JPS6147962A - Treatment of silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To process quickly a silver halide photosensitive material contg. a specific ratio of silver iodide by processing said photosensitive material with a bleaching agent contg. an org. acid ferric complex salt and having specific surface tension after exposing and developing process. CONSTITUTION:The bleaching agent contg. the org. acid ferric complex salt, for example, diethylene triamine pentaacetic acid ferric complex salt, for example, diethylene triamine pentaacetic acid ferric complex salt, diethylene triamine pentaacetic acid ferric complex salt, etc. having bleaching power is manufactured. A surface active agent, for example, the compd. expressed by the formula (where n denotes 10) or the like is added to the bleaching agent to adjust the surface tension thereof to <=55dyne/cm. The photosensitive material having high sensitivity is manufactured of the silver halide incorporated therein with >=0.5 mol% silver iodide. The photosensitive material is subjected to the imagewise exposing and developing process and thereafter the developed silver is bleached by the bleaching agent. Since the bleaching is executed by the bleaching agent having the small surface tension, the quick processing is made possible even with the photosensitive material which is hardly bleached and has high sensitivity.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing silver halide color photographic materials having rapid silver bleaching ability. [Prior Art] Generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material, after the color development process, the produced gold H silver is treated with a processing solution having bleaching ability. A process is set up. As processing liquids having bleaching ability, bleaching liquid, bleaching 22? liquid is known. When a bleaching solution is used, a bleaching step is usually followed by a step of fixing the silver halide with a fixing agent, but with a bleach-fixing solution, bleaching and fixing are performed in one step. Inorganic oxidizing agents such as red blood salts and chromium m salts are widely used as oxidizing agents for bleaching image silver in processing solutions that have bleaching ability in the processing of silver halide color photographic light-sensitive materials. . However, some serious drawbacks have been pointed out to the bleaching solutions containing these inorganic oxidizing agents. Although it is relatively good, there is a risk that it 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 silver halide solubilizers (fixing agents) such as thiosulfate salts in the same processing solution, and these agents cannot be used in bleach-fixing baths. It is almost impossible to use such oxidizing agents, which 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 gold Fj[41,1] have been proposed as having fewer pollution problems and meeting the requirements of speeding up and simplifying treatment, and being able to reuse waste liquid. Processing liquids containing oxidizing agents have come to be used. However, processing solutions using metal rust salts of organic acids have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow due to their slow oxidizing power. For example, iron(III) complex salt of ethylenediaminetetraacetate, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleach solution and bleach-fix solution in some places, but High-sensitivity silver halide color photographic materials based on silver and silver iodobromide emulsions, especially color papers for photography containing silver iodide as silver halide, color negative films for photography, and color reversal films with bleaching blades. is insufficient, and even after long-term processing, image silver remains as small as a scar, resulting in poor desilvering performance. This tendency is particularly noticeable in bleach-fix solutions in which an oxidizing agent and periosulfate and sulfite coexist because the redox potential is lowered. Therefore, in order to increase the silver source whiteness of bleaching solutions or bleach-fixing solutions containing organic acid metal complex salts, particularly ethylenediaminetetraacetic acid iron (m) complex salts, Japanese Patent Publication Nos. 45-8506 and 46-
No. 556, No. 53-9854, No. 45-8836,
JP-A-46-280, JP-A No. 54-71634, JP-A No. 49
It is known to add various bleaching accelerators, as described in US Pat. The reality is that it cannot be obtained. On the other hand, among aminopolycarboxylic acid metal complex salts, the present inventors have discovered diethylenetriaminepentaacetic acid iron(III) complex salt as an oxidizing agent having excellent oxidizing power particularly in a high pH region. Bleach solutions and bleach-fix solutions containing these oxidizing agents have a large silver source white edge when the pH is 4 or higher, especially 7 or higher, so they do not cause poor color restoration due to leucoization of cyan dye, which is noticeable in low pH ranges. It has extremely excellent performance in that it can be processed quickly. However, even with these oxidizing agents, the bleaching speed is insufficient as a bleaching agent for high-sensitivity silver halide color photographic materials containing silver iodide of 0.1 mol% or more, especially 0.5 mol% or more. It has become clear that this is insufficient and that the required rapid processing cannot be fully met. [Problems to be Solved by the Invention] The present invention has a technical object to provide a method for processing silver halide color photographic materials that has low toxicity, meets the requirements for pollution prevention, and has an excellent bleaching speed. Take it as a challenge. [Structure of the Invention] As a result of intensive research, the present inventor developed a silver halide color photographic light-sensitive material containing 0.5 mol% or more of silver iodide after imagewise exposure, and processed it with a processing solution having bleaching ability. In the method for processing a silver halide color photographic light-sensitive material, the surface tension of the processing liquid is 55 dyne/cm or less, and the processing liquid contains organic vinegar 2 selected from the group of ferric complex salts as a bleaching agent. At least one iron complex salt (A) or an organic acid f
: The pH of the following standard solution of fS2 iron complex salt is 5.0 to 8.0.
It has been found that the above technical problem (object) can be solved by containing at least one organic acid ferric complex salt (B) in which the difference in redox potential between the two is within 100+++V. [Organic acid ferric salt (A)] (1) Diethylenetriaminepentaacetic acid ferric rust salt (2) Diethylenetriaminepentaacetic acid ft52 iron complex salt (3) Cyclohene diaminetetraacetic acid ferric complex salt (4) Cyclohequinanediaminetetraphosphate JI2iron complex salt (5) Triethylenetetraminehexaacetic acid Jm2iron difference salt (6) Triethylenetetraminehexaphosphate ferric complex salt (7) Glycol ether diaminetetraacetic acid ferric salt (8) Glycol ether Ferric diaminetetraphosphate complex salt (9) 1.2-Diaminopropanetetraacetic acid #52 iron complex salt (10) 1.2-Diaminopropanetetraphosphate ferric complex salt (
11) Methyliminodiacetic acid m ferric complex salt (12) Methyliminodiphosphate ff12 iron complex salt [Reference solution of organic acid ferric complex salt of organic acid such as aminopolycarboxylic acid for redox potential measurement] Ferric chloride 0.23M aminopolycarboxylic acid Organic acids such as acids 0.305M ammonium 1,000 sulfate 1.0M ammonium sulfite
The pH is adjusted using 0.1M ammonia water and acetic acid, and the redox potential is measured. In a preferred embodiment of the present invention, the treatment liquid having bleaching ability has the following general formula CI) (a) to (i
) It has been found that the objects of the present invention can be more effectively achieved when at least one compound represented by the following formula is contained. General formula (1) % formula %) In the formula, R and R1' are a substituted or unsubstituted furkyl group having 1 to 30 carbon atoms, an alkylaryl group, an aryl group, "-CnFgo1. R3→5i-0+-1 (R3 is a substituted or unsubstituted alkyl group having 1 to 3G1% carbon atoms, an alkylaryl group,
represents an aryl group, (CHz)II (CF2)nH, and A is substituted or unsubstituted fullkylene' having 1 to 6 carbon atoms.
group, arylene group, furkylarylene group, B
, Bλ represents 10-1 Q-C-R1, Q is -H, -5Ox M, -
111: OOM, represents deprivation, Z is synonymous with the above Z1 or z2, and X is 1
represents a valent cation, X represents a monovalent anion,
and n represent integers from 1 to 30. Further, in another preferred embodiment of the present invention, the organic acid ferric complex salt is at least one selected from diethylenetriaminepentazoic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, and triethylenetetraminehexaacetic acid ferric complex salt. The present inventor has discovered that the object of the present invention can be achieved more effectively by using only one. The present invention will be explained in detail below. The organic acid ferric complex salt of the present invention itself has a high oxidizing power at pH 4 to 9, but the organic acid iron (m) complex salt of the present invention alone has a high sensitivity to halogens containing 0.5 mol% or more of silver iodide. However, the surface tension of a bleach solution or a bleach-fix solution containing the organic acid iron (m) complex salt cannot be fully demonstrated in silver oxide color photographic light-sensitive materials.
Surprisingly, it has been found that the delay in bleaching speed can be greatly accelerated by reducing the bleaching speed to less than m. A silver halide color photographic light-sensitive material to which the method of the present invention is applied contains silver iodide in an amount of 0.5 mol % or more. This allows the object of the present invention to be effectively achieved. Preferably 1 mol% iodide, most preferably 2 mol%
When the above content is contained, the object of the present invention can be achieved more effectively. Furthermore, the surface tension of the processing solution having bleaching ability according to the present invention is 55 dyne in order to effectively achieve the object of the present invention.
/c+++ or less, but preferably 50
dyne/cm or less, most preferably 40drn
e/cm or less. The surface tension of the treatment solution having bleaching ability according to the present invention is 55 d.
yne/cm or less, the general formula CI) (a) ~
This can be effectively achieved by adding one or more compounds represented by the general formula (I).
) of (a), (b), (C) or (d), particularly preferably (a) or (
The method is to use a compound represented by b). Among these, particularly preferably used compounds are those in which R is an alkylaryl group and B is an oxygen atom, but the most preferred are those in which R is an ethylene group, a propylene group, a hydroxyethylene group, or a hydroxypropylene group. , n is 3
This is the case for an integer of ~20. The surface tension of the treatment solution with bleaching ability used in the treatment of the present invention is determined from "Analysis and Testing Methods for Surfactants" (co-authored by Fumio Kitahara, Shigeo Hayano, and Betsu Hara, published March 1, 1982, flT
In the present invention, the value of surface tension is measured by a general measuring method at 20°C. Specific examples of compounds represented by the general formula [U] are listed below in the margins, but the compounds are not limited thereto. [Exemplary compounds] (1-1) 0,2H2sO+OH,Cl-120
+nH(1-2') 018H3!5O-(OH2
0H20+nHH (Summer -6) 01□H2,NH-(OH2
0H20+nH (Summer -7') 01□H,5Coo
SoO□)140+nH(1-9) 012H2sC
O0Mm(+ -10) O,,H3,C00K(+
-11) 0.2l-125S03N*(1-12
) 0,2H250SO3Na(+ -13)
CHH230000H20H(OH)OH2080
,Na(1-14) 0□1H2300MHOH2
0H20803N&(1-15) 01□H2,00
MH+cH20H20+n0H20H20503N&(
1-16) (HH23-00M-CH20H2S
O3NrtOH3 (r -17) 015H3□-00M-OH20H
2So3Nm0H,OH20H (1-19) 007H33-00M-C! H20H
04H to 2So3. (1-20) 01□H2300M-CH2SO3
NaOH3 (1-21) 015f(,1-Co-N-0H20
H2803NaOH3 (1-22)01□H25-8O2NHOH20H20
00M & (1-23) 05HuOOOOOH20
H-00005H11S O3N a (1-24) O, H1□0OOOH20H-00
008H1703Na C Toshi SO3Na 03Na (Summer -27) IOC! H20H20000H2
0HOOOO□H40H heat 803 N m (1-28) 0. , H3sO+0H20H20−>
n803N&0H3014H29 OH3 2H5 OH3 (02H40-)nH (f -35) 08H17NHOH2C! H2NH
OJ(20H2NH-OH100OH-HCl(1-3
7) 01□H25-NHOH20H2000H (1
-38) 01□H□, -N-fOH20H2cO
0M&>2(1-39) 017HgNHOH20H
2SO3Na'Hot (Summer -43) C□21(
, NH2・OH3000HH3 H3 OH. 02H. l-l3 0H1 OH3 OH3 0H1 CI-I. (OH20H20+1SH OIl. 011゜0, I-I 5 2H5 OH3 O2H. OH. OH. H3 H3 0H3 0H. 2H11 H3 OHOOOO, l'1゜SO3Na (1-78) Na0350H0000Hz (OF2
0F2), n0H2CooCH2(OFOF3) iH
(1-79) C2H. 0H2-0000H, 0H-04H. 803 N & 02 H5 (1-80) 04H. 01(2C!0OOH,0HO6H,3803Na
O4Hg SO3Na 02H5 03Na C1-86) υki3 L, II 3' The above compound used in the present invention is usually 0.01g1
It may be used in a concentration range of i to 100 g/jL, but the surface tension of the bleach or bleach-fix solution to be added should be 55 dyn.
It is used within the range of e/am or less. These compounds of the present invention that lower the surface tension of the processing solution having bleaching ability to 55 dyne/cm or less may be added to the tank solution from the replenisher, or may be added by being attached to the photosensitive material from the prebath. Furthermore, the compound of the present invention may be incorporated into a light-sensitive material and dissolved and added to the processing solution having bleaching ability of the present invention. In the present invention, processing with a processing solution having bleaching ability means
This means processing with a bleach solution or a -bath bleach-fix solution, but the effect of the present invention is better achieved when a -bath bleach-fix treatment is performed. The following explanation will mainly be made regarding this one-bath bleaching and fixing treatment. The bleach-fix solution of the present invention contains an organic acid ferric complex salt (A) or (B) as a bleaching agent. Organic acid ferric complex 11! (A) can be used by arbitrarily selecting one type from the above-mentioned 12 types, and two or more types can also be used in combination as necessary. Organic! Among the above 12 kinds of compounds of #M2 iron M salt (A), the following are particularly preferable. (1) Diethylenetriaminepentaacetic acid ferric complex salt (■) Cyclohexanediaminetetraacetic acid ferric complex salt (m)) Liethylenetetramine 6#ferric acid complex salt (B
) is a group of multiple organic acid ferric complex salts regulated by redox potential, and one type can be arbitrarily selected and used from these, and two or more types can be used in combination as necessary. can. In the present invention, the oxidation-reduction potential of a standard solution of a ferric complex salt such as aminopolycarbon WIt is 25°C.
The pH value was measured using a platinum electrode using an ordinary pH meter, and a calomel electrode was used as a comparison electrode. Regarding the relationship between pH and potential of ferric complex salts of organic acids such as aminopolycarboxylic acids, data for ferric complex salts alone are known. However, the favorable effect of the present invention is exhibited only with organic acids such as aminopolycarboxylic acids, which have a small difference in redox 1 position over a wide PH range when measured with the bleach-fixing base $ solution of the present invention. This was a surprising discovery as it was completely unknown. Specific organic complex salts 2 of aminopolycarboxylic acids having redox potential within the range of the present invention include, but are not limited to, the following. (1) Diethylenetriamine pentaphosphate ferric complex salt (2) Diethylenetriamine pentaphosphate ferric complex salt (3) Cyclohexanediaminetetraacetic acid ferric complex salt (4) Cyclohexanediamine tetraphosphate ferric complex salt (5) Triethylenetetramine hexaacetic acid complex salt Ferric complex salts (8) Triethylenetetramine hexaphosphate ferric complex salts The ferric complex salts of organic acids according to the invention include free acids (hydrogen salts), alkali metal salts such as sodium salts, potassium salts, lithium salts, etc. or ammonium salt, or water-soluble amine salt such as triethanolamine salt, preferably potassium salt, sodium salt and ammonium salt. At least one of these ferric complex salts may be used, but 2N or more can also be used in combination. The amount used can be arbitrarily selected and must be selected depending on the amount of silver in the photosensitive material to be processed and the composition of silver halide, but it is generally used at a lower concentration than other 7-minoboricarponates because of its high oxidizing power. For example,
It can be used in an amount of 0.01 mol or more per 1 fL of the liquid used, preferably 0.05 to 0.8 mol - Jk. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment. The bleaching solution and bleach-fixing solution of the present invention have a pH of 0.2 to 8.5.
can be used, preferably 4 to 8, more preferably 5.5
~Used in 8,5. The temperature of the treatment used is below 80°C, preferably below 55°C, most preferably below 45°C.
Use at temperatures below °C to prevent evaporation. The treatment time is preferably within 8 minutes, more preferably within 8 minutes. By setting the heating time to within 8 minutes, it is possible to significantly suppress the generation of stain due to uninvented organic acid ferric complex salt 1 salt. That is, failures can be minimized by increasing the opening area and shortening the processing time. Preventing this staining has been a difficult problem because conventional bleaching agents are not fast enough. In the present invention, the opening area of a processing tank having bleaching ability in automatic development used in continuous processing refers to the area of the opening of the processing tank, and generally corresponds to the air contact area of the processing solution. Conventionally, it has been recommended that the Ijl 1 mouth area (air contact area) be made small in order to improve the storage stability of the liquid and suppress evaporation. However, in the bleach-fix solution of the present invention, oxidation of sulfite by organic acid ferric complex salts such as aminopolycarboxylic acids is difficult to occur, and it has been found that storage stability does not deteriorate even if the opening area (air contact area) is not narrowed. did. Therefore, in the present invention, the open space (air contact area) in bleaching and reducing treatment is set to 8 crn' or more per liter of treatment liquid, more preferably 8 crn' or more, particularly preferably 9 cm'
More preferably, it is 10 crn' or more. The upper limit may be determined from the viewpoint of preventing evaporation. Furthermore, as a method of widening this opening area (air contact area), a (spherical) float made of plastic acid or other material capable of forming a thin film of the processing liquid is floated and stirred to form a thin film of the processing liquid with the float. A method in which air oxidation is promoted while at the same time or while entraining air is also a preferred method. Open surface with this invention! The oxidation of ferrous complex salts in near-natural conditions due to the expansion of li (air contact surface vL) progresses effectively while preventing contamination with other processing solutions due to staining and liquid scattering. This method is extremely effective when a day's processing is completed in a few hours, that is, when the processing time of an automatic processor is extremely short and the stop time is long (only temperature control is performed while the automatic processor is stopped). Specifically, it is effective when the actual processing operation rate of continuous processing of the automatic processor is less than 8 hours per day (24 hours). Particularly preferably within 4 hours. This has been achieved for the first time because the organic acid ferric complex salt of the present invention has high oxidizing power and can bleach-fix color negative films that are difficult to bleach in one bath. This treatment method is completely unimaginable with diiron complex salts. This is because these are bleach-fix solutions that have been used for color paper, and automatic processors for color paper have little stoppage time and long actual processing time, so the air fixing solution based on the opening area of the processing tank is less effective. This is because it was thought that Surprisingly, however, the organic acid ferric complex salt of the present invention is resistant to aeration by forced bubbling and oxidation by oxidizing agents such as persulfates, harsh hydrogen water, and bromates when a small amount of a color developing agent is present. However, it has been found that continuous treatment for a long period of time causes a problem of rapid increase in yellow stain. On the other hand, it has been found that when the surface area of the treatment tank is expanded and oxidation is performed slowly, the #1 complex salt is oxidized appropriately without staining. In this method, the oxidation rate of ferrous complex salts is somewhat weaker than in forced aeration, but there is no problem in practice.
However, the larger the opening area (air contact area) of the processing tank, the better. The bleaching solution of the present invention can contain various additives together with *organic acid ferric complex salt as a bleaching agent as described above. As additives, it is particularly desirable to contain alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. , pH1m agents such as oxalates, acetates, carbonates, phosphates, solubilizers such as triethanolamine,
Acetylacetone, phosphonocarboxylic acid, polyphosphoric acid,
Organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid,
Those known to be commonly added to bleaching solutions, such as 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. In addition to potassium bromide, the halogen compounds mentioned above include hydrochloric acid, hydrogen bromide, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. can also be used. The silver halide fixing agent to be included in the bleach fixing agent of the present invention, 27I&, is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, potassium thiosulfate, etc., which is used in ordinary fixing processing. Typical examples include thiokm salts such as ammonium thiocyanate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents are 5g/i or more, preferably 50g/i or more,
More preferably 70g/! It can be used in an amount that can dissolve more than L. The bleach-fixing solution of the present invention contains a pH buffering agent consisting of various salts such as boric acid, borax, sodium hydroxide, ammonium hydroxide, etc., alone or in combination, as in the case of the above-mentioned bleaching solution. A combination of two or more types can be contained. Furthermore, various optical brighteners, antifoaming agents, or antifoaming agents can be contained. In addition, preservatives such as hydroxyamine, hydrazine, sulfite salts, isomeric bisulfites, 9-adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, and oxycarboxylic acids. , organic chelating agents such as polycarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, and methanol. , dimethylformamide, dimethyl sulfoxide, and other organic solvents may 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. It may be fixed,
A prebath containing a bleach accelerator may also be used as a processing solution prior to bleaching or bleach-fixing. After bleaching and fixing (or bleach-fixing), stabilizing treatment may be performed without washing with water, or washing with water and subsequent stabilizing processing may be performed.In addition to 0 or more steps, hardening, neutralization, black and white development,
Typical examples of preferred processing methods include the following steps, in which known auxiliary steps such as inversion and washing with a small amount of water may be added as necessary. (1) Color development → bleach-fix → water washing (2) color development pass bleach fixing → small amount washing pass water washing (3) color development → bleach-fix → water washing → stable (4) color development → bleach-fix → stable (5) color development Development → Bleach-fix → 1st stability → 2nd stability (6)
Direct washing (or stable) after color development → 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 → stable (10) color development → bleaching → fixing → first stable → t52 stable (11) color development → bleaching Wash with a small amount of water → fix → wash with a small amount of water → wash with water → stabilize (12) Color development → wash with a small amount of water → bleach → wash with a small amount of water → fix →
Washing with a small amount of water → Washing with water → Stabilizing (13) Color development Stopping → Bleaching → Washing with a small amount of water → Fixing → Washing with a small amount of water → Washing with water → Stable (14) Black and white development → Washing with water (or stable) → Reversing → Color development → Bleaching → Fixing → Washing with water ( (or omitted) Pass stabilization (15) Pre-hardening → Neutralization → Black and white development → Stop Pass Color development → Bleaching → Fixing → Washing (or omitted) → Stabilization Among these processing steps, the effects of the present invention are more noticeable. (1), (2), (3), (4), (5
). The processing steps (6) and (7) having the bleach-fixing steps are more preferably used in the present invention. It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention, after these inorganic metal salts are formed into metal complex salts together with various chelating agents. Addition is also a preferred method. It is preferable to add a chelating agent and/or a ferric complex salt thereof other than the present invention to the bleach-fixing solution of the present invention.
)) It is preferable to use 0.45 mol % or less when the diiron complex salt is 1 mol %. The black-and-white developer used in the processing of the present invention is a so-called black-and-white first developer used in the processing of color photographic light-sensitive materials, or a black-and-white developer used in the processing of black-and-white photographic materials. It can contain various additives added to. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone;
Preservatives such as sulfite, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate, and inorganic or organic accelerators such as potassium bromide, 2-methylenebenzimidazole, and methylbenzthiazole. Examples include inhibitors, water softeners such as polyphosphates, and surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds. 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 amine phenol and p-phenylene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer 11, more preferably about 1 g to about 15 g per 11. Examples of aminophenol-based developers include o-amine phenol, p-7 minophenol, 5-7 minnow 2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like. A particularly useful aromatic primary amine color developer is X. It is an N-dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted.Among these, a particularly useful compound is N,N-diethyl-p- Phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(toethyl-dodecylamino)-toluene, N-ethyl-β-methane Sulfonamidoethyl-3-methyl-4-aminoaniline sulfate, toethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N,N-diethylaniline, 4
-amino-N-(2-methoxyethyl)-toethyl-3
-methylaniline-P-)/reninsulfonate and the like. The paraphenylenediamine color developing agent C 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 gold m-sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, l-hydroxy Water softeners and thickeners such as ethylene-1,1-diphosphonic acid may optionally be included. The pH of the color developer is 1, usually 7 or higher, and most commonly about 10 to about 13. 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 in which a color former is contained in the light-sensitive material (U.S. Pat. No. 2,378,879,
2,801,171), as well as an external development method in which a coloring agent is contained in the developer (see U.S. Pat. No. 2,252,
No. 718, No. 2,582,243, No. 2,590.1
For example, the cyan coloring agent is based on a naphthol or phenol structure, and indaniline is formed by coupling. Those that form pigments, magenta color formers include those having a skeletal structure of 5-vitezolone ring having an active methylene group, and yellow color formers include benzoylacedoanilide and bivallylacetanilide having active methylene chains. Those having an acylacedoanilide structure such as those 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. In addition, as protective colloids for these silver halides, natural products such as gelatin, as well as synthetic colloids can be used. Silver halide emulsions include
Conventional photographic additives such as stabilizers, hardeners, sensitizing dyes, surfactants, etc. may also be included. It is preferable that the silver halide color photographic light-sensitive material of the present invention has a colloidal silver dispersion layer.The colloidal silver dispersion layer may be a filter layer or an antihalation layer, and the colloidal silver dispersion layer may be further dispersed in an emulsion layer. The method for making these colloidal silver dispersions, which may be prepared by
No. 3-27740, No. 49-43201, No. 45-1
No. 4890, JP-A-51-89722 and British Patent 1
．． It is synthesized and coated by the general method described in No. 032,871 and the like. The bleaching solution and bleach-fixing solution according to the present invention include color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies,
It can be applied to silver halide color photographic light-sensitive materials such as color reversal films for TVs and color reversal papers.
The present invention is most suitable for processing high-sensitivity color photographic materials having a sensitivity of +g/dm" or more. [Examples] The present invention will be explained in detail below with reference to Examples, but the embodiments of the present invention are limited thereby. 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 colloidal silver emulsion layer are provided on the triacetate film base. A sensitive silver halide emulsion layer was coated so that the total i amount was 99 mg per 100 cm. , the blue-sensitive silver halide emulsion layer contains α-(4-nitrophenoxy)-α-pivalyl 5- as a yellow coupler.

[γ-(2,4-di-t-aminophenoxy)butyramide]-2-chloroacetanilide was used, and 1-(2,4,8-)lichlorophenyl was used as a magenta coupler in the green-sensitive silver halide emulsion layer. )-3-(
[α-(2,4-di-t-amylphenoxy)-7cetamido]benzamide)-3-pyrazolone and 1-(2
,4,8-)lichlorophenyl)-3-((α-(2,
4-di-t-amylphenoxy)-7cetamido]benzamide)-4-(4-methoxyphenylazo)-5-
Use pyrazolone as a cyan coupler in the red-sensitive silver halide emulsion layer! -Hydroxyate (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. Further, as the silver halide emulsion, a silver iodobromide emulsion containing silver iodide in the ratio shown in Table 1 was used. The silver halide color negative light-sensitive material thus obtained was used as a sample. After exposing this sample to light using a conventional method, the following treatment was performed. Processing process Processing temperature (“0”) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 Bleach fixing
37.8 1 minute to 30 minutes 3 washes 30
~34 2 min 4 stable 30~34
Drying for 1 minute and 5 minutes The following color developing solution, bleach-fixing solution, and stabilizing solution were used. [Color developer] Charcoal potassium 30g Sodium sulfite 2.0g and Droxyamine sulfate 2.0g Potassium bromide
1.2g sodium hydroxide
3.4g Toethyleneto β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.
8 g of water was added to make the solution 1000 ml, and the pH was adjusted to 10.1 with sodium hydroxide for 7 AI. [L white fixer] '# Machine acid-resistant iron complex salt 0.2 mol ammonium thiosulfate 130IIi ammonium sulfite (50% solution) Add 3ral water to make 1000sjL, ammonia water (28% solution)
The pi was adjusted to 7.0. [Stabilizing solution] Formalin (35% aqueous solution) 7. Ora!
;LC5Hti 0 (GHz C11z 0)
Add to H1, OmJl water to make 1QOhfL. The bleach-fix solution contained the compounds shown in Table 1 (see below) as ammonium salts of organic acid iron (III) complexes. In addition, nalo exemplified compound (I-7) was added until the surface tension reached 30 dyne/cm, and the desilvering completion time of each sample was compared. In Table 1 and Examples, organic acid iron (III) complex salts (1) to (12) are as follows. No. Iron (m) complex salt (1) Diethylenetriaminepentaacetic acid ferric complex salt (2
) Diethylenetriaminepentaphosphate ferric complex salt (3)
Cyclohexanediaminetetraacetic acid ferric complex salt (4)
Cyclohexanediamine 4-end is ferric complex salt (5) Triethylenetetraminehexaacetic acid ferric complex salt (6) Triethylenetetraminehexaphosphate ferric complex salt (7) Glycol ether diamine tetraacetic acid ff12 iron complex salt (8) Glycol ether diamine Ferric tetraphosphate complex salt (9) 1.
2-diaminopropanetetraacetic acid ferric complex salt (10) I
, 2-diaminopropane tetraphosphate ferric complex salt (11)
Methyliminodiphosphoric acid ferric complex salt (12) Methyliminodiphosphoric acid ferric complex salt As shown in Table 1 above,
) (EDTA-Fe (m)) In bleach-fix solutions containing complex salts, the time to complete desilvering increases as the content of silver iodide increases, and when an emulsion containing 1 mol% or more of silver iodide is used. In some cases, the silver was not completely desilvered for even 30 minutes. In comparison, it has been found that the 7-minoboricarboxylic acid iron complex salt of the present invention effectively exhibits its effects when the silver iodide content is 5 mol % or more. In addition, one of these a-acid ferric complex salts (2), (a), (8), (7), (8)
, (a) , Do) , When similar experiments were conducted in place of (12), almost the same effect as when the ferric complex salt (11) of the present invention was added was shown. Example 2 The same photosensitive material sample as used in Example 1 (however, 0
．． The same development process was carried out using a compound containing 5 mol% silver iodide, but the exemplified compound added to the bleach-fix solution (I-7
), the amount of nglO added was varied to adjust the surface tension values shown in Table 1 and Table 2. The results of bleaching completion time are shown in the same table. As shown in Table 2 above, by using the organic acid iron (m) complex salt of the present invention and reducing the surface tension to 55d7ne/cm or less, the bleaching completion time was significantly shortened. In addition, these organic acid fjS2 iron complex salts can be used in the second method of the present invention.
Iron complex salts (2), (4), (8), (7), (8), (9
), (10), and (12) were carried out in a similar experiment, and the results showed almost the same effect as when the ferric complex salt (II) of the present invention was added.

Claims (1)

Scope of Claims: (1) A silver halide color photographic material containing 0.5 mol% or more of silver iodide is developed after imagewise exposure, and processed with a processing solution having bleaching ability. In a method for processing photographic light-sensitive materials, the surface tension of the processing liquid is 55 dy.
ne/cm or less, and the treatment liquid is an organic acid ferric complex salt (A) selected from the following ferric complex salt group as a bleaching agent.
The difference in redox potential when the pH of at least one of the following reference solutions of organic acid ferric complex salts is between 5.0 and 9.0 is 1
1. A method for processing a silver halide color photographic light-sensitive material, comprising at least one organic acid ferric complex salt having a voltage of 00 mV or less. [Organic acid ferric complex salt (A)] (1) Diethylenetriaminepentaacetic acid ferric complex salt (2) Diethylenetriaminepentaphosphate ferric complex salt (3) Cyclohexanediaminetetraacetic acid ferric complex salt (4) Cyclohexanediaminetetraphosphate ferric complex salt Ferric complex salt (5) Ferric triethylenetetramine hexaacetic acid complex salt (6) Ferric triethylenetetramine hexaphosphate complex salt (7) Ferric glycol ether diamine tetraacetic acid complex salt (8) Ferric glycol ether diamine tetraphosphate Complex salt (9) 1,2-diaminopropanetetraacetic acid ferric complex salt (1
0) 1,2-diaminopropane tetraphosphate ferric complex salt (11
) Ferric methyliminodiacetic acid complex salt (12) Ferric methyliminodiaphosphate complex salt [Organic acid ferric complex salt standard solution for redox potential measurement] Ferric chloride 0.23M Organic acid 0.305M Ammonium thiosulfate 1.0M Ammonium sulfite The pH is adjusted using 0.1M ammonia water and acetic acid, and the redox potential is measured. (2) The treatment liquid with bleaching ability has the following general formula (I) (a
2. The method for processing a silver halide color photographic material according to claim 1, which comprises at least one compound represented by (i). General formula (I) (a) R-B-(AO)-_nQ (b) R-Q (c) R-B-A-Q (d) R-B-A-B_1-Q (e) R- Z (f) Z_1-A-Q_1 (g) Z_2-A-Q (h) Z-B-R (i) R-B-A-B_1-R_1 In the formula, R and R_1 have 1 to 30 carbon atoms. Substituted or unsubstituted alkyl group, alkylaryl group, aryl group, -C_nF_2_n_+_1, ▲ Numerical formula, chemical formula, table, etc. ▼ (R_3 is substituted or unsubstituted alkyl group, alkylaryl group, aryl with 1 to 30 carbon atoms ), -(CH_2)_m(CF_2)_nH, A represents a substituted or unsubstituted alkylene group, arylene group, or alkylarylene group having 1 to 6 carbon atoms, and B and B_1 represent -O- , ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, -NH-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Q represents -H, −
SO_3M, -COOM, -OSO_3M, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COOR_1 (R_1 and R_2 are synonymous with R_3 above), Q
_1 is -SO^■_3, -COO^■, -O-SO^■
＿3 stands for Z_1, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, and Z_2 represents ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z is synonymous with Z_1 or Z_2 above, and M
represents a monovalent cation, X represents a monovalent anion, and m and n represent integers of 1 to 30. (3) Claim 1, wherein the organic acid ferric complex salt is diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid ferric complex salt. Or the method for processing a silver halide color photographic light-sensitive material according to item 2. (4) The method for processing a silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the processing solution having bleaching ability is a bleach-fix solution. (5) A method for processing a silver halide color photographic light-sensitive material according to claim 4, characterized in that a one-bath bleach-fix treatment using a bleach-fix solution is carried out directly following the color development treatment.