JPS606508B2 - Silver halide color photographic material processing method - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter referred to as a color photographic processing method) for developing, bleaching, and fixing a silver halide color photographic light-sensitive material that has been exposed to light. The present invention relates to a color photographic processing method capable of shortening the processing time and performing sufficient bleaching to form color photographic images of good quality. Generally, in order to obtain a color image by developing a silver halide color photographic material that has been exposed to light, after the color development step,
The developed silver image is bleached with an oxidizing agent (bleaching agent), and then desilvered and fixed with a fixing agent. In contrast to this type of method in which bleaching and fixing are performed in separate processing steps, a method called bleach-fixing is a method that simplifies the processing steps and completes bleaching and fixing simultaneously in one step for the purpose of speeding up processing and saving labor. A processing method has been proposed. The bleaching solution used in the bleaching process contains a bleaching agent such as a metal rust salt of an organic acid such as red dish salt, ferric chloride or iron salt of ethylenediaminetetraacetate. The bleach-fixing solution used in the bleach-fixing process is generally an aqueous solution containing a bleaching agent and a fixing agent as main ingredients, and the bleaching agent may include, for example, the same red blood salt, ferric chloride, or Metal complex salts of organic acids such as ethylenediaminetetraacetic iron chain salts are used, and as fixing agents that coexist with these bleaches, sodium thiosulfate,
Fixing agents commonly used in fixing silver halide photographic light-sensitive materials, such as thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate and sodium thiocyanate, or thiourea, are used. Red blood salt and ferric chloride as bleaching agents are good bleaching agents in that they have high oxidizing power. However, bleaching solutions or bleach-fixing solutions that use red blood salt as a bleaching agent release cyanide through photodecomposition, which poses a pollution problem, so measures must be taken to completely render the wastewater harmless. No. In addition, bleaching agents using ferric chloride have a very low pH and extremely high oxidizing power, so they have the disadvantage that the materials in the processing machine that is filled with them are easily corroded, and they also It has the disadvantage that iron hydroxide is precipitated in the emulsion layer during the processing step, resulting in so-called staining. For this reason, a cleaning process using an organic chelating agent must be performed after bleaching, resulting in faster processing.
It is not suitable for the purpose of labor saving, and also has problems in terms of pollution control. Compared to red dish salt and ferric chloride, metal complex salts of organic acids such as ethylenediaminetetraacetate iron complex salts are less toxic and are advantageous in terms of pollution control, so their use as bleaching agents has been recommended in recent years. However, organometallic complex salts have a relatively low oxidizing power and insufficient bleaching power, and those using them as bleaching agents can be used to produce low-sensitivity silver halide color photographic light-sensitive materials based on silver chlorobromide emulsions. In the case of bleaching treatment or bleach-fixing treatment, the desired purpose can be achieved to a certain extent, but silver halide, which is mainly composed of silver chlorobromoiodide or silver iodobromide emulsion and which is color sensitized and highly sensitive, can be used. When processing color photographic materials, especially silver halide color reversal photographic materials that use emulsions with a high silver content, the bleaching action is insufficient and desilvering is poor, and the bleaching or bleach-fixing efficiency is low and the purpose cannot be achieved. Have difficulty. From the viewpoint of pollution prevention, it is desirable to use a metal complex salt of an organic acid such as iron salt of ethylenediaminetetraacetate as a bleaching agent, but as mentioned above, this results in insufficient bleaching power. Unless these points are resolved, the objective of rapidly processing high-sensitivity color photographic materials cannot be achieved. Conventionally, it has been proposed to add various bleach accelerators to a bleaching solution or a bleach-fixing solution using a metal complex salt of an organic acid such as ethylenediaminetetraacetic acid iron anchor salt as a bleaching agent as a means of increasing the bleaching ability of the solution. As such a bleaching accelerator, for example, Japanese Patent Publication No. 45-8
Thiourea derivatives such as those described in Japanese Patent No. 506, selenourea derivatives such as those described in JP-A-46-28 and five-membered ring capto as described in British Patent No. 1138842. Compound, Special Publication 1976-5
Examples include aliphatic amines as described in Japanese Patent No. 56, thiourea derivatives, thiazole derivatives, thiadiazole derivatives as described in Swiss Patent No. 336,257. However, many of these bleach accelerators do not necessarily have a satisfactory bleach accelerating effect;
In addition, although the bleaching promotion effect is excellent, the stability in the processing solution is
Many of them have the disadvantage that the effective life of the processing solution is short due to the lack of heat and that they cannot withstand long-term storage. A first object of the present invention is to provide a color photographic processing method that has low toxicity, meets the requirements of pollution prevention, and has excellent bleaching speed. A second object of the present invention is to provide a bleaching accelerator that can increase the bleaching rate by incorporating the bleaching accelerator into a prebath of bleaching or bleach-fixing using a metal anchor salt of an organic acid as a bleaching agent. It is. The third object of the present invention is that when it is contained in a bleach solution or a bleach-fix solution, it does not undergo decomposition due to oxidation, and since silver ions are hardly dissolved, side reactions do not occur and it lasts for a long period of time. To provide a bleaching accelerator that can obtain a highly stable processing solution that can withstand the use of water, has low consumption and replenishment during processing, and is advantageous in terms of cost and pollution. The fourth object of the present invention is to accelerate bleaching without containing bleach accelerators that have an adverse effect on silver recovery in processing solutions that require silver recovery, such as bleach-fix solutions. It is an object of the present invention to provide a bleach accelerator that can recover silver ions without any problem. The fifth object of the present invention is to provide a bleach accelerator that can maximize its bleach accelerating effect by selecting an arbitrary pH that satisfies the solubility, stability, bleach accelerating effect, etc. of the bleach accelerator. A sixth object of the present invention is to increase the bleach-fixing speed in color photographic processing that involves a bleach-fixing step, shorten the processing time, and to enable sufficient bleach-fixing processing even when the material concentration of the bleach and bleach-fix solutions is lowered. It is an object of the present invention to provide a bleach-fixing accelerator which is capable of obtaining color photographic images of good image quality. As a result of various studies on bleaching acceleration methods that do not have the above-mentioned drawbacks, the inventors of the present invention have determined that after the exposed silver halide color photographic light-sensitive material is developed, the bleaching step and the fixing step are carried out using separate processing solutions. or, when the bleaching step and the fixing step are performed using one processing solution, that is, a bleach-fixing solution, the bleaching solution uses an organic acid metal key salt as an oxidizing agent;
In the bleach-fixing solution and/or the processing solution preceding the bleaching solution or bleach-fixing solution, the following general formula [1],

This is achieved by containing at least one compound represented by [0] and [m] (hereinafter referred to as the compound of the present invention) and subjecting it to bleaching or bleach-fixing. General formula [1] General formula

[0] General formula [m] The general formula [1],

In [0] and [m], R,
, R2, R3 and R4 are each a hydrogen atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms (e.g. methyl, ethyl, n-propyl, i-propyl, n-butyl, i-
Butyl "sec-butyl, t-butyl, n-amyl, i
-amyl, t-amyl, etc.) or R5, R6, R7, R8, R9 and R,o are each a hydrogen atom, a hydroxy group, a carbonyl group, an alkyl group having 1 to 5 carbon atoms (for example, the above-mentioned each group) or R, . and R
, 2 are each a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms (for example, each group mentioned above), X, and For example, each group mentioned above), Y is an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl,
n-propyl, i-propyl, etc.) "Number of carbon atoms 1
~3 alkoxy groups (e.g. methoxy, ethoxy, n-
each group such as propoxy, i-propoxy), sulfo group, amino group, nitro group, a and b are each an integer of 1 to 5, c, d, e, f, g and j are each an integer of 0 to 5, and h and i each represent 1 or 2. However, d and f do not take 0 at the same time.The compound of the present invention is a carboxyl group having at least one mercapto group and at least one carboxy group in the carbon chain nucleus or carbon ring nucleus. It is an acid thiol type compound, and it has been found that the compound of the present invention is effective for the purpose of the present invention.Next, typical specific examples of the compound of the present invention will be listed. is not limited to these. Exemplary compounds
)ku7> (8) Ku9) Ku1〇><11) (12) (13> (14) (15) (16) Ku17> (18) (19> (20) (21) (22) (23) (24) 25) (26) <27) (28) (29) (30) (31) The compounds of the present invention are described, for example, in the Journal of Organism. Chemistry (Journal of0r Hinanic C
hemistry) Volume 35, Page 3647 (i970), Acta Chemica Scandinavia (ActaCh
em; ca Scandinavica) Volume 5, No. 690
(1951), Vol. 14, p. 1980 (i962)
King) and The Q Chemistry e of Functional. Group "The Chemistry. Of. The Thiol$ Group" (The Chemistry of fhada c
tional groups “The Chemistry”
yofthethiolgroup” No. 165-265
Page (John Wjley & Sons. Inc. 19
It can be easily synthesized according to the method described in (published in 1974). In the present invention, the exposed silver halide photographic material is subjected to photographic processing including the steps of developing, bleaching and fixing to obtain a color photographic image. Bleaching and fixing may be carried out in independent steps, or both may be carried out in one step using a bleach-fix solution. Development usually means color development, but also includes a combination of black and white development and color development, such as in reversal color processing. These steps of development, bleaching and fixing do not necessarily have to be carried out consecutively, and other steps can be carried out before and after each step. Such additional processes include ``for example, dural vulgar, stop case, ``neutral vulgar'', stable vulgar, and water washing (
(including rinsing), and further bleaching and fixing steps can be added as necessary. The compound of the present invention can be contained in a bleach solution or a bleach-fix solution, or in a solution used in a step before the treatment step with a bleach solution or a bleach-fix solution, a so-called pre-treatment solution. In this case, the pretreatment liquid refers to a treatment liquid after a developing step, and before a bleaching solution or a bleach-fixing solution. The pretreatment solution is usually used immediately before the bleaching or bleach-fix solution treatment step, but it does not necessarily have to be immediately before, and another processing solution may be used between the pretreatment solution and the bleach or bleach-fix solution. You may. When a bleaching or bleach-fixing step is performed immediately following the developing step, the desired bleaching accelerating effect cannot be obtained even if the compound of the present invention is contained only in the developer. The compound of the present invention may be contained only in the bleach solution or bleach-fix solution or a pretreatment solution thereof, or may be contained in both the bleach solution or bleach-fix solution and the pretreatment solution. That is, a desirable bleaching accelerating effect can be obtained in any of these addition modes. The amount of the compound of the present invention to be added to these solutions varies depending on the type of processing solution, the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc. About 0.01~ per liquid
Good results are obtained in the range of 25 females. However, in general, when the amount added is small, the effect of promoting bleaching is small, and when the amount added is larger than necessary, precipitation may occur and contaminate the photographic materials being processed. It is preferable to determine the optimal range as appropriate depending on the case. When adding the compound of the present invention to a treatment liquid, it is generally dissolved in water, an alkaline aqueous solution, etc. beforehand, but if necessary, it may be dissolved and added using an organic solvent. However, it has no effect on its bleaching promotion effect. The metal salt of an organic acid as a bleaching agent used in the bleaching solution or bleach-fixing solution used in the bleaching process of the present invention oxidizes the metallic silver produced during development and converts it into silver halide, while at the same time leaving the color former free. Since it has the effect of causing the coloring part to develop color, its structure is that metal ions such as iron, cobalt, copper, etc. are substituted with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferable organic acid used to form such a metal complex salt of an organic acid is, for example, the following general formula [
There are aminopolycarboxylic acids represented by [W] or [V]. General formula [W] HOCO-A, -Z-A2-COO General formula [V] [In each of the above general formulas, A,, A2, A3, A4, A5 and F are each substituted or unsubstituted hydrocarbon group, Z represents a hydrocarbon group, an oxygen atom, a sulfur atom, or (A? is a hydrocarbon group or a lower aliphatic carboxylic acid). ) These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula [W] or [V] include the following. Ethylenediaminetetraacetic acidDethylenediaminebentaacetic acidethylenediamine-N-(B-oxyethyl)-N,N
',N'-Triacetic acid propylenediaminetetraacetic acidnitrilotriacetic acidcyclohexanediaminetetraacetic acid iminodiacetic aciddihydroxyethylglycine ethyl etherdiaminetetraacetic acidgeIJ coleetherdiaminetetraacetic acidethylenediaminetetrapropionic acidphenylenediaminetetraacetic acidethylenediaminetetraacetic acid Disodium salt Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Dethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(8-oxyethyl)-N,N',N'
- Sodium triacetate Propylene diamine sodium tetraacetate Sodium nitrilotriacetate Sodium cyclohexane diamine tetraacetate The bleaching solution used in the present invention contains the metal rust salt of an organic acid as described above as a bleaching agent, and also contains various Additives may be included. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, ammonium bromide, and the like. It is also known that pH buffering agents such as shelf salts, oxalates, acetates, carbonates, and phosphates, polyaminocarboxylic acids or their salts, alkylamines, and polyethylene oxides can be added to ordinary bleaching solutions. Those listed above can be added as appropriate. In the case where the bleaching step is carried out using a bleach-fix solution in the present invention, the bleach-fix solution contains a metal complex salt of an organic acid as described above as a bleaching agent, and also contains a thiosulfate, a halogen such as thiocyanic acid, thioureas, etc. A bleach-fixing solution containing a silver halide fixing agent is applied.Alternatively, a bleach-fixing solution containing a bleaching agent and a small amount of a halogen compound such as potassium bromide in addition to the silver halide fixing agent, or vice versa, is used. A bleach-fix solution containing a large amount of a halogen compound such as potassium bromide, or a special bleach-fix solution containing a combination of bleach and a large amount of a halogen compound such as potassium bromide may also be used. In addition to potassium bromide, the above-mentioned halogen compounds include hydrogen chloride, hydrogen bromide, lithium bromide, ammonium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with silver halide to form water-soluble anchor salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in conventional fixing processes. Thiosulfates such as ammonium sulfate (potassium thiocyanate, sodium thiocyanate,
Typical examples include thiocyanate salts such as ammonium thiocyanate, and thiourea tothioether. In addition, the bleach-fix solution contains shelf acid, shelf sand,
Sodium hydroxide, potassium hydroxide, sodium carbonate
Potassium carbonate, sodium bicarbonate, potassium bicarbonate may contain pH buffering agents consisting of various salts such as acetic acid, sodium acetate, ammonium hydroxide, etc. alone or in combination of two or more. It can also contain a photobrightener, antifoaming agent, or surfactant.Also, it can contain a guarantee agent such as hydroxylamine, hydrazine, or a bisulfite adduct of an aldehyde compound, an organic chelating agent such as aminopolycarboxylic acid, or a nitrocontaining agent. A type of stabilizer such as alcohol nitrate, an organic solvent such as methanol, dimethyl sulfoamide, dimethyl sulfoxide, etc. can be appropriately contained.The black and white developer used in the development process of the present invention is generally known. It is called a black-and-white first developer, which is used in the processing of color photographic light-sensitive materials, or it is used in the processing of black-and-white photographic materials, and it contains various well-known additives that are generally added to black-and-white developers. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, securing agents such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. , potassium bromide, inorganic or organic inhibitors such as 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and surface supernatants consisting of iodine and mercapto compounds. Examples include development inhibitors, etc. The primary aromatic amino color developer used in the color developer in the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenolic and p-phenylenediamine derivatives.These compounds are more stable than their free states and are therefore generally used in the form of salts, such as hydrochlorides or sulfates. The compound is
Generally, the concentration is from about 0.1 g to about 30 g per night of color developer, more preferably about 1 g per night of color developer.
Use at a concentration of ~15g. Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxy-toluene, and 2-oxy-3-amino-
Includes 104-dimethyl-benzene, etc. A particularly useful primary aromatic amino color developer is an N,N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful examples include N,N-jethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, and 2-amino- 5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-8-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-3-hydroxyethylaminoaniline, 4-amino-3 -Methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, and the like. The alkaline color developer used in the present invention contains, in addition to the first aromatic amino color developer, various components normally added to color developers, such as sodium hydroxide, sodium carbonate, and sodium carbonate. It may optionally contain an alkaline agent such as potassium, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, and the like. The pH value of the developer solution is usually 7 or higher, most commonly about 10 to about 13. Silver halide color photographic materials processed according to the present invention in the presence of the compounds of the present invention include: When processing a known color photographic material, preferably a coupler-containing multilayer negative color photographic material or a color print photographic material, or a color photographic material made for reversal color processing. In addition, color X-ray photographic materials and single-layer special color photographic materials can also be processed.Alternatively, the coupler may be present in the developer and processed without any problem. No problem. The silver halide photographic light-sensitive materials applicable to the present invention are those using an internal development method in which a coupler is contained in the light-sensitive material (for example, U.S. Pat. No. 2,376,67, No. 2;
801?171), as well as external development methods in which a coupler is contained in the developer (for example, U.S. Pat. No. 2,252,718 and U.S. Pat. No. 2,592,243).
2,590,97, etc.). Moreover, any couplers generally known in the art can be used. For example, cyan couplers are based on naphthol or phenol structures and form indoaniline dyes upon coupling, magenta couplers have a 5-pyrazolone ring with an active methylene group as their backbone structure, and yellow couplers are active. Any type of penzoylacetanilide, bivalylacetanilide, or acylacetanilide structure having a methylene chain, with or without a substituent at the coupling position, can be used. Thus, as the coupler, both so-called 2-equivalent couplers and 4-equivalent couplers can be applied. Silver halide emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. It may be. Furthermore, as protective colloids for these silver halides, natural products such as gelatin, as well as various products obtained by synthesis can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardening agents, sensitizing dyes, and surfactants. When the compound of the present invention is contained in a pretreatment solution for a bleach or bleach-fix solution, various compositions can be used as the pretreatment solution. The pretreatment liquid with the simplest composition is an aqueous solution in which the compound of the present invention is simply dissolved, but it may also contain acids such as acetic acid or shelf acid, alkalis such as sodium hydroxide, sodium sulfite,
An aqueous solution appropriately containing salts such as sodium acetate, sodium thiosulfate, and sodium chlorate (sodium carbonate, sodium bicarbonate, etc.) can also be advantageously used as the pretreatment liquid. Any pH value can be used for the pretreatment liquid. Both of these can effectively exhibit the effects of the present invention, but staining may occur if the pH is too high, so it is generally preferable to use the solution at a pH of 9 or less. In addition, if necessary, we may also use anti-settling agents made of various chelate compounds, hardening agents made of various compounds including alum and aldehyde compounds, pH buffering agents, fixing agents for halogen salts, and sulfite ``hydroxylamine.'' Antioxidants such as hydrazine, anti-swelling agents such as sodium sulfate and magnesium sulfate, surfactants, etc. may be contained between the pre-treatment liquid and the bleaching liquid or bleach-fixing liquid. In such cases, when the compound of the present invention is added to the pretreatment solution, the same bleaching acceleration effect can be obtained.However, the compound of the present invention When the compound of the present invention is contained only in the pretreatment solution, it is more desirable that the pretreatment solution be used in the step immediately before the bleaching solution or bleach-fixing solution. If these processing solutions are added to the fixing processing solution and processing with these processing solutions is performed immediately following the color development process, the bleaching accelerating effect may not be achieved due to the contamination of the color developing solution as with conventional bleaching accelerators. Further, even when the compound of the present invention is used in a relatively large amount, it does not cause fixation inhibition and no fogging is observed. 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 and a green-sensitive silver halide emulsion layer are formed thereon. A filter layer containing yellow colloidal silver and a sound-sensitive silver halide emulsion layer were coated so that the total amount of silver was 90 parts per 100 cm of fin.At this time, a yellow coupler was added to the sound-sensitive silver halide emulsion layer. Q-(4nitrophenoxy)-Q-pivalyl-5-
[y-(2,4-di-t-amylphenoxy)butyramide]-2-chloroacetanilide was used, and 1-(2,4
,6-trichlorophenyl)-3-{Q-(2,4-di-t-amylphenoxy)-acetamido]penzamide}-5-pyrazolone and 1-(2,4,6-trichlorophenyl)-3-{ [Q-(2,4-di-t-amylphenoxy)acetamide]penzamide}-4-(
1-4-methoxyphenylazo)-5-pyrazolone was used as a cyan coupler in the red-sensitive silver halide emulsion layer.
Using hydroxy-N-{Q-(2,4-t-amylphenoxy)butyl}-2-naphthamide, a sensitizing dye, a hardening agent and a spreading agent were added to each emulsion layer at the same rate. The silver halide color negative light-sensitive material thus obtained was used as a sample.This sample was exposed to a certain amount of light using a tungsten light source with the color temperature adjusted to 490 pK using a filter, and then subjected to the following processing. Processing process Processing time Color development
3 minutes 19 seconds bleach fixing
Wash with water for 1 to 20 minutes Stable for 2 minutes
The 1 minute drying temperature is 37. The treatment was carried out using a floating ○, and a treatment solution prepared according to the following formulation was used. [Color development] Sodium metashelate 25.0g Sodium sulfite 2.0g Hydroxylamine sulfate 2. 0g potassium bromide 05g sodium hydroxide 3. Linked N-ethyl-N-8-methoxyethyl-3-methyl-4-aminoaniline-tosyl salt 6. Add 0g water and adjust to pHIO with sodium hydroxide. Adjust to 1 [stable] Formalin (35% aqueous solution) 7. Add 1 g of water to the bleach-fix solution.Use a processing solution with the following formulation.Among these, bleach-fix solutions (A) to (Q) are bleach-fix solutions for comparative processing that are not based on the present invention. Fixer (E) or (L)
) is a bleach-fix solution containing the compound of the present invention. Next, the composition of each bleach-fix solution used is shown. Bleach-fix solution (A) Ethylenediaminetetraacetic acid diammonium salt
7.5g ethylenediaminetetraacetate iron(m) complex salt 100.0g sodium sulfite 10.0g ammonium thiosulfate 100. 0g with water 1.pH6.2 with ammonium hydroxide Bleach-fix solution (B) Ethylenediaminetetraacetic acid diammonium salt
7.5g ethylenediaminetetraacetate iron (m) rust salt 100.0g sodium sulfite 10. Sodium thiosulfate 90. female thiourea
10. 1. With thigh water 1. PH6.2 with ammonium hydroxide Bleach-fix solution (C) Ethylenediaminetetraacetic acid diammonium salt
7.5g Ethylenediaminetetraacetate iron (m) complex salt 100.0g Sodium sulfite 10.0g Ammonium thiosulfate 100.0gHS-
C Koichi COO day 5. Female ammonium hydroxide pH 6.2 bleach-fix solution (D) Ethylenediaminetetraacetic acid diammonium salt
7.5g Ethylenediaminetetraacetate iron (m) complex salt 100.0g Sodium sulfite 10. Female ammonium thiosulfate 100. Female HS-CH2CH2CQ-SH 5.
PH with 0g water and ammonium hydroxide
6.2 Bleach-fix solution (E) Ethylenediaminetetraacetic acid ammonium salt
7.5g ethylenediaminetetraacetate iron (m) rust salt 100.0g sodium sulfite 10. Female ammonium thiosulfate 100.0g Exemplary compound (12) 5. Memizase
1. pH6.2 with ammonium hydroxide Bleach-fix solution (F) Ethylenediaminetetraacetic acid diammonium salt
7.5g Ethylenediaminetetraacetic acid iron (blood) salt 100.0g Sodium sulfite 10. Female ammonium thiosulfate 100.0g Exemplary compound (
13) 8. cough water
1 night with ammonium hydroxide to pH 6.2 Bleach-fix solution (G) Ethylenediaminetetraacetic acid diammonium salt
7.5g ethylenediaminetetraacetate iron (m) rust salt 100. Sodium sulfite 10.0g Ammonium thiosulfate 100. Female Exemplary Compound (15) 10. With female water
1. pH6.2 with ammonium hydroxide Bleach-fix solution (H) Ethylenediaminetetraacetic acid diammonium salt
7.5g Ethylenediaminetetraacetate iron (m) Tsuba salt 100.0g Sodium sulfite 10.0g Ammonium thiosulfate 90.0g Ammonium bromide 150. Cough Exemplary Compound (2)
0) 5. female water 1
PH6.2 with ammonium hydroxide Bleach-fix solution (1) Ethylenediaminetetraacetic acid diammonium salt
7.5g ethylenediaminetetraacetate iron (m) rust salt 100.0g ammonium thiocyanate 90. Female ammonium bromide 150. Female exemplified compound (
21) 5. With female water
pH6.2 with ammonium hydroxide In each process, the bleach-fixing completion time (clearing time) of the film processed with each bleach-fix solution (A) to (1) and the time when the film was subjected to short-time (2 minutes) bleach-fixing treatment The bleach-fixing performance measured by neutral density was compared. The results are shown in Table 1 below. The bleach-fixing completion time is the time required for all bleached silver and unbleached silver in the exposed and unexposed areas to be desilvered and removed from the processing film system, and the neutral density is the time required for all of the bleached silver and unbleached silver in the exposed and unexposed areas to be removed from the processing film system. and unbleached silver combined white light density. Table 1 As is clear from Table 1, the bleach-fix solution (A), which is a conventionally known bleach-fix solution containing a high concentration of ethylenediaminetetraacetate iron (m) key salt as a bleaching agent, and the same conventional formulation containing thiourea Bleach-fixing solution (B) containing as a bleaching accelerator "Bleach-fixing solution (C) and (D) containing a compound similar to the compound of the present invention as a bleaching accelerator are used. In addition, it can be seen that the neutral concentration is large for a short period of time in all of these cases, indicating that the so-called bleach-fixing is incomplete. High-sensitivity negative light-sensitive materials cannot be sufficiently bleach-fixed by treatments not based on the invention.On the other hand, when bleach-fix solutions (E) to (1) containing the compounds of the invention are used, It can be seen that desilvering is completed in a much shorter time.Furthermore, the neutral concentration during short processing is a low and desirable value, indicating that the desilvering property is very good.Furthermore, the bleach-fix solution (E It was confirmed that the dye images obtained by processing using (1) to (1) had no problems in photographic properties such as color density and linearity on the characteristic curve, and the dyes had good storage stability. As shown, the bleach-fixing solutions (E) to (1) containing the compounds of the present invention have very excellent bleach-fixing performance.After color development in the above treatment, water washing treatment or stop-fixing treatment is performed. When bleach-fixing was performed, results similar to those shown in Table 1 were obtained, confirming that there is no substantial difference in bleaching effect even in such a treatment process. (E) to (1) each at a pH of 5
．． When the treatment was performed using two different types, 0 and 7.5, the same results were obtained, and it was confirmed that there was virtually no effect of pH. Incidentally, the lower the pH of the bleach-fix solution, the higher the oxidizing power can be obtained, but since deterioration of the solution due to hypolysis becomes a problem, it is preferable to use the bleach-fix solution at a pH value in the range of 4.0 to 7.5. Example 2 The same sample used in Example 1 was exposed to a certain amount of light using a tungsten light source with the color temperature adjusted to 4900K using a filter, and then subjected to the following treatment. The processing includes color development for 3 minutes and 15 seconds, bleaching for 1 minute to 6 minutes and 30 seconds, fixing for 8 minutes, washing with water for 4 minutes, and stabilization for 1 minute, followed by drying. Each treatment was 37.8oo±0. Do it with 0. In each treatment, the processing solution used in Example 1 was used for color development and stability.
For bleaching and fixing, a processing solution with the following formulation was used. Bleach solution (
A)** Ammonium bromide 150.0g Kodak Bleeding Agent (BL-)
175.0' glacial acetic acid
10.5 Sodium nitrate
35. female water 1
Ammonium hydroxide has a pH of 6. 2 ** Eastman Kodak Company's Kodak Process C-
41 Prescription bleaching solution for large-scale preparation (B) Ethylenediaminetetraacetic acid diammonium salt
20.0g Ethylenediaminetetraacetic acid iron (m) complex salt i50.0g Ammonium bromide 150.0g Sodium nitrate 35.0g Glacial acetic acid
with 10.0g water
PH6.2 with ammonium monohydroxide Bleach solution (C) Ethylenediaminetetraacetic acid diammonium salt
20.0g Ethylenediaminetetraacetate iron (m) complex salt 95.0g Ammonium bromide 150. Female sodium nitrate 35.0g glacial acetic acid
10. Female HS-CH2-C
OO day 5.0g ammonium hydroxide pH6.2 bleaching solution (D) Ethylenediaminetetraacetic acid diammonium salt
20.0g Ethylenediaminetetraacetic acid iron (m) rust salt 95.0g Ammonium bromide 150.0g Sodium nitrate 35.0g Glacial acetic acid
10.0gHS-CQ
C day 2C payment-SH 5.0g with water
6.2 Bleach solution (E) Ethylenediaminetetraacetic acid diammonium salt
20.0g Ethylenediaminetetraacetic acid iron (m) complex salt 65.0g Ammonium bromide 150.0g Ammonium nitrate 35.0g Glacial acetic acid
10.0g Exemplary Compound (12) 5. With female water
1 night with ammonium hydroxide to pH 6.2 Bleach solution (F) Ethylenediaminetetraacetic acid diammonium salt
20.0g Ethylenediaminetetraacetic acid iron (machi) Suzu salt 65.0g Ammonium bromide 150.0g Ammonium nitrate 35.0g Glacial acetic acid
10.0g Exemplary Compound (20) 5.0g with water
1. pH6.2 with ammonium hydroxide Bleach solution (G) Ethylenediaminetetraacetic acid diammonium salt
20.0g Ethylenediaminetetraacetate iron (m) Tsuba salt 65.0g Ammonium bromide 150. thigh glacial acetic acid
10.0g Exemplary Compound (21) 5.0g with water
pH 6.2 with ammonium hydroxide fixer ammonium thiosulfate 120. Sodium sulfite 20.0g with water
1) For each treatment using each of the bleaching solutions (A) to (G), the bleaching completion time of the film and the neutral density when bleaching for a short time (1 minute) were measured and the bleaching performance was compared. The results are shown in Table 2 below. In Table 2, the bleaching completion time is the bleaching time required for all the silver in the exposed and unexposed areas to be removed from the film system by the next fixing process, and the neutral density is the bleaching time required for all the silver in exposed and unexposed areas to be removed from the film system. and the combined white light optical density of unbleached silver. As is clear from Table 2, the conventionally known bleaching solution (A) is mainly composed of ethylenediaminetetraacetate iron (blood) anchor salt bleaching agent and contains ammonium bromide for halogenation;
A bleaching solution (B) containing a high concentration of iron (m) complex salt of ethylenediaminetetraacetate as a bleaching agent with a similar conventional formulation, and a bleaching solution (C) containing a compound similar to the compound of the present invention.
) and (D), the bleaching completion time is long. All of these had high neutral concentrations during short-time treatment, indicating that the so-called bleaching treatment was incomplete. On the other hand, when bleaching solutions (E) to (G) containing the compounds of the present invention are used, desilvering can be achieved in a much shorter time than in conventional formulations, even though the main oxidizing agent is small. You can see that it is completed. This means that it is possible to provide a material that is advantageous in terms of reducing processing costs and preventing pollution caused by discharge of bleaching solution.
Furthermore, the neutral concentration during short-time treatment is low and shows a desirable value, indicating high bleaching performance. It has also been confirmed that commercially available reversal color films can be similarly bleached successfully by using a bleaching solution containing the compound of the present invention. As described above, by using the compound of the present invention, it is possible to eliminate the need for the red blood salt bleaching solution conventionally used in processing reversal color films, and to provide a processing composition that is extremely advantageous in terms of pollution control. .Also,
The pH of bleaching solutions (E) to (G) was set to 4.5 and 7, respectively.
．． When the treatment was carried out by changing to the two types of No. 5, results similar to those shown in Table 2 were obtained, and it was confirmed that the fence had virtually no effect. The lower the pH of the bleaching solution, the higher the oxidizing power, but it is desirable to use the bleaching solution within a pH range of 2.0 to 7.5. The dye images obtained by processing using the bleaching solutions (E) to (G) according to the present invention are compared with the dye images obtained by the control processing of Example 1 in terms of color density and linearity on the characteristic curve. It was confirmed that there was no inferiority in performance and that the storage stability of the dye was good.Example 3 An antihalation layer and a gelatin layer were provided on a triacetate film base, and on top of this, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a green layer were formed in order. The sensitive silver halide emulsion layer and the sound-sensitive silver halide emulsion layer were coated so that the total amount of silver was 60 strips per 100 cm.At this time, the sound-sensitive silver halide emulsion layer was coated with a 2-equivalent yellow coupler. (B-2-methoxybenzoyl-Q-chloroacetamide)-3''-(4'''-1t-amylphenoxy)penzanilide was used, and the green-sensitive silver halide emulsion layer contained a 4-equivalent magenta coupler and 1-phenyl-
3-n-amyl-5-pyrazolone was used, a 4-equivalent cyan coupler was used in the red-sensitive silver halide emulsion layer, and 5-(n-benzyl-N-n-valerylamino)-1-naphthol was used in each emulsion layer. Conventional additives such as sensitive dyes, hardeners and spreading agents were added. The thus obtained silver halide reversal color sensitive material was used as a sample. This sample was exposed to a certain amount of light using a tungsten light source with the color temperature adjusted to 490 pK using a filter, and then subjected to the following treatments. (Processing process) Pre-processing time Hardening 3 minutes Medium Sum 1 minute 1st phenomenon 6 minutes Stop 2 minutes X water wash 4 minutes color development 9 minutes before bath 2 minutes bleach-fix 1-2 minutes 2nd wash
Stable for 3 minutes, dried for 1 minute Each treatment solution had the following formulation. [Anterior dura] 6-Nitrobenzimidazole nitrate 0.03g Sodium sulfite (anhydrous) 0.8g Tetrahydro-2,3-dimethoxyfuran 5M Sodium sulfate (anhydrous) 136g formalin (35% aqueous solution) 3-monopotassium bromide
1 with 3.0g water
Part 1: PH4 with carp sulfuric acid. Adjust to 9. [Neutralization] Hydroxylamine sulfate 20g Sodium bromide 18g Glacial acetic acid
Sodium acetate
2 Warm Sodium Sulfate (Anhydrous)
45g sodium hydroxide 6.
Adjust the pH to 54QI with 0g water and glacial acetic acid or sodium hydroxide. [First development] Kardraphos
2g phenidone
0.25g sodium sulfite (anhydrous)
50.0g hydroquinone
6.0g Sodium carbonate (monohydrate)
30.0g potassium bromide
2.0g Sodium thiocyanate 1.
3g Sodium hydroxide 6.0% Potassium iodide (0.1% aqueous solution) 6.0% Water
1. [Stop] Sodium acetate 1. Glacial acetic acid
36 Crying Water 1
[Color development] Kardraphos 5.
0g Tertiary Sodium Phosphate 40.0g
Sodium hydroxide 5.0g Ethylenediamine 2.0g Penzyl alcohol 5.8-t-butylamine borane 0.1g Citrazic acid 1. Tour Kodak CD-13
11.3g sodium sulfite
5. 1 so [cheap with female water]
[1g] Formalin (35% aqueous solution) 7.0
1 with water [Bleach fixation] Ethylenediaminetetraacetic acid diammonium salt
log ethylenediaminetetraacetic acid iron (machi) complex salt 75g sodium sulfite 1og ammonium thiosulfate 90g water
1. pH 6.3 with ammonium hydroxide aqueous solution (A) shelf sand (Na2B407110 days 20
2 Meyanagi acid 40
g 1〆PH with water
8.2 Formerly known (B) Glacial acetic acid
30.0g sodium hydroxide 2. Add water to pH 1 to 4
．． 1 Zenzoku (C) Shelf sand (Na2 ear 07/10 20)
20g shelf acid
40gHS-CH2-COO day
IO. 0g water 1soPH
8.2 Pre-bath (D)
Shelf sand 2 female shelves acid
40gHS-CH2CH2C
Q-SH 5g with water
1〆PH
8.2 Former proverb (E) shelf acid
40g shelf sand 20g
Exemplary compound (12) with 5g water
1soPH
8.2 Formerly known (F) Glacial acetic acid
30 [sodium hydroxide
2. Trout Exemplary Compound (13)
1 pH with 1 female water
4.0 Pre-bath (G) Sodium bicarbonate 2 Sodium carbonate
12.0g Exemplary compound (15)
1 PH at separation
9.7 Sodium sulfite (H) 6.0
g glacial acetic acid 12.0'
Sodium acetate 10. Female sodium thiosulfate 120.0g Sodium hydroxide 2. Female exemplified compound (20
) 1 evening PH at Shimizu
4.6
Exemplary compound (1) Exemplary compound (21) 1 pH in water
7.9 Processing was carried out at 38oo for prefixing and bleach-fixing, and at 29.60 for other treatments. The time taken to complete the bleach-fixing of the film in each treatment was measured, and the neutral density of the film after 3 minutes of bleach-fixing treatment was measured to compare the bleach-fixing performance of the films using pre-treatment. The results are shown in Table 3 below. The bleach-fixing completion time is the time required for all the silver salt in the unexposed and exposed areas to be desilvered and removed from the system (so-called clearing time), and the neutral density is the sum of the dye and residual silver. . This is the optical density due to white light. As is clear from Table 3, when a preform containing no compound of the present invention is used, bleach-fixing is incomplete with the commonly known bleach-fixing solutions for cuff paper processing. On the other hand, when processing with a precursor containing the compound of the present invention, bleach-fixing was completed in a surprisingly short time even with a bleach-fixing solution with weak oxidizing power, and the neutral concentration was also compared with the sample treated separately as a standard. The lack of color indicates that bleach-fixing is carried out without any problems. In addition, the dye images obtained by bleach-fixing with pre-wetting treatment containing the compound of the present invention have a higher color density and density than dye images obtained by standard processing using a red blood salt bleaching solution. It was confirmed that there was no inferiority in photographic properties such as linear retention on the characteristic curve, and the storage stability of the dye was also good. In addition, the same results as shown in Table 3 were obtained in all cases in which bleach-fixing treatment was performed via water washing treatment after the generous treatment.

Claims (1)

[Scope of Claims] 1. After developing the exposed silver halide color photographic light-sensitive material, an organic compound containing at least one of the compounds represented by the following general formulas [I], [II] and [III] is processed. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises carrying out photographic processing using a processing solution having bleaching ability containing a metal complex salt of an acid or a processing solution preceding the processing solution. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 , R_2, R_3 and R_4 are each a hydrogen atom, hydroxy group, alkyl group having 1 to 5 carbon atoms, or ▲ Numerical formula, chemical formula, table, etc. ▼ , R_5, R_6, R_7, R_8, R_9 and R_1_0 are each a hydrogen atom , hydroxy group, carboxy group, number of carbon atoms 1-
5 alkyl group or ▲ Numerical formula, chemical formula, table, etc. ▼, R_1_1 and R_1_2 are each a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms, and X_1 and X_2 are each a hydrogen atom, a carboxy group, or a carbon atom Number 1~
5 alkyl group, Y is an alkyl group having 1 to 3 carbon atoms,
an alkoxy group, a sulfo group, an amino group, a nitro group or a hydroxy group having 1 to 3 carbon atoms; a and b are each an integer of 1 to 5; c, d, e, f, g and j are each an integer of 0 to 5; integer and h and i are each 1 or 2
represents. However, d and f never take 0 at the same time. ]