JPH0570142B2 - - Google Patents

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 with improved 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, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate have relatively good bleaching power for image silver, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body.
It has unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers such as thiosulfates in the same processing solution, and it is difficult to use these oxidizing agents in bleach-fixing baths. This makes it difficult to achieve the goal of speeding up and simplifying the process. 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, metal complex salts of organic acids such as aminopolycarboxylic acid metal complex salts have been used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling recycling of waste liquid. Treatment liquids have come to be used. 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. . For example, iron() complex salt of ethylenediaminetetraacetate, which is considered to have the strongest bleaching power among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleaching solution and a bleach-fixing solution in some places, but silver bromide, iodine, etc. High-sensitivity silver halide color photographic materials based on silver bromide emulsions, especially color papers for photography, color negative films for photography, and color reversal films that contain silver iodide as silver halide, lack bleaching power. Even after long-term processing, traces of image silver remain, resulting in poor desilvering performance. This tendency is particularly noticeable in bleach-fix solutions in which oxidizing agents and thiosulfates and sulfites coexist because the redox potential decreases. In recent years, the use of DIR compounds has been known as one of the techniques for improving the graininess and sharpness of photographic images. This DIR compound reacts with the oxidized form of the color developing agent to imagewise release a development inhibitor, inhibiting silver development, thereby preventing the dye cloud from becoming large and improving graininess. Although this technique is extremely effective in improving image quality, it has the disadvantage that the released inhibitor is adsorbed onto the silver surface, deteriorating the desilvering performance. In addition, for the purpose of improving the stability of dye images during long-term storage and reducing the amount of silver halide used, development suppression with low diffusivity as described in JP-A No. 57-35858, etc. Although a method using a coupler that releases an agent is known, this technique also has the disadvantage of poor desilvering performance. Furthermore, tetrazaindene derivatives and 6-aminopurine derivatives, which are used as emulsion stabilizers, are removed in high-sensitivity light-sensitive materials because of their low redox potential in bleach-fix solutions that coexist with thiosulfates and sulfites. This is one of the factors that worsens silver quality. Therefore, a processing method with good desilvering performance has been strongly desired. [Problems to be Solved by the Invention] Therefore, the present invention provides a silver halide color photographic light-sensitive material that is quick and has sufficient silver bleaching power even when image improvement technology and image quality storage improvement technology are used. A technical problem is to provide a processing method using a processing liquid having a bleaching ability. [Structure of the Invention] A method for processing a silver halide color photographic light-sensitive material according to the present invention which solves the above-mentioned technical problem contains silver iodobromide or silver chloroiodobromide containing 0.1 mol% or more of silver iodide. It has at least one photosensitive silver halide emulsion layer with a total coated silver amount of 20 mg/d.
^m2 or more, and the solubility product with silver ions is 1×
After imagewise exposure, a silver halide color photographic light-sensitive material containing at least one compound that dissolves an inhibitor that forms a silver salt of 10 ^-9 or less during development processing is processed, and diethylenetriaminepentaacetic acid 2 is used as a bleaching agent. Iron complex salt, cyclohexanediaminetetraacetic acid 2
It is characterized in that it is treated with a treatment liquid having bleaching ability that contains an iron complex salt or a ferric triethylenetetraminehexaacetic acid complex salt. Furthermore, in a preferred embodiment of the present invention, the processing solution having bleaching ability is a bleach-fixing solution, and it has been found that the object of the present invention can be achieved more effectively by this. The present invention will be explained in detail below. DIR compounds have traditionally been used to improve image quality, especially for the purpose of improving sharpness, but development inhibitors released or dissolved during development enhance the edge effect and improve sharpness, but they When silver is adsorbed to the surface and during the bleaching process, especially in the bleach-fix solution where the oxidation-reduction potential is low, so-called desilvering failure is likely to occur. In particular, when color developer components adhere to the surface of light-sensitive materials during continuous processing and become mixed in, this becomes an even bigger problem, and this problem cannot be solved at all with the ethylenediaminetetraacetic acid iron() complex salts that are currently commonly used on the market. That's a problem. However, after various studies, the present inventor found that diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid ferric complex salt was used in the bleaching solution or bleach-fixing solution, and such light-sensitive materials Surprisingly, the inventors discovered that the desilvering properties were improved when certain DIR compounds were used, leading to the present invention. As a result of further investigation, we decided to include a compound in the photosensitive material that is eluted during the development process and an inhibitor that creates a silver salt with a solubility product with silver ions of 1×10 ^-9 or less. If you use complex salts,
The inventors have discovered that the above-mentioned effects can be obtained in a similar manner, and have completed the present invention. The solubility product in the present invention has the general meaning described in the Chemical Encyclopedia (published by Kyoritsu Shuppan Co., Ltd., September 15, 1971, 14th edition of the reduced edition), volume 9, page 399, etc. It has the same meaning as , and more specifically, it refers to the product of the concentration of silver ions and the inhibitor (gram ions/) at 25°C when the silver ions constitute the inhibitor and the poorly soluble silver salt. Any compound may be used to elute the inhibitor that forms a silver salt having a solubility product of 1×10 ^-9 or less with silver ions during the development process, but especially DIR
Compounds, tetrazaindene derivatives, and 6-aminopurine derivatives are preferably used. Among these, DIR compounds are particularly preferably used in order to give good results in achieving the object of the present invention. Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development are also included in the present invention, such as U.S. Pat. No. 3,297,445, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
No. 15271, No. 53-9116, No. 59-123838, No. 59
Examples include those described in No.-127038. The DIR compound used in the present invention is a compound that can react with an oxidized form of a color developing agent to release a development inhibitor. A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting effect when released from the active site is introduced into the active site of the coupler. , U.S. Patent No. 3227554, U.S. Patent No. 4095984,
It is described in No. 4149886, etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. Additionally, the present invention utilizes U.S. Patent No. 3,652,345,
No. 3928041, No. 3958993, No. 3961959, No.
No. 4052213, Japanese Patent Publication No. 53-110529, No. 54-13333
It also includes compounds that release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 55-161237. Furthermore, JP-A-54-145135, JP-A No. 56-
When reacted with oxidized color developing agents such as those described in No. 114946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Alternatively, the present invention also includes a so-called timing DIR compound, which is a compound that releases a development inhibitor through an elimination reaction. In addition, as described in JP-A-58-160954 and JP-A-58-162949, the above timing group is present in the coupler core that produces a completely diffusible dye when it reacts with an oxidized color developing agent. It also includes bound timing DIR compounds. According to the present invention, more preferred DIR compounds can be represented by the following general formulas () and (). General formula () Coup-inhibitor In the formula, Coup is a coupler component capable of coupling with the oxidized form of a color developing agent, such as open-chain ketomethylene compounds of acylacetanilides, pyrazolones, pyrazolotriazoles, and pyrazolinobenzimidazoles. and dye-forming couplers such as indazolones, phenols, and naphthols, and coupling components that do not substantially form dyes such as acetophenones, indanones, and oxazolones. The inhibitor in the above formula is a compound that inhibits the development of silver halide, and preferred compounds include benztriazole, 3-octylthio-1,
There are heterocyclic compounds and heterocyclic mercapto compounds such as 2,4-triazole and the like. Examples of the heterocyclic group include a tetrazolyl group, thiadiazolyl group, oxadiazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, triazolyl group, and the like. in particular,
1-phenyltetrazolyl group, 1-ethyltetrazolyl group, 1-(4-hydroxyphenyl)tetrazolyl group, 1,3,4-thiazolyl group, 5-methyl-1,3,4-oxadiazolyl group , benzthiazolyl group, benzoxazolyl group, benzimidazolyl group, 4H-1,2,4-triazolyl group, etc. General formula () Coup-TIME-inhibitor In the formula, the inhibitor is the same as defined in the above general formula (). In addition to those defined by the general formula (), Coup also includes coupler components that produce completely diffusible dyes.
TIME is represented by the following general formulas (), () and (), but is not limited to these. General formula ()

[Formula] In the formula, X represents an atomic group necessary to complete a benzene ring or a naphthalene ring. Y is -O
-, -S-,

[Formula] (where R ₃ represents a hydrogen atom, an alkyl group, or an aryl group), and is bonded to the coupling position. Moreover, R ₁ and R ₂ are
Each represents the same group as R ₃ above,

The group [Formula] is substituted in the ortho or para position to Y and is bonded to a heteroatom contained in the inhibitor. General formula ()

[Formula] In the formula, W is a group having the same meaning as Y in the above general formula (), and R ₄ and R ₅ are also each represented by the general formula ()
This group has the same meaning as R ₁ and R ₂ in . R ₆ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic residue, and R ₇ is a hydrogen atom, an alkyl group, an aryl group,
Represents a heterocyclic residue, an alkoxy group, an amino group, an acylamido group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyan group. And this timing base is determined by W
Binds to the coupling position of Coup,

[Formula] is attached to the heteroatom of the inhibitor. Next, an example of a timing group that releases an inhibitor by an intramolecular nucleophilic substitution reaction is shown by the general formula (). General formula ()

[Exemplary compounds]

(D-1)

[ka] (D-2)

[C] (D-3)

【formula】 (D-4)

【formula】 (D-5)

【formula】 (D-6)

[ka] (D-7)

[ka] (D-8)

[ka] (D-9)

[ka] (D-10)

[ka] (D-11)

[ka] (D-12)

[C] (D-13)

【formula】 (D-14)

[ka] (D-15)

[C] (D-16)

【formula】 (D-17)

[ka] (D-18)

【formula】 (D-19)

【formula】 (D-20)

【formula】 (D-21)

【formula】 (D-22)

[ka] (D-23)

[ka] (D-24)

[ka] (D-25)

[ka] (D-26)

[C] The above DIR compound is disclosed in U.S. Pat.
No. 3615506, No. 3632345, No. 3928041, No.
No. 3933500, No. 3938996, No. 3958993, No. 3933500, No. 3938996, No. 3958993, No.
No. 3961959, No. 4046574, No. 4052213, No.
No. 4063950, No. 4095984, No. 4149886, JP-A-Sho
No. 50-81144, No. 50-81145, No. 51-13239,
No. 51-64927, No. 51-104825, No. 51-105819
No. 52-65433, No. 52-82423, No. 52-
No. 117627, No. 52-130327, No. 52-154631, No. 117627, No. 52-130327, No. 52-154631, No.
No. 53-7232, No. 53-9116, No. 53-29717, No. 53-29717, No.
No. 53-70821, No. 53-103472, No. 53-110529,
No. 53-135333, No. 53-143223, No. 54-13333
No. 54-49138, No. 54-114241, No. 57-
No. 35858, No. 54-145135, No. 55-161237, No.
No. 56-114946, No. 57-154234 and patent application No. 1983-
It can be synthesized by the method described in No. 44831, No. 57-45809, etc. The amount of the DIR compound contained in the light-sensitive material is generally in the range of 1 x 10 ^-3 mol to 1 x 10 ^-1 mol per mol of silver. The tetrazaindene derivative used in the present invention is
It is known as a stabilizer for silver halide emulsions in photographic light-sensitive materials, and those represented by the following general formula () have particularly favorable effects. General formula ()

[Formula] In the formula, m and n are integers of 1, 2 or 3,
R ₈ and R ₉ each represent a hydrogen atom, an alkenyl group having 1 to 4 carbon atoms which may have a substituent, an alkyl group, or an aryl group which may have a substituent. As the tetrazaindene derivative, those represented by the general formula () are particularly effective, but specific examples of tetrazaindene derivatives more effectively used in the present invention are shown below, but the invention is not limited to these. . [Exemplary compounds] A-1 4-hydroxy-1,3,3a,7-tetrazaindene A-2 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene A-3 4-hydroxy-6-hydroxy-1,
3,3a,7-tetrazaindene A-4 4-hydroxy-6-butyl-1,3,
3a,7-tetrazaindene A-5 4-hydroxy-5,6-dimethyl-
1,3,3a,7-tetrazaindene A-6 2-ethyl-4-hydroxy-6-propyl-1,3,3a,7-tetrazaindene A-7 2-allyl-4-hydroxy-1, 3,
3a,7-tetrazaindene A-8 4-hydroxy-6-phenyl-1,
3,3a,7-tetrazaindene These compounds are listed in Japanese Patent Publication No. 18102/1986, No. 44-
It can be synthesized by referring to the description in No. 2533 and the like. Among these compounds, those having a hydroxyl group at the 4th position are preferred, and those having a hydroxyl group at the 4th position and an alkyl group or an aryl group at the 6th position are more preferred. The 6-aminopurine derivatives used in the present invention include those known as stabilizers for silver halide emulsions in photographic light-sensitive materials, but those represented by the following general formula () exhibit particularly preferable effects. General formula ()

[Formula] In the formula, R ₁₀ is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and R ₁₁ is a hydrogen atom or a C 1 to 4 alkyl group which may have a substituent. Represents an alkyl group or an aryl group which may have a substituent. As the 6-aminopurine derivative in the present invention, those represented by the general formula () are particularly effective. Specific examples of 6-aminopurine derivatives that can be used more effectively are shown below, but the invention is not limited thereto. do not have. [Exemplary compounds] B-1 6-aminopurine B-2 2-hydroxy-6-aminopurine B-3 2-methyl-6-aminopurine B-4 6-amino-8-methylpurine B-5 6-amino -8-phenylpurine B-6 2-hydroxy-6-amino-8-phenylpurine B-7 2-hydroxymethyl-6-aminopurine These tetrazaindene derivatives and 6-aminopurine derivatives are preferably silver halide 1 When used in the range of 5 mg to 18 g per mole, good effects are achieved for the purpose of the present invention. Furthermore, the solubility product with these silver ions is 1×
Among the compounds that form silver salts with a solubility product of 1×10 ⁻¹ or less, those having a solubility product of 1×10 ⁻¹¹ or less exhibit the effects of the present invention more preferably. Furthermore, it is known that DIR compounds, tetrazaindene derivatives, and 6-aminopurine derivatives can be added to ordinary silver halide emulsions to improve image quality and suppress aging fog that occurs during emulsion production. It is completely unknown that desilvering performance is improved when used in combination with diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid ferric complex salt. It wasn't. In the present invention, processing with a processing liquid having bleaching ability means processing with a bleaching liquid or a one-bath bleach-fixing solution, but the effect of the present invention is best achieved by performing a one-bath bleach-fixing treatment. This is the case. The following explanation will mainly be made regarding this one-bath bleach-fixing process. The ferric complex salt of an organic acid according to the present invention is a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, or a lithium salt, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt. However, preferably the potassium, sodium and ammonium salts are 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 aminopolycarboxylate salts because of its high oxidizing power. Can be used in For example, it can be used in an amount of 0.01 mol or more, preferably 0.05 to 0.6 mol per working solution. In addition, it is desirable to use the replenisher after concentrating it to maximize its solubility in order to achieve high concentration and low replenishment. The bleaching solution and bleach-fixing solution of the present invention have a pH of from 0.2 to
It can be used with a value of 9.5, preferably 4.0 or more, more preferably 5.0 or more. The treatment temperature is 80°C or lower, preferably 55°C or lower to prevent evaporation. The bleaching solution of the present invention is a diethylenetriaminepentaacetic acid ferric complex salt, a cyclohexanediaminetetraacetic acid ferric complex salt, or a triethylenetetraminehexaacetic acid ferric complex salt.
Various additives can be included along with the iron complex salt. As additives, in particular alkali halides or ammonium halides, such as potassium bromide,
It is desirable to contain sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like. In addition, PH buffers such as borates, oxalates, acetates, carbonates, and phosphates, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, etc. Those known to be added to ordinary bleaching solutions, such as acids, alkylamines, and polyethylene oxides, can be added as appropriate. The bleach-fix solution of 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 containing a large amount of a halogen compound such as potassium bromide or ammonium bromide. It is also possible to use a fixing solution, as well as a special bleach-fixing solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide. As the above-mentioned halogen compound, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. can also be used. can. The silver halide fixing agents contained in the bleach-fixing solution of the present invention include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and 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. Note that the bleach-fix solution of the present invention contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and hydroxide. Consists of various salts such as ammonium
A PH buffer may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. In addition, preservatives such as hydroxyamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids,
Organic chelating agents such as polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitro alcohol and nitrate, solubilizers such as alkanolamines, stains such as organic amines, etc. Inhibitors, other additives, and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide can be appropriately contained. In the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after color development. Alternatively, 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), it is possible to perform stabilizing treatment without washing with water, or to perform washing with water and
Stabilization treatment may then be performed. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. A typical example of a preferred treatment method includes the following steps. (1) Color development → bleach-fix → water washing (2) color development → bleach-fix → small amount of water washing → water washing (3) color development → bleach-fix → water washing → stable (4) color development → bleach-fix → stable (5) color development → Bleach-fixing → 1st stable → 2nd stable (6) Color development → washing with water (or stable) → bleach-fixing → washing with water (or stable) (7) Color development → stop → bleach-fixing → washing with water (or stable) (8) Color development → bleaching → washing with water → fixing → washing with water → stabilizing (9) Color development → bleaching → fixing → washing with water → stabilizing (10) Color development → bleaching → fixing → first stable → second stable (11) color development → bleaching → A small amount of water washing → Fixing → A small amount of water washing → Water washing → Stabilization (12) Color development → A small amount of water washing → Bleaching → A small amount of water washing → Fixing → A small amount of water washing → Water washing → Stabilization (13) Color development → Stop → Bleaching → A small amount of water washing → Fixing → A small amount of water washing → Water washing → Stable (14) Black and white development → Water washing (or stable) → Reversal → Color development → Bleaching → Fixation → Water washing (or omitted) → Stable (15) Prehardening → Neutralization → Black and white development → Stop → Color development →
Bleaching → Fixing → Washing (or omitting) → Stabilization Among these processing steps, the effects of the present invention are more noticeable, so (1), (2), (3), (4), (5), (6)
A processing step having the bleach-fixing step (7) is more preferably used in the present invention. 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 may be any of the known aromatic primary amine color developing agents that are widely used in various color photographic processes. Included. These developers 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. In addition, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer.
More preferably, a concentration of about 1 g to about 15 g per portion is used. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxy-toluene, 2-amino-
Included are 3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like. A particularly useful aromatic primary amine color developer is an aromatic primary amine color developer having an amino group having at least one water-soluble group, and particularly preferably a compound represented by the following general formula (). It is. General formula ()

[Formula] In the formula, R ₁₃ represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and may have a substituent. R ₁₄ and R ₁₅ represent a hydrogen atom, an alkyl group, or an aryl group,
These groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. At least one of R ₁₄ and R ₁₅ is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, or [(--CH ₂ -) _q O-] _p R ₁₆ . This alkyl group may further have a substituent. In addition, _R16 represents a hydrogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q represent 1 to 5 carbon atoms.
represents an integer. Next, compounds represented by the above general formula () will be listed, but the compounds are not limited thereto. [Exemplary compound] (E-1)

【formula】 (E-2)

【formula】 (E-3)

【formula】 (E-4)

【formula】 (E-5)

【formula】 (E-6)

【formula】 (E-7)

【formula】 (E-8)

【formula】 (E-9)

【formula】 (E-10)

【formula】 (E-11)

【formula】 (E-12)

【formula】 (E-13)

【formula】 (E-14)

【formula】 (E-15)

【formula】 (E-16)

[Formula] These p-phenylenediamine derivatives represented by the general formula () can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, phosphate, p-toluenesulfonate, and sulfite. , oxalate, benzenedisulfonate, etc. can be used. In the present invention, among these p-phenylenediamine derivatives represented by the general formula (),
R ₁₄ and/or R ₁₅ are [−(CH ₂ −) _q O−] _p R ₁₆ (p, q
and R ₁₆ have the same meanings as above), the effects of the present invention are particularly well exhibited. The treatment liquid with bleaching ability of the present invention has a surface tension of
It is preferable that it is 55 dyne/cm or less. The surface tension of the treatment solution with bleaching ability used in the treatment of the present invention can be determined from the "Analysis and Testing Methods for Surfactants"
(Co-authored by Fumio Kitahara, Shigeo Hayano, and Ichiro Hara, published March 1, 1982, published by Kodansha Co., Ltd.). This is the value of surface tension according to 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 a common surfactant is preferably used. These surfactants that lower the surface tension of the processing solution with 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 adhering to the photosensitive material. good. Furthermore, the surfactant may be contained in the photosensitive material 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 (4) are preferably used from the viewpoint of achieving the desired effects of the present invention. General formula (1)

[Formula] In the formula, one of R ₁ and R ₂ represents a hydrogen atom, and the other represents a group represented by the formula -SO ₃ M (M represents a hydrogen atom or a monovalent cation). A ₁ represents an oxygen atom or a group represented by the formula -NR ₅ - (R ₅ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). R ₃ and R ₄ each represent an alkyl group having 4 to 16 carbon atoms. However, R ₃ , R ₄
Alternatively, the alkyl group represented by R ₅ may be substituted with a fluorine atom. General formula (2) A ₂ -O-(B)m-X In the formula ( ₁₎ , A ₂ is a monovalent organic group, such as an alkyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms (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, and the substituent preferably has 3 to 12 carbon atoms. alkyl groups (e.g. propyl,
(butylpentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.), and the aryl group includes phenyl, tolyl, xynyl, biphenyl, naphthyl, etc., and preferably phenyl group. Or it is a 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, and m represents an integer from 4 to 50. X ₁ represents a hydrogen atom, SO ₃ Y or PO ₃ Y ₂ , and Y
is a hydrogen atom, an alkali metal (Na, K or Li, etc.)
Or represents ammonium ion. General formula (3)

[Chemical formula] In the formula, R ₆ , R ₇ , R ₈ and R ₉ each represent a hydrogen atom, an alkyl group, or a phenyl group, but R ₆ , R ₇ ,
The total number of carbon atoms of R ₈ and R ₉ is 3 to 50.
X ₂ is a halogen atom, hydroxyl group, sulfate group, carbonate group,
Indicates anions such as a nitrate group, an acetate group, and a p-toluenesulfonic acid group. General formula (4)

embedded image In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom or an alkyl group, and M has the same meaning as in general formula (1). n and p each represent 0 or an integer of 1 to 4, and are values satisfying 1≦n+p≦8. 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. patent
Nos. 2376679 and 2801171), as well as external development methods (U.S. patent
2252718, 2592243, and 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, pivalyl acetanilide such as benzoylacetanilide having an active methylene chain, and those having an acylacetanilide structure, with or without a substituent at the coupling position, can be used. Thus, as the coloring agent, both so-called 2-equivalent couplers and 4-equivalent couplers can be used. As the silver halide emulsion that can be used, silver iodobromide or silver chloroiodobromide containing 0.1 mol % or more of silver iodide is used in at least one photosensitive emulsion layer. Furthermore, as protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, hardeners, sensitizing dyes, and surfactants. When the silver halide color photographic light-sensitive material according to the present invention includes a colloidal silver dispersion layer, the effects of the present invention are particularly well exhibited. The colloidal silver dispersion layer may be a filter layer or an antihalation layer,
Furthermore, it may be dispersed in the emulsion layer. How to make these colloidal silver dispersions is described in Japanese Patent Publications No. 43-27740, No. 49-43201, No. 45-
No. 14890, Japanese Patent Application Publication No. 51-89722 and British Patent
Synthesized by the general method described in No. 1032871 etc.
Painted. The bleaching solution and bleach-fixing solution of the present invention can be applied to color negative films, color positive films, and color reversal films for slides having a total coated silver amount of 20 mg/dm ² or more.
It can be applied to silver halide color photographic materials such as color reversal films for movies and color reversal films for TV, but in particular silver iodide of 0.1 mol% is used.
It is most suitable for processing high-sensitivity color photographic materials containing silver iodobromide or silver chloroiodobromide and having a total coated silver amount of 20 mg/dm ² or more. [Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer,
A filter layer containing yellow colloidal silver and a blue-sensitive silver halide emulsion layer with a total silver amount per 100 cm ²
It was applied at a dose of 90 mg. The above emulsion layer is silver iodobromide with a molar percentage of silver iodide of about 4.5%, and in this case,
The blue-sensitive silver halide emulsion layer contains α-(4-nitrophenoxy)-α-pivalyl- as a yellow coupler.
5-[γ-(2,4-di-t-aminophenoxy)
[Butylamide]-2-chloroacetanilide was used, and Exemplary Compound (D-18) was used as the DIR compound. The green-sensitive silver halide emulsion layer contains 1-(2,4,6-trichlorophenyl)-3-{[α-(2,4-di-t-amylphenoxy)-acetamido]benzamide}- as a magenta coupler. 3-pyrazolone and 1-(2,4,6-trichlorophenyl)-3-{[α-(2,4-di-t-amylphenoxy)-acetamido]benzamide}-4-(4
-methoxyphenylazo)-5-pyrazolone was used, and 1-hydroxy-N-{α-(2,4-t
-amylphenoxy)butyl}-2-naphthamide was used, and additives such as a sensitizing dye, a hardening agent, and a spreading agent were added to each emulsion layer.The thus obtained silver halide color negative photosensitive material was used. This was used as film sample (1). Furthermore, a similar film sample (2) was prepared from this film sample (1) except that the DIR compound was removed. These samples were exposed to light in a conventional manner and then subjected to the following treatments. Processing process Processing temperature (°C) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 Bleach-fixing 37.8 Listed in Table 1 3 Washing with water 30-34 2 minutes 4 Stability 30-34 1 minute 5 Drying Color developer, bleach-fixing The following liquids and stabilizing liquids were used. [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxyamine sulfate 2.2g Potassium bromide 1.2g Diethylenetriaminepentaacetic acid 2.0g Sodium hydroxide 3.4g N-ethyl-N-β-hydroxyethyl-3-
Methyl-4-aminoaniline sulfate 4.6g Water was added to make up to 1000ml, and the pH was adjusted to 10.05 with sodium hydroxide. [Bleach-fix solution] Organic acid ferric complex salt (shown in Table 1) 0.3 mol Nitrilotriacetic acid 5.0 g Ammonium sulfite (50% solution) 10 ml Ammonium thiosulfate (70% solution) 240 ml Add water to make up to 1000 ml, add ammonia water ( 28
% solution) to adjust the pH to 7.0. [Stabilizer] Formalin (35% aqueous solution) 7.0ml

[Formula] Add 1.0ml water to make 1000ml. The time required for the bleach-fixing process until the amount of residual silver in the organic acid ferric complex salt and film sample became 0.5 mg/dm ² as shown in Table 1 below was determined. The results are summarized in Table 1.

[Table] As is clear from Table 1 above, the desilvering performance of conventionally used organic acid ferric complex salts such as EDTA and Fe is not sufficient, and
In the case of EDTA/Fe, when a DIR compound is used in the film, the desilvering performance is further deteriorated.
Furthermore, even if the DTPA/Fe of the present invention is used alone, a considerable desilvering performance can be obtained, but it is still not sufficient. However, when the organic acid ferric complex salt of the present invention is used and a DIR compound is used in the light-sensitive material, it is surprisingly found that the desilvering performance is improved. Furthermore, among the organic acid ferric complex salts of the present invention, (DTPA・Fe＞CyDTA・Fe＞TTHA・
It can be seen that the desilvering performance is better in the order of Fe). However, during development of the DIR compound (D-18), the solubility product of the eluted inhibitor with silver ions was 10 ^-16.2 . Example 2 In Experiment 4 of Example 1, an experiment similar to Example 1 was conducted except that the filter layer containing yellow colloidal silver was removed from film sample (1) as a film sample. Even though the amount decreased, it actually took about 20 seconds longer. This shows that the effect of the present invention is further enhanced when a colloidal silver dispersed layer is present. Example 3 DIR compound (D
-18) to (D-5), (D-6), (D-10), (D-
When experiments similar to those in Example 1 were carried out by replacing 12) and (D-24), almost the same results were obtained.
However, the solubility product of the inhibitor eluted during development of each DIR compound with the silver ion is (D-5), (D-6)
is about 10 ^-14.8 , (D-10), (D-12) is about 10 ^-16.2 ,
(D-24) was approximately 10 ^-12.9 .

Claims (1)

[Scope of Claims] 1. It has at least one photosensitive silver halide emulsion layer containing silver iodobromide or silver chloroiodobromide containing 0.1 mol% or more of silver iodide, and the total coating amount of silver is Silver halide color photographic photosensitive material containing at least one compound that dissolves during development processing an inhibitor that forms a silver salt with a solubility product of 20 mg/dm ² or more and a solubility product with silver ions of 1×10 ^-9 or less After imagewise exposure, the material is developed and treated with a processing solution having bleaching ability containing diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid complex salt as a bleaching agent. A method for processing a silver halide color photographic light-sensitive material. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution having bleaching ability is a bleach-fix solution.