical specific examples thereof include:
Examples include, but are not limited to, the following: [Exemplary compounds]

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‖ ‖ C ₆ H ₁₃

SS

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CH ₂ = CH ‖ ‖ CH = CH ₂

SS

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C ₂ H ₅ ‖ ‖ C ₂ H ₅

SS

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CH ₃ ‖ ‖ CH ₃

SS

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C ₂ H ₅ ‖

S

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[Table] ｜ ｜
Na Na

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_CH3 ‖

S

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‖ C ₂ H ₅

N.H.

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C ₂ H ₅ ‖

O

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CH ₃ CO COCH ₃

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[Exemplary compounds]

(A-1) Nickel chloride (A-2) Nickel nitrate (A-3) Nickel sulfate (A-4) Nickel acetate (A-5) Nickel bromide (A-6) Nickel iodide (A-7) Phosphorus Nickel acid (A-8) Bismuth chloride (A-9) Bismuth nitrate (A-10) Bismuth sulfate (A-11) Bismuth acetate (A-12) Zinc chloride (A-13) Zinc bromide (A-14) Zinc sulfate (A-15) Zinc nitrate (A-16) Cobalt chloride (A-17) Cobalt nitrate (A-18) Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate (A-21) Chloride Magnesium (A-22) Magnesium sulfate (A-23) Magnesium acetate (A-24) Calcium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate (A-28) Barium nitrate (A-29) Strontium chloride (A-30) Strontium acetate (A-31) Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A-34) Manganese acetate (A-35) Lead acetate ( A-36) Lead nitrate (A-37) Titanium chloride (A-38) Stannous chloride (A-39) Zirconium sulfate (A-40) Zirconium nitrate (A-41) Ammonium vanadate (A-42) Metavanazine Ammonium acid (A-43) Sodium tungstate (A-44) Ammonium tungstate (A-45) Aluminum chloride (A-46) Aluminum sulfate (A-47) Aluminum nitrate (A-48) Yttrium sulfate (A-49) ) Yttrium nitrate (A-50) Yttrium chloride (A-51) Samarium chloride (A-52) Samarium bromide (A-53) Samarium sulfate (A-54) Samarium acetate (A-55) Ruthenium sulfate (A-56) ) Ruthenium chloride These metal compounds of the present invention may be used alone or in combination of two or more. The amount used is 0.0001 metal ions per liquid used.
Preferably from mol to 2 mol, particularly preferably 0.001
It ranges from 1 mole to 1 mole. The processing liquid having bleaching ability of the present invention can contain various additives together with the peroxide of the present invention as a bleaching agent as described above. As additives for the bleach-fixing properties, in particular alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide,
It is desirable to contain potassium iodide, sodium iodide, ammonium iodide, etc. Also borate,
PH buffers such as oxalate, acetate, carbonate, phosphate,
Solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamines, polyethylene oxides, etc. are known to be added to ordinary bleaching solutions. It is possible to add as appropriate. The processing liquid having bleaching ability of the present invention includes a bleach-fixing liquid having a composition in which a small amount of a halide such as potassium bromide is added, or conversely, a composition having a composition in which a large amount of a halide such as potassium bromide or ammonium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halide such as potassium bromide can also be used. Silver halide fixing agents to be included in the bleach-fix solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. thiosulfates, potassium thiocyanate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate, thioureas, thioethers, high concentrations of bromides,
Typical examples include iodides. These fixing agents can be used in an amount within the range of dissolving 5g/or more, preferably 50g/or more, more preferably 70g/or more. The bleach-fix solution may contain various PH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. Alternatively, a combination of two or more types may be contained. Furthermore, various optical brighteners, antifoaming agents, or antifungal agents can be contained. Preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds,
Other additives and organic solvents such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be included as appropriate. Other desirable compounds that can be added to the bleaching solution of the present invention to promote bleaching properties include tetramethylurea, trisdimethylamide phosphate, ε-caprolactam, N-methylpyrrolidone, N-methylmorpholine, and tetraethylene glycol. Examples include monophenyl ether, acetonitrile, glycol monomethyl ether, and the like. In the processing method of the present invention, it is preferable to carry out the bleaching of the present invention immediately after color development; It's okay. The method of the present invention includes independent steps of development, bleaching, and bleach-fixing, but here, development means black-and-white development and color development, and a method involving only color development or a method including both black-and-white development and color development is also used. . The above steps do not necessarily have to be consecutive, and various processing steps can be included before and after each of the above steps. Such a step is called an auxiliary step, and the auxiliary steps include a stop bath, a stop fixing bath, a hardening bath, a neutralization bath, a water wash, a rinse, an image stabilizing bath, and the like. From the viewpoint of simplifying the processing steps, the bleaching solution or bleach-fixing solution according to the present invention is preferably applied to a processing process in which bleaching or bleach-fixing is carried out immediately after color development. However, in the bleach-fix solution of the present invention, it may be more preferable that no developing agent or halogen ions are mixed into the bleach-fix solution.
Also, depending on the type of color photosensitive material to be processed and other requirements, water washing treatment, rinsing treatment, stop treatment, bleach-fixing treatment, pre-bleach-fixing bath (so-called conditioner for efficient bleach-fixing) or hardening treatment after color development, depending on the type of color photosensitive material to be processed and other requirements. It is more desirable to carry out bleach-fixing after suitably undergoing one or more treatments such as the following. Further, for a special purpose, after the bleach-fixing process, it is optional to perform a separate process with a bleach-fixing solution or a fixing solution that is not according to the present invention. That is, it is optional to place a bleach or bleach-fix solution according to the present invention at any processing process location to remove image silver. Next, specific examples of treatment processes will be shown, but the present invention is not limited to the following process examples. Dural mater - Neutralization - Development - Stop - Washing - Color development -
Stop - Bleach - Fix - Wash - Final treatment - Drying Development - Wash - Reversal - Color development - Adjustment - Bleach - Fix - Wash - Final treatment - Drying Color development - Bleach - Fix - Wash - Final treatment -
Drying Color development - bleaching - small amount of water washing - fixing - pre-washing - water washing - final treatment - drying Color development - bleach-fixing - preliminary washing - water washing - final treatment - drying Color development - bleach-fixing - final treatment - drying Color development - bleaching - Fixing - Final treatment - Drying Final treatment means washing with water or JP-A No. 57-8543, No. 58
−57903 etc. is to perform waterless washing treatment,
Particularly, in terms of resource saving and image preservation, the waterless washing process has favorable effects. The thickness of the photographic constituent layers (gelatin film thickness) of the color light-sensitive material of the present invention refers to the photographic constituent layers excluding the support, that is, the subbing layer, antihalation layer, intermediate layer, at least three emulsion layers, filter layer, and protective layer. This is the total thickness of all hydrophilic colloid layers, such as a layer, and the thickness of a dried photographic constituent layer. The thickness is measured using a micrometer, and in the present invention, the total thickness of the photographic constituent layers is 20 μm or less, particularly preferably 18 μm or less. The silver halide in the silver halide emulsion layer used in the present invention contains silver iodide grains, but in order to maximize the sensitivity and photographic properties of color light-sensitive materials and the bleach-fixing performance of the present invention, silver iodide grains are required. is preferably 3 mol % to 25 mol % from the viewpoint of photographic properties and bleach-fixing properties. In the present invention, if the content exceeds 25 mol%, the photographic properties are more preferable, but the bleach-fixing properties are significantly reduced. In the present invention, more preferably 3
It contains silver iodide in an amount of mol % to 20 mol %. The black colloidal silver dispersion layer for preventing halation used in the present invention has a sufficiently high optical density in the visible region (especially red light) for light incident from the support surface or emulsion surface of the color photosensitive material. It is necessary to have it. Furthermore, it is necessary that the color light-sensitive material has a sufficiently low reflectance for light incident on the emulsion surface. From the viewpoint of reflectance and bleach-fixing properties, colloidal silver with sufficiently fine particles is desirable, but colloidal silver with absorption from yellow to yellow is preferable.
Since the color becomes yellow-brown and the optical density against red light does not increase, the grains must be coarse to some extent, and physical phenomena centering on these silver grains are likely to occur, causing bleaching and fixing at the boundary with the silver halide emulsion layer. It is thought that the sex will deteriorate. Bleach-fixability is particularly important when the silver halide emulsion layer contains at least 3 mol % of silver iodide grains, especially when the silver halide emulsion layer closest to the support contains at least 3 mol % of silver iodide grains. The phenomenon of decrease in
It can be seen that the method of the present invention is effective because it is noticeable in multilayer color light-sensitive materials having three or more silver iodide-containing emulsion layers. Some core-shell emulsions used in the present invention are described in detail in JP-A-57-154232, etc., but preferred color photographic materials have a core silver halide composition of 0.1 to 20 moles of silver iodide. %, preferably 0.5 to 10 mol%,
The shell is composed of silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or a mixture thereof. Particularly preferably, the shell is a silver halide emulsion comprising silver iodobromide or silver bromide. Further, in the present invention, preferable effects can be obtained by forming the core as a substantially monodisperse silver halide grain and setting the thickness of the shell to 0.01 to 0.5 μm. The color light-sensitive material of the present invention is characterized in that it is made of silver halide grains containing at least 3 mol% of silver iodide, has an antihalation layer made of black colloidal silver as the bottom layer, and is photographic without the support. The thickness of the constituent layer (gelatin thickness) is 25 μm or less. In particular, silver halide grains containing silver iodide in the core and/or shell are used, and silver bromide, silver chloride,
By hiding the core of silver halide grains made of silver chlorobromide, silver iodobromide, or a mixture thereof using a shell having the above-mentioned specific thickness, the silver halide grains containing silver iodide can have a high density. The purpose is to make use of the particle's ability to increase sensitivity while concealing the disadvantageous characteristics of the particle. A silver halide emulsion having silver halide grains having a shell having the above-described specific thickness can be produced by coating these shells with silver halide grains contained in a monodisperse emulsion as a core. When the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 20 mol % or less. To make the core a monodisperse silver halide grain,
Particles of desired size can be obtained by the double jet method while keeping pAg constant. In addition, the production of highly monodisperse silver halide emulsions was developed by JP-A-Sho.
The method described in No. 54-48521 can be applied. A preferred embodiment of this method is a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. Therefore, it is to manufacture. At this time, the time function of addition rate, PH,
By appropriately selecting pAg, temperature, etc., a highly monodisperse silver halide emulsion can be obtained. 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 width of the distribution (%) by the relational expression: standard deviation/average particle size x 100 = width of the distribution (%), then the width of the distribution that can meaningfully control the absolute thickness of the coating is It is preferable that the monodispersity is 20% or less, more preferably 10% or less. Next, the thickness of the shell covering the core must be such that it does not hide the desirable qualities of the core, and on the contrary, it must be thick enough to hide the unfavorable qualities of the core. That is, 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 silver halide solution and a soluble silver solution onto a monodisperse core by a double gel method. For example, substantially monodisperse silver halide grains with an average grain size of 1 μm containing 2 mol% silver iodide are used as the core, and the coating thickness is varied by using 0.2 mol% silver iodobromide as the shell. According to experiments, for example
When a shell with a thickness of 0.85 μm was produced, the monodisperse silver halide grains produced by this method had a 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 filaments of developed silver had come out. 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.As a result, the thickness of the shell was determined by the absolute thickness regardless of the average grain size of the core. as 0.5 μm or less (preferably
It was found that a large number of well-developed silver filaments were produced at a diameter of 0.2 μm or less, resulting in sufficient optical density, and that the core's ability to increase 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. Preferably, the thickness limit is 0.01 μm. Furthermore, when confirmed by a highly monodisperse core with a distribution width of 10% or less, the preferred shell thickness is 0.01~
The thickness is 0.06 μm, and the most preferable thickness is 0.03 μm 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 the rapid development and fixing properties are achieved due to the high This is due to the shell whose thickness is regulated as described above by the dispersible core and the synergistic effect between the silver halide compositions of the core and shell, so if the thickness regulation of the shell can be satisfied, the shell can be As the constituent silver halide, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used. Among these, silver bromide, silver iodobromide, or a mixture thereof is preferred from the viewpoint of compatibility with the core, performance stability, and storage stability. In the photosensitive silver halide emulsion used in the present invention, when silver halide precipitates of the core and shell are formed,
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, and combinations thereof can be used. Excess halogen compounds generated during the preparation of the emulsion or by-products or unnecessary salts and compounds such as nitrates and ammonium may be removed. As a method for removal, a nude washing method, a dialysis method, a coagulation precipitation method, etc., which are commonly used in general emulsions, can be used as appropriate. Further, the emulsion used in the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. That is, activated gelatin; water-soluble gold salt, water-soluble platinum salt, water-soluble palladium salt, water-soluble rhodium salt,
Chemical sensitizers such as noble metal sensitizers such as water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; chemical sensitizers such as polyamines, reduction sensitizers such as stannous chloride, etc. alone or in combination. I can feel it. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular restrictions on the optical sensitization method for emulsions, and for example, optical sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, trimethine dyes, or merocyanine dyes may be used alone or in combination (for example, supersensitization). Can be sensitized. U.S. patents for these technologies
No. 2688545, No. 2912329, No. 3397060, No.
No. 3615635, No. 3628964, British Patent No. 1195302,
No. 1242588, No. 1293862, OLS No. 2030326, OLS No. 2121780, Special Publication No. 1293862, OLS No. 2030326, OLS No. 2121780
It is described in No. 4936, No. 44-14030, 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. The silver halide emulsion used in the present invention further includes a silver halide emulsion in which the core grains are substantially monodisperse silver halide grains, in which the silver halide grains contained in the silver halide emulsion are formed. By coating the core grains with a shell, a monodisperse silver halide emulsion with a substantially uniform shell thickness can be obtained. It can be used as is with its particle size distribution, or it can be prepared by blending two or more types of monodisperse emulsions with different average particle sizes at any time after grain formation to obtain a predetermined gradation. Good too. The silver halide emulsion used in the present invention contains a substantially monodisperse core with a distribution width of 20% or less in a proportion equal to or higher than that of an emulsion obtained by coating a shell with a substantially monodisperse core. It is desirable that the silver halide grains of the present invention be included in all the silver halide grains. However, silver halide grains other than those according to the invention may also be included within a range that does not impede the effects of the invention. The silver halide other than those of the present invention may be of the core-shell type or may be of a type other than the core-shell type, and may be monodisperse or polydisperse. In the silver halide emulsion used in the present invention, it is preferable that at least 65% by weight of the silver halide grains contained in the emulsion be the silver halide grains of the present invention, and almost all of them are silver halide grains of the present invention. It is desirable that In the present invention, the silver halide emulsion contains at least 3
This includes emulsions containing tabular silver halide grains containing mol % of 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 thereof are the above-mentioned silver iodide-containing core shell grains, and the silver halide grains are tabular silver halide grains containing iodide ( The silver iodide-containing tabular silver halide grains may be of the core-shell type or of other types.)
Any embodiment, such as a mixture with the above, is included in the present invention. The silver iodide-containing 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. The tabular silver halide grains are disclosed in JP-A-58-113930, JP-A-58-113934,
No. 58-127921, No. 58-108532, No. 59-99433
No. 59-119350, etc., and in the present invention, the particle diameter is preferably 5 times or more the particle thickness, from the viewpoint of effects on color staining and image quality. is preferably 5 to 100 times, particularly preferably 7 to 30 times.
Furthermore, the particle diameter is preferably 0.3 μm or more, and those of 0.5 to 6 μm are particularly preferably used. When these tabular silver halide grains are contained in at least 50% by weight of at least one layer of 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 the core shell particles, it is preferable that the requirements described for the core shell are also satisfied. Generally, 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. Ru. In addition, "grain diameter" refers to the diameter of the projected surface of a tabular silver halide grain when observed in a direction perpendicular to the flat surface, and if it is not circular, the longest diameter is considered as the diameter of a circle. Assuming that, this diameter is used. 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 0.5 to 10 mol% is more preferable. 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, in an atmosphere with a relatively high pAg value of pBr1.3 or less, seed crystals containing tabular silver halide grains of 40% or more by weight are formed, and silver and halogen solutions are simultaneously added while keeping the pBr value at the same level. It can be obtained by growing seed crystals while adding 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, selection of the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc. When producing tabular silver halide grains, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary. The amount of silver halide solvent used is 1× of the reaction solution.
10 ^-3 to 1.0% by weight is preferred, particularly 1 x 10 ^-2 to 1
x10 ^-1 % by weight is preferred. For example, as the amount of halogen solvent used increases, the silver halide grain size distribution can be made monodisperse, thereby increasing the growth rate. 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, U.S. Pat.
No. 3271157, No. 3790387, No. 3574628, etc. can be referred to. When producing tabular silver halide grains, silver salt solutions (e.g.
AgNO ₃ aqueous solution) and halide solution (e.g.
A method of increasing the addition rate, amount, and concentration of KBr aqueous solution) is preferably used. For these methods there are e.g. British patents.
1335925, U.S. Patent No. 3672900, U.S. Patent No. 3650757,
No. 4242445, JP-A-55-142329, No. 55-
You can refer to the description in No. 158124, etc. The tabular silver halide grains 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 sensitized, or a combination thereof. is preferred. In the layer containing tabular silver halide grains,
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
It is preferably 0.5 μm to 5.0 μm, and more preferably 1.0 μm to 3.0 μm. Further, the coating amount (on one side) of tabular silver halide grains is preferably 0.5 g/m ² to 6 g/m ² , and 1 g/m ²
It is more preferable that it is 4 g/ ^m2 . Other constituents of the layer containing tabular silver halide grains, such as binders, hardeners, antifoggants, silver halide stabilizers, surfactants, spectral sensitizing dyes, dyes, ultraviolet absorbers, etc. There is no limit, for example, Research Disclosure Volume 176,
Reference may be made to the description on pages 22-28 (December 1978). Next, a silver halide emulsion layer (hereinafter referred to as an upper silver halide emulsion layer) existing outside (on the surface side) of the layer containing the above-mentioned tabular silver halide grains.
We will describe the configuration of 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 thereof. Especially spherical particles and/or diameter/
It is preferable that polyhedral particles having a thickness ratio of 5 or less account for 60% or more (weight ratio) of the whole. The average grain size of the silver halide grains used in the present invention is preferably 0.5 μm to 3 μm, and can be grown using a solvent such as ammonia, thioether, thiourea, etc., if necessary. The silver halide grains may be highly sensitive by gold sensitization, sensitization with other metals, reduction sensitization, sulfur sensitization, or a combination of two or more of these. preferable. As with the layer containing tabular silver halide grains, other structures of the upper emulsion layer are not particularly limited, and the description in Research Disclosure Vol. 176 mentioned above can be referred to. In addition, the emulsion used in the present invention is
It is also preferable to include epitaxially bonded silver halide grains described in No. 103725, No. 59-133540, No. 59-162540, and the like. The silver halide emulsion can contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazoliums, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, isoxazole-based, vinylsulfone-based, acryloyl-based, carbodiimide-based, maleimide-based Hardening agents such as chroman, methanesulfonic acid ester, and triazine; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Image stabilizers such as chroman, claman, bisphenol, and phosphite esters; Lubricants include 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. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl sodium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective.
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. Gelatin plasticizers include glycerin and glycol compounds, and thickeners include styrene-sodium maleate copolymer and alkyl vinyl ether.
Examples include maleic acid copolymers. In the color light-sensitive material of the present invention, hydrophilic colloids used to prepare emulsions and other hydrophilic colloid layer coating solutions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, casein, etc. Examples include proteins such as hydroxyethyl cellulose, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Examples of the support for the color photosensitive material of the present invention include glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films. For example, it may be a baryta paper, a polyethylene-coated paper, a polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material), and these supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Further, simultaneous coating of two or more layers by the methods described in US Pat. No. 2,761,791 and US Pat. No. 2,941,898 can also be used. The silver halide emulsion of the present invention is a combination of cyan, magenta, and yellow couplers with the silver halide emulsion of the present invention, which has been color-sensitized and adjusted to have red sensitivity, green sensitivity, and blue sensitivity, in order to be applied to color light-sensitive materials. The method and material used for color photosensitive materials may be used, such as the method and material used for color photosensitive materials. The color photosensitive material to which the bleach-fix solution of the present invention can be applied is an internal development method in which a coloring agent is contained in the photosensitive material (see U.S. Pat. Nos. 2,376,679 and 2,801,171).
In addition to external development methods (U.S. Pat. No. 2252718, U.S. Pat. No. 2592243, U.S. Pat.
2590970). Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are those based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta color formers are those whose skeleton structure is a 5-pyrazolone ring with an active methylene group, and yellow color formers are As such, those having an acylacetanilide structure such as benzoylacetanilide and pivallylacetanilide having an active methylene chain, with or without a substituent at the coupling position can be used. Thus, as the color former, both so-called 2-equivalent couplers and 4-equivalent couplers can be used. The black-and-white developer that can be used in the processing of the present invention is a commonly known black-and-white first developer used in processing color photographic materials, or a developer used in processing black-and-white photographic materials. It can contain various additives that are generally added to black and white developers. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. can be mentioned. The aromatic primary amine color developing agent used in the color developing solution used before processing with the bleach-fix solution of the present invention includes a variety of aromatic primary amine color developing agents that are widely used in various color photographic processes. . These developers are aminophenolic and p
-Includes phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than the free state. In addition, these compounds are generally preferably used at a concentration of about 0.1 g to about 30 g per 1 color developer, more preferably about 1 g per 1 color developer.
Use at a concentration of ~15g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3
-amino-1,4-dimethylbenzene and the like. Particularly useful aromatic primary amine color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compounds are N, N
-diethyl-p-phenylenediamine hydrochloride, N
-methyl-p-phenylenediamine hydrochloride, N,
N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β -Hydroxyethylaminoaniline sulfate, 4-amino-3
-Methyl-N,N-diethylaniline sulfate, 4
-amino-N-(methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate. 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 contains, in addition to the above-mentioned aromatic primary amine color developing agent, various types of color developing solutions that are usually added to color developing solutions. Ingredients, such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene Water softeners and thickeners such as -1,1-diphosphonic acid can optionally be included. The pH of this color developer is usually 7 or higher,
Most commonly from about 10 to about 13. The processing solution having bleaching ability according to the present invention can be used for color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, reversal color paper, etc. Although the present invention can be applied to color light-sensitive materials, it is particularly suitable for processing high-sensitivity color light-sensitive materials in which the total amount of coated silver is 20 mg/dm ² or more. [Example] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Following the layer structure adopted for high-sensitivity silver halide color photographic light-sensitive materials in the art, a black colloidal silver antihalation layer, a red-sensitive colloidal silver anti-halation layer, and a red-sensitive layer were added from the support side with various auxiliary layers interposed. A silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity silver halide emulsion layer was arranged on the outermost side of the blue-sensitive silver halide emulsion layer. . That is, samples were prepared according to the following procedure, but the film thickness was adjusted and the dry film thickness was varied while the amount of coated silver was kept constant. However, the following are standard coating conditions, and each formulation was adjusted to account for changes in film thickness. Layer 1: A dispersion of 0.8 g of black colloidal silver, which is highly absorbent to light in the wavelength range of 400 to 700 nm by reducing silver nitrate with hydroquinone as a reducing agent, was prepared in 3 g of gelatin, and an antihalation layer was applied.
(Dry film thickness 2.0 μm) Layer 2: Intermediate layer made of gelatin. (Dry film thickness
0.8μm) Layer 3...1.5g of low-sensitivity red-sensitive silver iodobromide emulsion (AgI; 7 mol%), 1.6g of gelatin and 0.80g
1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-[δ-(2,
4-di-t-amylphenoxy)butyl]-2
- Naphthamide (hereinafter referred to as cyan coupler (C-
1)), 0.028 g of 1-hydroxy-4-
[4-(1-hydroxy-8-acetamide-
3,6-disulfo-2-naphthylazo)phenoxy]-N-[δ-(2,4-di-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC-
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved in 1). Layer 4...1.1g of highly sensitive red-sensitive silver iodobromide emulsion (AgI; 6 mol%), 1.2g of gelatin and 0.23g
cyan coupler (C-1), 0.15g dissolved in 0.020g colored cyan coupler (CC-1)
A highly sensitive red-sensitive silver halide emulsion layer containing TCP. Layer 5: 0.04 g of dibutyl phthalate (hereinafter referred to as DBP) in which 0.07 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1)) was dissolved and 1.2 g of gelatin. An intermediate layer containing. Layer 6...1.6g of low-sensitivity green-sensitive silver iodobromide emulsion (AgI; 12 mol%), 1.7g of gelatin and 0.30g
1-(2,4,6-trichlorophenyl)-3
-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.20 g of 4,4-methylenebis-11 −(2,
4,6-trichlorophenyl)-3-[3-(2,
4-di-t-amylphenoxyacetamide)
benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-2)), 0.066 g of 1-(2,4,6-toluchlorophenyl)-4-
(1-naphthylazo)-3-(2-chloro-5-
octadecenyl succinimide anilino)-5
- A low-sensitivity green-sensitive silver halide emulsion layer containing 0.3 g of TCP in which three types of couplers: pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) are dissolved. Layer 7...1.5g of highly sensitive green-sensitive silver iodobromide emulsion (AgI; 10 mol%), 1.9g of gelatin and
0.093g magenta coupler (M-1), 0.094g
of magenta coupler (M-2) and 0.049g of colored magenta coupler (CM-1) were dissolved.
Highly sensitive green-sensitive silver halide emulsion layer containing 0.12g of TCP. Layer 8: Yellow filter layer containing 0.2 g of yellow colloidal silver, 0.11 g of DBP in which 0.2 g of antifouling agent (HQ-1) was dissolved, and 2.1 g of gelatin.
(Dry film thickness 1.2μm) Layer 9...0.95g of low-sensitivity blue-sensitive silver iodobromide emulsion (AgI; 7 mol%), 1.9g of gelatin and 1.84g
α-[4-(1-benzyl-2-phenyl-
3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-2-chloro-5-
0.93g of [γ-(2,4-di-t-amylphenoxy)butanamide]acetanilide (hereinafter referred to as yellow coupler (Y-1)) dissolved
A low-speed blue-sensitive silver halide emulsion layer containing DBP. Layer 10...1.2g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (AgI; 6 mol%), 2.0g of gelatin and 0.46g
The yellow coupler (Y-1) of
Highly sensitive blue-sensitive silver halide emulsion layer containing 0.23g DBP. Layer 11...Second protective layer made of gelatin. Layer 12...first protective layer containing 2.3 g of gelatin. However, the silver iodobromide emulsions contained in the red-sensitive emulsion layers of layers 3 and 4 and the silver iodobromide emulsions contained in the green-sensitive emulsion layer of layer 7 are as follows (A) to (C). particles were used. Emulsion (A): A core-shell type emulsion with an average grain size of 2.0 μm (the shell is a low-iodium silver iodobromide with a thickness of 0.04 μm) Emulsion (B): A core-shell type tabular emulsion with an average grain size of 3.5 μm (the shell is a Emulsion (C); spherical emulsion with an average grain size of 2.0 μm The dry film thickness of the photographic constituent layers of the finished sample is as follows:
35μm, 30μm, 27μm, 25μm, 22μm, 20μm,
There were eight types, 18μm and 15μm. 24 types of samples were obtained in combination with emulsions. However, the film thickness and black colloidal silver content of the antihalation layer and the film thicknesses of the gelatin intermediate layer and yellow filter layer were not changed at all. Another sample was prepared by coating the same emulsion on a transparent polyethylene terephthalate film base without the bottom colloidal silver antihalation layer. Similarly, 24 types of samples were obtained. The average amount of coated silver for all samples was adjusted to 60 to 70 mg/dm ² . Each sample was treated using a treatment solution prepared according to the following treatment steps and the following formulation. Process Temperature Time Color development 41℃ 3 minutes Pre-bleaching bath 38℃ 30 seconds Bleaching bath 38℃ 10 seconds to 5 minutes Washing with water 33℃ 1 minute Fixing 33℃ 3 minutes Washing with water 33℃ 2 minutes Stability 33℃ 30 seconds [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g Potassium bromide 1.2g Magnesium chloride 0.6g Sodium hydroxide 3.4g N-ethyl-N -β-hydroxyethyl-3-
Methyl-4-aminoaniline sulfate 4.6g Add water to make 1 and pH with sodium hydroxide.
Adjusted to 10.1. [Pre-bleaching bath] Sodium sulfite 10.0g Sodium acetate 8.0g Glacial acetic acid 23ml Water was added to bring the solution to 1, and the pH was adjusted to 3.8 with sodium hydroxide or acetic acid. [Bleach solution] Sodium persulfate 60g Sodium chloride 20g Sodium dihydrogen phosphate (anhydrous) 9.0g Phosphoric acid (85%) 2.5ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 1.0g Gelatin 0.5g Water was added to make 1, and the pH was adjusted to 2.3 with sodium hydroxide or phosphoric acid. [Fixer] Sodium thiosulfate 150g Sodium sulfite 12g Add water to make 1. [Stabilizing solution] Formalin (37% solution) 10ml Add water to make 1. Exemplary compound-2 of the present invention was added in a pre-bleaching bath.
1.5g was added per silver, and the bleaching time was changed in two steps, 1 minute and 3 minutes, and the bleaching ability was compared based on the amount of residual silver. The results are shown in Table 1.

[Table] As is clear from the results in Table 1, the photographic constituent layer film thickness (gelatin film thickness) is When is large, the time to complete bleach-fixing is extremely long, but as the film thickness of the photographic constituent layer (gelatin film thickness) becomes thinner, it rapidly decreases.
It can be seen that the change is greatest around 25 μm. or,
Bleaching accelerators are not effective when the thickness of the photographic constituent layer (gelatin film thickness) is large, but they can be extremely effective when the photographic constituent layer (gelatin film thickness) is thinned. I understand. On the other hand, in the case of spherical silver iodobromide emulsions other than those of the present invention, there is almost no effect of the film thickness of the photographic constituent layer (gelatin film thickness), and the time required to complete bleach-fixing is also extremely short. Materials without an antihalation layer are difficult to put to practical use as high-sensitivity photographic materials such as high-sensitivity color light-sensitive materials for photographing. Example 2 Samples Nos. 1 to 16 (having an antihalation layer) in Example 1 were used and treated with a pre-bleaching bath to which 1.5 g of the exemplary compound of the present invention and the comparative compound were added as shown in Table 2. did. All experiments were conducted in the same manner as in Example 1. The results are shown in Table 2.

[Table] As is clear from Table 2, the compounds of the present invention have more favorable bleaching properties (desilvering properties) than compounds other than those of the present invention, in all cases for samples with film thickness within the range of the present invention. Indicated. Further, the accelerator used is the compound of the present invention, -28, -70, -85,
−100, −101, −144, −148, −152,
−156, −157, −158−2, −3,
−5, −6, −33, −1, −70, −
The experiment was repeated using 75, -1, and -11, but in each case, the same effect as -145 or -34 was shown. Example 3 Using the samples of Example 1 with photographic constituent layers having film thicknesses of 30 μm and 20 μm, the silver iodide mol% of the red-sensitive emulsions of layers 3 and 4 was 1 mol%, 3 mol%, and 5 mol%. Sample 20 changed to mol%, 10 mol% and 20 mol%
Seeds (No. 25-44) were created. Table 3 shows the results of the same treatment as in Example 1. However, the bleaching accelerator added to the pre-bleaching bath is Exemplary Compound-33 of the present invention.
And so.

【table】

[Table] As is clear from the above results, when the film thickness is 30 μm, the molar percentage of silver iodide in the emulsion of the present invention used in the red-sensitive emulsion layer close to the colloidal silver-containing antihalation layer increases. Therefore, the bleaching property decreases rapidly. However, the film thickness of the photographic constituent layer was reduced to 20μm.
It can be seen that the bleaching property hardly deteriorates even if the mole % of silver iodide increases when the ratio is below.

Claims (1)

[Scope of Claims] 1. A photographic constituent layer comprising a black colloidal silver-containing antihalation layer and a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support; Among the emulsion layers, the layer closest to the antihalation layer contains core-shell silver halide grains containing 3 mol % or more of silver iodide and having a shell thickness of 0.5 μm or less, and the thickness of the emulsion layer is the same as that of the photographic constituent layers. When a silver halide color photographic light-sensitive material having a total particle size of 20 μm or less is developed after imagewise exposure and processed with a processing bath having a silver bleaching ability containing peroxide as a bleaching agent, the processing bath and/or its 1. A method for processing a silver halide color photographic material, which comprises adding 0.05 to 50 g of at least one compound represented by the following general formulas [] to [] to a bath prior to bathing. General formula [] General formula [] General formula [] General formula [] General formula [] General formula [] [In the above general formula, Q represents an atomic group necessary to form a heterocycle containing one or more N atoms (including those in which at least one 5- to 6-membered unsaturated ring is fused to this) , A is [formula] [formula] [formula] [Formula] -SZ' or _n represents a monovalent heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused), and B is a residue having 1 to 6 carbon atoms. represents an alkylene group, M represents a divalent metal atom, X and
X′ represents =S, =O or =NR″, and R″ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (a 5- to 6-membered unsaturated group), and Y represents [Formula] or [Formula], and Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, Represents a nitrogen heterocyclic residue or [Formula], Z' represents Z or an alkyl group, and R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue ( (including those _with at least one 5- to 6-membered unsaturated ring condensed thereto) or _an amino group;
R ₄ , R ₅ , R and R' are each a hydrogen atom, carbon number 1
-6 alkyl group, hydroxy group, carboxy group, amino group, acyl group having 1 to 3 carbon atoms, aryl group, or alkenyl group. However, R ₄ and
R ₅ may represent -B-SZ, and R and R', R ₂
and R ₃ , R ₄ and R ₅ may each be cyclized with each other to form a heterocyclic residue (including one in which at least one 5- to 6-membered unsaturated ring is fused thereto). R ₆ and R ₇ each represent [Formula] [Formula] or [Formula], and R ₉ is an alkyl group or -(CH ₂ ) n ₈ SO ₃ ○-
(however, when R ₈ is −(CH ₂ ) n ₈ SO ₃ ○−, l
represents 0 or 1. ) G○− is an anion, m ₁ or
m ₄ and n ₁ to n ₈ are each an integer of 1 to 6, m ₅
represents an integer from 0 to 6. R ₈ represents a hydrogen atom, an alkali metal atom, [Formula] or an alkyl group. However, Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 carbon atoms, and q represents an integer of 1 to 10.
A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further condensed with a 5- to 6-membered unsaturated ring. Note that the compound represented by the above general formula includes enolized compounds and salts thereof. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the compounds represented by the general formulas [] to [] are the following compounds. 【table】 /
_CH3 ‖

S
[Table] 3 Processing of the silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that the thickness of the photographic constituent layer of the silver halide color photographic light-sensitive material is 18 μm or less. Method. 4 Each of the silver halide emulsion layers contains 3 mol% to
Claim 1, characterized in that it contains silver halide grains containing 25 mol% silver iodide.
A method for processing a silver halide color photographic light-sensitive material according to item 1, 2 or 3. 5. Processing of a silver halide color photographic light-sensitive material according to any one of claims 1 to 4, characterized in that a bleach-fixing process is carried out after color development and after a fixing process. Method.