JPS6026210B2 - 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 material (hereinafter referred to as a color photographic processing method) for developing, bleaching and fixing an exposed silver halide color photographic material, and in particular to a method for processing a silver halide color photographic material (hereinafter referred to as a color photographic processing method). The present invention relates to a color photographic processing method capable of shortening 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 (hereinafter referred to as a color photographic material) that has been exposed to light, after the color development step, it is bleached with a developed silvering agent (bleaching agent). Next, a step of derailing and fixing with a fixing agent is performed. 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 blood salt, ferric chloride, or ethylenecyaminetetraacetate iron complex; The bleach-fixing solution used in the process is generally an aqueous solution containing a bleaching agent and a fixing agent as main ingredients, and the bleaching agent may be, for example, the same red blood salt, ferric chloride, or ethylene as in the bleaching solution. Metallic salts of organic acids such as iron diaminetetraacetate are used, and thiosulfates such as sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate, and sodium thiocyanate are used as fixing agents to coexist with these bleaching agents. A fixing agent commonly used for fixing silver halide photographic materials, such as thiocyanate or thiourea, is used. Red blood salt and ferric chloride as bleaching agents are good bleaching agents in that they have a large oxidizing power. However, a bleach solution or a bleach-fix solution using red blood salt as a bleaching agent releases cyanide through photodecomposition and poses a pollution problem, so treatment must be taken to completely render the waste solution harmless. 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 used in the processing machines that are filled with them are susceptible to corrosion. It has the disadvantage that iron hydroxide is precipitated in the emulsion layer during the water washing process, resulting in so-called staining. For this reason, bleach must be subjected to a cleaning process using an organic chelating agent, which is not suitable for the purpose of rapid processing and labor saving, and also poses problems in terms of pollution control. Compared to red blood salt and ferric chloride, ethylenediamine Metal key salts of organic acids, such as iron tetraacetate, have little toxicity and are advantageous in terms of pollution control, so their use as bleaching agents has been recommended in recent years. However, organometallic salts have a comparatively high oxidizing power of 4 and insufficient bleaching power, and the use of this as a bleaching agent can, for example, bleach low-sensitivity color light-sensitive materials mainly made of silver chlorobromide emulsions. Although the desired purpose can be achieved by processing or bleach-fixing, high-sensitivity color light-sensitive materials that are mainly composed of silver chlorobromoiodide or silver iodobromide emulsions and are color sensitized, Particularly when processing a color light-sensitive material for reversal using a high-dose emulsion, the bleaching action is insufficient, desilvering is poor, and the bleaching or bleach-fixing efficiency is low, making it difficult to achieve the intended purpose. From the viewpoint of pollution prevention, it is desirable to use a metal rust salt of an organic acid such as ethylenediaminetetraacetic acid iron salt as a bleaching agent, but as mentioned above, this results in insufficient bleaching power. Unless this point is solved, the purpose of rapidly processing high-sensitivity color light-sensitive materials cannot be achieved. Conventionally, bleaching solutions or bleaching agents using metal salts of organic acids such as iron salts of ethylenediaminetetraacetic acid have been used. It has been proposed to add various bleach accelerators to the fixer solution as a means of increasing its bleaching ability. Examples of such bleaching accelerators include, for example, Japanese Patent Publication No. 45-85
Thiourea derivatives as described in JP-A No. 06, selenourea derivatives as described in JP-A-46-280, five-membered rings as described in British Patent No. 11x Paper No. 42. Caputo compound, Special Publication No. 46-556
Examples include aliphatic amines as described in Swiss Patent No. 336,257, thiourea derivatives, thiazole derivatives, thiadiazole derivatives as described in Swiss Patent No. 336,257. However, many of these bleaching accelerators do not necessarily have a satisfactory bleaching effect, and even if they have an excellent bleaching accelerating effect, they lack stability in the processing solution, so the harmful life of the processing solution is short. Also, it has the disadvantage of not being able to withstand long-term storage, or the bleaching accelerating effect cannot be obtained when it is included in the so-called pre-treatment solution used in the process before processing with bleach or bleach-fix solution. Many have. A first object of the present invention is to provide a color photographic processing method that has low plexus, meets the requirements of pollution control, and has an excellent bleaching speed. A second object of the present invention is to provide a color photographic processing method using a bleaching accelerator capable of increasing the bleaching rate in bleaching or bleach-fixing using an organic acid metal keyboard as a bleaching agent. . A third object of the present invention is to provide a color photograph using a bleaching accelerator that can increase the bleaching rate and provide a stable processing solution when incorporated into a bleaching solution or a bleach-fixing solution. The object of the present invention is to provide a processing method. A fourth object of the present invention is to use a bleach accelerator that can increase the bleaching rate even when included in a pretreatment solution used in a step before processing with a bleach solution or bleach-fix solution. The object of the present invention is to provide a color photographic processing method with the following advantages. A fifth object of the present invention is to use a bleach-fix accelerator that can increase the bleach-fix speed, shorten the processing time, and obtain color photographic images of good quality, especially in a color photographic processing method that includes a bleach-fix step. The object of the present invention is to provide a color photographic processing method with the following advantages. The above object of the present invention is to perform the bleaching step and the fixing step using separate processing solutions after developing the exposed color photosensitive material, or to perform the bleaching step and the fixing step in one processing solution. That is, it is carried out using a bleach-fix solution, and at that time,
In the treatment solution used in the step before the treatment step with the bleach or bleach-fix solution and/or their treatment solution, a heterocyclic double base body having at least one nitrogen atom and in the molecular structure. It has been found that this can be achieved by containing a compound having at least two mercabuto groups (hereinafter referred to as the compound of the present invention) and using a metal tin salt of an organic acid as a bleaching agent. The compound of the present invention is a dimer of a heterocyclic compound containing at least one nitrogen atom and has at least two mercabuto groups, and the heterocycle is preferably a 5- to 6-membered ring. These heterocycles may contain one or more nitrogen atoms or sulfur atoms. When linking heterocycles and dimerizing them, the two heterocycle monomers may be linked directly, or the monomers may be linked together based on one ALK--(S)-n, = 1 to 4), etc. They may be connected by . Here, ALK is an alkylene group having 1 to 10 carbon atoms, R
represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The compound of the present invention only needs to be a dimer of a heterocycle containing at least one nitrogen atom and having at least two mercabuto groups in its molecular structure, and the heterocycle may be any arbitrary compound. (particularly a group imparting water solubility). Further, in the present invention, the heterocycle includes a fused heterocycle. Preferred substituents include a hydroxy group, a carboxy group, an amino group, a benzenesulfonic acid group, and the like.
It has been known that compounds having a sulfur atom that has a high affinity with silver have a bleaching accelerating effect. In particular, compounds having a mercabuto group were said to have a high bleaching accelerating effect. However, compounds having a mercapto group have the disadvantage that they are easily oxidized and do not have a lasting bleaching accelerating effect, and that they react with silver ions in the treatment solution to form scale-soluble silver salts and produce precipitates. In particular, heterocyclic compounds having two or more mercabuto groups tend to form soluble salts with silver and precipitate in the treatment solution, making it difficult to exhibit a bleaching accelerating effect and, on the contrary, having the disadvantage of inhibiting filtration bleaching. The present inventors have conducted various experiments to improve this drawback, and were surprised to find that by using a dimer of a striped nitrogen-containing heterocyclic hekabuto compound, precipitation occurred in the treatment solution, and the addition amount could be reduced. We found that a surprisingly high bleaching accelerating effect can be obtained regardless of the degree of treatment, and furthermore, even when the treatment solution is stored for a long period of time, precipitation is unlikely to occur, and furthermore, the bleaching accelerating effect hardly deteriorates. Understood. Next, examples of specific compounds used in the present invention will be listed, but the compounds used in the present invention are not limited to these. Exemplary Compounds Compounds of the present invention are described, for example, in the Journal of the American Chemistry Society (JomM1 of
he American Chemical Society
) No. 69, p. 2674 (1947), Journal of Organic Chemistry (Joumalo)
Vol. 33, p. 1275 (1968), Journal of the Society of Chemical Industry: Transactions (J○umal ○f the SMiety ○f)
Chemical industry: Tramaccio
n) Volume 52, No. 272 (1933) and Chemistry of Functional Group The Chemistry of Thiol Group (meChemi
STBI ofFuMtionaIGroupes;Che
mistryof hicI Groups: Jho
hnWiley&SonsIM. 1974 Issue No. 16
(preparation Thiols) on pages 3-269
．． It can be easily synthesized according to the method described in ). In the present invention, a color photographic image is obtained by subjecting the exposed silver halide photographic material to photographic processing including the steps of developing, bleaching, and fastening. 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 drying do not necessarily have to be carried out consecutively, and other steps can also be carried out before and after each step. Such additional steps include, for example, hardening bath, neutralizing bath, stabilizing bath, and water washing (
(including rinsing), and bleaching and fixing steps may be added as necessary. The compound of the present invention is contained in a solution used in a step before the processing step using a bleach solution or a bleach-fix solution, the so-called processing 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 bleach or bleach-fix solution, but it does not necessarily have to be immediately before, and other processing solutions may be used between the pretreatment solution and the bleach or bleach-fix solution. May intervene. When performing a bleaching or bleach-fixing process immediately following the developing process,
Even if the compound of the present invention is contained only in the developer, the desired bleaching accelerating effect cannot be obtained. 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 depends on the type of processing solution, the type of photographic material to be processed,
Although it varies depending on the processing temperature, the time required for the intended processing, etc., it is about 0.01 to 150 per 1 part of the processing liquid.
Good results can be obtained in the evening range. 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 each individual case. When adding the compound of the present invention to the treatment solution,
Generally, it is added after being dissolved in water, an alkali, an organic acid, etc., but even if it is added after being dissolved in an organic solvent if necessary, the bleaching accelerating effect is not affected in any way. 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. It has the effect of causing the coloring part to develop color, and its structure is one in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as Hakama acid and citric acid. The most preferable organic acid used to form such a metal salt of an organic acid is, for example, the following general formula [
1] or

There is an aminopolycarboxylic acid represented by [0]. General formula [1] General formula

[0] [In each of the above general formulas, A,, A2, A3, A4, N and N are each substituted or unsubstituted hydrocarbon group, Z is a hydrocarbon group, oxygen atom, sulfur atom or >N-A7 (A7
represents a hydrocarbon group or lower aliphatic carboxylic acid). ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. The general formula [1] or

Representative examples of the aminopolycarboxylic acid represented by [0] or other aminopolycarboxylic acids include the following. Ethylenediaminetetraacetic acidDethylenediaminebentaacetic acidethylenediamine-N-(8-oxyethyl)-N,N
′, N-triacetic acid propylene diamine tetraacetic acid nitrilotriacetic acid cyclohexane diamine tetraacetic acid iminodiacetic acid dihydroxyethylglycine ethyl ether diamine tetraacetic acid glycol ether diamine tetraacetic acid ethylene diamine tetrapropionic acid phenylene diamine tetraacetic acid ethylene diamine tetraacetic acid disodium salt Ethylenediaminetriacetic acidtetraacetic acidtetra(trimethylnium)
Salt Ethylenediamine Tetraacetic Tetrasodium Salt Dethylenetriamine Pentasodium Bentaacetate Salt Ethylenediamine-N-(8-oxyethyl)-N,N',N
'-Triacetic acid sodium salt Propylenediaminetraacetic acid sodium salt Nitrilotriacetic acid sodium salt Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used in the present invention contains the above-mentioned metal tin salt of an organic acid as a bleaching agent, and Various additives may be included. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium nalides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. It is also known that pH buffering agents such as shelf salts, hakamate salts, carbonates, and hydrofluoric acid salts, aminopolycarboxylic acids or their salts, alkyl amines, and polyethylene oxides are added to ordinary bleaching solutions. It is possible to add as appropriate. In the present invention, when the bleaching step is carried out using a bleach-fix solution, the bleach-fix solution contains a metal fin salt of an organic acid (for example, iron rust salt) as a bleaching agent, as well as thiosulfate and thiocyanic acid. A liquid having a composition containing a silver halide fixing agent such as a salt or a thiourea is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a composition in which a large amount of a halogen compound such as potassium bromide is added. A bleach-fix solution consisting of
Furthermore, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide may also be used. In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide,
Ammonium iodide and the like can also be used. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-dropping salt, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, and bromides and iodes such as thioureas and thioethers. In addition, for the bleach-fix solution, shelf acid, shelf sand,
Sodium hydride, potassium hydroxide, sodium carbonate,
pH buffering agents consisting of various salts such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, polyvinylpyrrolidone, etc., various optical brighteners, antifoaming agents, or surfactants can also be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or stabilizers such as nitroalcohol nitrates, methanol, dimethylformamide, dimethyl sulfoxide, etc. It is possible to appropriately contain organic solvents such as the like. The black and white developer used in the development process of the present invention is commonly known as a black and white first developer used in the processing of color photographic materials. First, it may contain various well-known additives that are added to black and white developers. Typical additives include 1-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites,
Accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, hardened water such as polysonic acid salts. Examples include a softening agent, a surface overdevelopment inhibitor consisting of a certain amount of iodide or a mercapto compound, and the like. The primary aromatic amine 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 generally used in the form of salts, such as hydrochloride, sulfate or paratolfene sulfonate, since they are more stable than in the free state. In addition, these compounds generally have a concentration of about 0.1 to about 30 in color developer 1, more preferably,
The color developer is used at a concentration of about 1 to about 15 minutes. Examples of aminophenol-based developers include o-
These include aminophenol, P-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like. Particularly useful primary aromatic amino acids/
The 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 compound agents include N,N-jethyl-P-phenylenediamine hydrochloride, N-methyl-P-phenylenediamine hydrochloride, N,N-dimethyl-P-phenylenediamine hydrochloride, and N,N-dimethyl-P-phenylenediamine hydrochloride.
-phenylenediamine hydrochloride, 2-amino-5-(N-
Ethyl-N-dodecylamine/)-toluene, N-ethyl-N-8-methanesulfonamidoethyl-3-methyl-
4-aminoaniline sulfate, N-ethyl-N-8-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-
methoxyethyl) 1N-ethyl-3-methylaniline,
Examples include P-toluenesulfonate.
In addition to the above-mentioned primary aromatic amino color developer, the alkaline color developer used in the present invention further contains:
Various components normally added to color developing solutions, such as alkali metal sulfites such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides,
Benzyl alcohol, water softeners, thickeners, and the like can also be optionally included. The pH value of this color developer is usually 7 or higher, most commonly about 9.5 to about 13. C, which is treated according to the invention in the presence of a compound of the invention. Silver germide color photographic material is a known color photographic material,
Particularly advantageous use when processing multilayer negative-working color photographic materials or color print photographic materials, preferably containing couplers, or when processing color photographic materials prepared for reversal color processing. It is also possible to process color X-ray photographic materials and single-layer special color photographic materials. Alternatively, there is no problem in processing the coupler in the presence of the developer. The silver halide photographic material applicable to the present invention uses an internal development method (for example, U.S. Pat. No. 237,667, U.S. Pat. No. 2,8011
In addition to external development methods in which a color former is contained in the developer (for example, U.S. Pat. No. 22527, etc.)
18, 2592243, 2590970, etc.). Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta color formers have a 5-pyrazolone ring with an active methylene group as a backbone structure, and yellow color formers have has a penzoylacetanilide, pivalylacetanilide, or acylacetanilide structure with an active methylene chain, and also those with a substituent at the coupling position,
You can use any of them even if you don't have one. As described above, both so-called 2-equivalent couplers and 4-equivalent couplers can be used as color formers. As silver halide emulsions that can be used, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. It may be something. In particular, the effects of the present invention are fully exhibited in the case of silver iodobromide and chlorobromide. Furthermore, as protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. The halogenated emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants. When the compound of the present invention is incorporated into a premix of a bleach or bleach-fix solution, various compositions can be used as the premix. The simplest composition is an aqueous solution in which the compound of the present invention is simply dissolved; A water-repellent solution containing appropriate salts such as sodium chloride, sodium carbonate, and sodium bicarbonate can also be advantageously used as a precursor. Any prefix can be used, and any of them can effectively reduce the effect of the present invention, but if the pH is too high, stiso may occur, so in general, pH 12 is used. Preferably used below. In the pre-bath, if necessary, anti-settling agents made of various chelate compounds, hardeners made of various compounds including amethysts and aldehydes, pH buffers, halogen salts, etc. are fixed. Antioxidants such as sulfites, hydroxylamine and hydran, anti-swelling agents such as sodium sulfate and magnesium sulfate, surfactants and the like can be contained. For example, a washing process, a stopping process, a stopping fixing process, etc. can be interposed between the prefix and the bleach bath or bleach-fixing process.
Even in such cases, when the compound of the present invention is added to the premix, the same bleaching promoting effect can be obtained. However, when the compound of the present invention is contained only in the prebath, it is more desirable that the prebath be used in the step immediately before the bleaching or bleach-fixing step. If the compound of the present invention is contained in a bleach-fixing bath, and the treatment with these conditions is applied immediately following the color development process, it will not be possible to develop color development by special addition, like the bleach accelerator in the secondary bleaching process. The bleaching promotion effect does not decrease due to liquid contamination. Furthermore, even when the compound of the present invention is used relatively frequently, it does not inhibit fixation and no fogging is observed. Next, the present invention will be illustrated by examples, but the embodiments of the present invention are not limited thereto. Example 1 An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion are formed thereon. The layers were coated to give a total silver content of 90 parts per 100 parts. At this time, the sonic silver halide emulsion layer contains Q-(4nitrophenoxy)-pivalyl-5- as a yellow coupler.
[y-(2,4-di-t-amylphenoxy)butylamide]-2-chloroacetanilide was used as a magenta coupler in the green-sensitive silver halide emulsion layer.
,6-trichlorophenyl)-3-{[Q-(2,4-di-t-amylphenoxy)-acetamide]penzamide}-5-pyrazolone and 1-(2,4,6-trichlorophenyl)-3-{[Q- (2.4-di-t-amylphenoxy)acetamide]penzamide}-41(41methoxyphenylazo)-5-pyrazolone was used as a cyan coupler in the red-sensitive silver halide emulsion layer.
-Hydroxy-N-{Q-(2.4-t-amylphenoxy)butyl}-2-naphthamide was used, and sensitizing dyes, hardeners, and spreading agents were added to each emulsion layer at a uniform rate. . The silver halide color negative light-sensitive material thus obtained was used as a sample. Using a tungsten light source on this sample, the color temperature was set to 490 pK using a filter.
After exposure to a certain amount of light, the following processing was performed. Processing process Processing time Color development 3 minutes 15 seconds Bleach-fixing 1 minute to 2 minutes Washing 2 minutes Stable 1 minute Drying was adjusted according to the following recipe The processing temperature was 37.8 pm and each processing solution was used. [Color development] Sodium metasherate 25.0 Sodium sulfite 2.0 Hydroxylamine sulfate 2.0 Potassium bromide
0.5# sodium hydroxide
3.4 tN-ethyl-N-3-methoxyethyl-3-methyl-4-aminoaniline tosyl salt 6.0 t water was added and the pH was adjusted to 0.1 with sodium hydroxide. Stable liquid formalin (35% aqueous solution) 7.0
Bleach-fix solutions (1) to (2) below are comparative bleach-fix solutions, and (1) are bleach-fix solutions to which the compound of the present invention has been added. Next, the composition of the bleach-fix solution used will be described. Bleach-fixing solution Ethylenediaminetetraacetate diammonium salt 7.5% Ethylenediaminetetraacetate iron (m) ammonium complex salt
100.0 Sodium polysulfite
10.0Ammonium tathiosulfate
100.0 ta water
1 ammonium hydroxide, pH 6.2 Bleach-fix solution {BI ethylenediaminetetraacetic acid diammonium salt 7.5 ethylenediaminetetraacetic acid iron (m) ammonium mirror salt
100.0 ta sodium sulfite
10.0 Sodium tathiosulfate
90.0 Tathiourea
10.0 At Yusui 1
pH 6.2 bleach-fix solution with ammonium hydroxide ethylenediaminetetraacetic acid diammonium salt 7.5 ethylenediaminetetraacetic acid iron plate) ammonium rust salt
100.0 ta sodium sulfite
10.0Ammonium tathiosulfate 1
00.0 PH6.2 Bleach-fix solution with ammonium hydroxide 7.5 ethylenediaminetetraacetic acid iron plate) Ammonium tsuba salt
100.0 Sodium polysulfite
10.0Ammonium tathiosulfate
100.0 in evening water 1 evening in ammonium hydroxide PH6.2 Bleach-fix solution 'E} Ethylenediaminetetraacetic acid diammonium salt 7.59 Ethylenediaminetetraacetic acid iron dish) Ammonium complex salt
75.0 ta sodium sulfite
10.0Ammonium tathiosulfate
100.0 ta Exemplary compound (1)
1.0 ta water
1 So ammonium hydroxide PH6.2 bleach-fix solution {F
' Ethylenediaminetetraacetic acid diammonium salt 7.5 Ethylenediaminetetraacetic acid iron blood) Ammonium rust salt
100.0 ta sodium sulfite
10.0Ammonium tathiosulfate
100.0ta Exemplary compound [4'
1.8% with water 1〆Ammonium hydroxide to pH6.2 Bleach-fix solution) Ethylenediaminetetraacetic acid diammonium salt 7.5% Ethylenediaminetetraacetic acid iron (m) ammonium salt
100.0 ta sodium sulfite
10.0Ammonium tathiosulfate
100.0ta Exemplary compound '7'
1 with 0.6# water
PH6.2 with ammonium hydroxide Bleach-fix solution 5) Ethylenediaminetetraacetic acid diammonium salt 7.5% Ethylenediaminetetraacetic acid iron (m) ammonium complex salt
100.0 ta sodium sulfite
10.0Ammonium tathiosulfate
90.0 Ammonium bromide
150.0 ta Exemplary compound (11)
0. By syneresis PH6.2 with ammonium hydroxide Bleach-fix solution 0) Ethylenediaminetetraacetic acid diammonium salt 7.5% Ethylenediaminetetraacetic acid iron plate) Ammonium tsuba salt
100.0 ammonium tathiocyanate
90.0 Ammonium bromide
150.0 ta Exemplary compound (IQ
5.0% with water, pH 6.2 with ammonium hydroxide. The bleaching performance was compared. The results are shown in Table 1 below. The bleach-fix completion time is the time required until all of the bleached silver and unbleached silver in the exposed and unexposed areas are desilvered and removed from the processed film system. Table 1 As is clear from Table 1, thiourea is added as a bleaching accelerator to the same conventional formulation of a bleach-fixing solution containing a high concentration of ethylenediaminetetraacetic acid salt as a bleaching agent. and Bleach-fix column B', a bleach-fix solution containing a compound similar to the compound of the present invention as a bleach accelerator {
It can be seen that when q is used, the bleach-fixing completion time is long in all cases. It is clear that the bleach-fixing completion time becomes longer and the accelerating effect is affected by the storage stability compared to same-day processing when the processing solution is stored. As described above, high-sensitivity negative light-sensitive materials cannot be bleach-fixed in a sufficiently stable manner by treatments not based on the present invention using a bleach-fix solution or a dish. On the other hand, when bleach-fixing solutions containing the compounds of the present invention (none, zero) are used, desilvering is completed in a much shorter time even with a small amount of bleach accelerator added. . Furthermore, when the processing solution is stored for a long period of time, the bleach-fixing completion time is almost the same as that of same-day processing, showing a desirable value, which also shows that the storage stability is high. Furthermore, dye images obtained by processing using bleach-fix solutions {E} to (1) are comparable in photographic properties such as color density and linear retention on characteristic curves, and the storage stability of the dyes is also good. This was confirmed. As described above, the bleach-fixing solution [E] (1) containing the compound of the present invention has very excellent bleach-fixing performance. In addition, after performing color development in the above processing, when bleach-fixing was performed after washing with water, stopping processing, or stopping and stabilizing processing, results similar to those shown in Table 1 were obtained, and in such processing steps, It was confirmed that there was no substantial difference in bleaching effect. In addition, similar results were obtained when the pH of the bleaching solution (D) was changed to 5.0 and 7.5, confirming that there is virtually no effect of pH. Note that the lower the pH of the bleach-fix solution, the higher the oxidizing power that can be obtained; however, deterioration of the solution due to hypolysis may become a problem, so the pH value should be 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 by 490 K' using a filter, and then subjected to the following treatment. Developing for 3 minutes and 15 seconds, fog whitening for 1 minute to 6 minutes and 30 seconds, washing for 2 minutes, fixing for 8 minutes, washing for 4 minutes, and stabilizing for 1 minute, and then drying. Each process is 37.8oo± 0.200. In each treatment, the processing solution used in Example 1 was used for color development and stabilization, and the processing solution with the following formulation was used for bleaching and fixing. Bleach solution Ammonium Bromide 150.0 Takoda Tsuku Freeting Agent (BL-・)
175.0 Z Glacial Acetic Acid
10.5 and sodium nitrate
35.0 ta water
IZ ammonium hydroxide pH6.2 Bleach solution Tsukuda Ethylenediaminetetraacetic acid diammonium salt 20.0 Taethylenediaminetetraacetic acid iron (m) ammonium key salt
150.0 Ammonium bromide
150.09 Sodium nitrate
35.0 ta glacial acetic acid
10.0 In the evening water I
Z pH6.2 with ammonium hydroxide Bleach solution [C' Ethylenediaminetetraacetic acid diammonium salt 20.0 tethylenediaminetetraacetic acid iron dish) Ammonium rust salt
150.0 Ammonium bromide
150.0ta sodium nitrate
35.0 ta glacial acetic acid
10.0 PH6.2 bleaching solution with ammonium hydroxide ■ Ethylenediaminetetraacetic acid diammonium salt 20.0 Taethylenediaminetetraacetic acid iron (m) ammonium salt
95.0 Ammonium bromide
150.0ta sodium nitrate
35.0 ta glacial acetic acid
10.0 In evening water 1 So Ammonium hydroxide PH6.2 Bleach solution {E' Ethylenediaminetetraacetic acid diammonium salt 20.0 Taethylenediaminetetraacetic acid iron (m) ammonium rust salt
65.0 Ammonium bromide
150.0 ammonium nitrate
35.0 ta glacial acetic acid
10.0 evening Exemplary compound '1'
with 1.5 t water
PH6.2 with ammonium hydroxide Bleach solution 'F} Ethylenediaminetetraacetic acid diammonium salt 20.0 Taethylenediaminetetraacetic acid iron (m) ammonium key salt
65.0 Ammonium bromide
150.0 ammonium nitrate
35.0 Tanabacetic acid
10. M Exemplary Compound '4-
1.0% of water, 1 night of ammonium hydroxide to pH 6.2 bleaching solution) Ethylenediaminetetraacetic acid diammonium salt 20.0% of ethylenediaminetetraacetic acid iron plate) Ammonium chain salt
65.0 Ammonium bromide
150.0 polyglacial acetic acid
10.0 evening Exemplary compound (11)
with 0.75 ta water
1 night PH6.2 fixer with ammonium hydroxide Ammonium thiosulfate 120.0 T Sodium sulfite 20.0 #Water
IZ bleach solution (G)
For each treatment using each, the bleaching completion time of the film was measured in the same day treatment after preparation of the treatment solution and the treatment after one treatment solution was present, 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 bleach solution ■, which is mainly composed of ethylenediaminetetraacetate lead Km fin-groove salt whitening agent and contains ammonium bromide for halogenation, has the same secondary formulation as a bleaching agent. When using a bleaching solution containing a high concentration of ethylenediaminetetraacetate iron (m) rust salt [B-, a bleaching agent containing a compound similar to the compound of the present invention [q and I know it's long. Furthermore, it can be seen that in bleaching solutions C and D containing compounds similar to the compounds of the present invention, the bleaching completion time was longer due to storage of the treatment solution, and the bleaching promotion effect was deteriorated by storage. In contrast, a bleaching solution containing the compound of the present invention [
9 to 9), it can be seen that desilvering is completed in a much shorter time than in the conventional formulation, even with less oxidizing base agent. 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 bleaching completion time when the treatment solution was allowed to stand for a long period of time showed a desirable value with no significant difference from that on the same day, which also shows that the bleaching accelerating effect is highly stable. 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 dish 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. . In addition, the bleaching solution (p)
When the treatment was carried out by changing H to 4.5 and 7.5, results similar to those shown in Table 2 were obtained, and it was confirmed that there was virtually no effect of pH. Note that the lower the pH of the bleaching solution, the higher the oxidizing power, so it is desirable to use the bleaching solution within a pH value range of 2.0 to 7.5. The dye images obtained by processing using the bleach solution (G) according to the present invention are comparable in photographic performance such as color density and linear retention on the characteristic curve, and the storage stability of the dye is also good. confirmed. Example 3 An antihalation layer and a gelatin layer were provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a recording-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer were sequentially applied thereon in order of the total recording amount. It was applied at a rate of 60/9 per 100 enemies. At this time, the blue-sensitive silver halide emulsion layer contains 4-(Q-2-methoxybenzoyl-Q-
(Chloroacetamide)-(4...1-t-amylphenoxy)penzanilide was used, a 4-equivalent magenta coupler was used in the green-sensitive silver halide emulsion layer, and 1-phenyl-31n-amyl-5-pyrazolone was used in the green-sensitive silver halide emulsion layer. For the sensitive silver halide emulsion layer, 4-equivalent cyankabra and 5-(n-penzyl-N-n-valeryl amine/)-1 naphthol were used, and each emulsion layer contained the usual sensitizing dye, hardener, spreading agent, etc. The silver halide reversal color photosensitive film thus obtained was used as a sample.The sample was heated to a color temperature of 49 by using a filter using a tungsten light source.
After adjusting the temperature to 0 and K and exposing a certain amount of light, the following processing was performed. (Processing process) Duration before treatment 3 minutes Medium 1 minute 1st spot 6 minutes stop 2 minutes 1st washing 4 minutes color development 9 minutes before setting 2 minutes bleach fixing 1-20 minutes 2nd washing 3 minutes stabilization Drying for 1 minute Each treatment solution had the following formulation. [Anterior dura mater] 6-Nitrobenzimidazole nitrate 0.03 tate Sodium sulfite (anhydrous) 0.8 tatetrahydride. 12.3-dimethoxyfuran 5 Z Sodium sulfate (anhydrous) 136 Tuff formalin (35%
aqueous solution) 30 Z potassium bromide
3.0 ta water
Adjusted to 4.9 with Isosulfuric acid for 1 night and 1 night. [Neutralization] Hydroxylamine sulfate 20% Sodium bromide 18% Glacial acetic acid
10 desk sodium acetate
24 Sodium sulfate (anhydrous)
45 Sodium hydroxide
60 ta water
1. Adjust the pH to 5.0 with glacial acetic acid or sodium hydroxide. [First development] Cardrafos 2, Fenidone 0.25 t Sodium sulfite (anhydrous) 50.0 t Hydroquinone 60 t Sodium carbonate (1
water salt) 30.0 Potassium bromide
2.0 Sodium tathiocyanate
1.3 ta sodium hydroxide
6.0 [Potassium iodide (0.1% aqueous solution) 6.0
1〆 [Stop stop] Sodium acetate 10 tye acetic acid
36 [with water]
1〆[Color development site] Kardraphos 5.0 t Sodium phosphate 40.0 t Sodium hydroxide 5.0 t T ethylenediamine 2.0 T benzyl alcohol 5.8 t Butylaminoborane 0.1 t Citrazine acid
1.3 Takodatsu CD-3
11.3 Sodium sulfite
5.0 ta water
IZ [Fixer] Ammonium thiosulfate 120 t Sodium sulfite 2M water
1 [Stable] Formalin (35% aqueous solution) 7.0 [1 night with water [Bleach-fix solution] Ethylenediaminetetraacetic acid diammonium salt 10 nights Ethylenediaminetetraacetic acid iron dish salt 75 nights Sodium sulfite
10 ammonium tathiosulfate
90 ta water
1. Pre-treated with ammonium hydroxide 28% aqueous solution at pH 6.3 Kazetana sand (N foundation B407.1 Sail 20)
20 tanacid 40
IZpH in the evening water
8.2 Pretreatment liquid 'B' female acetic acid 3
0.0 Sodium hydroxide 2.
1 PH with 4 ta of water
4.1 Pre-treatment liquid) Shelf sand (N secretion B407.10 days 20)
20 tatyl acid
40 evening HSe NT {day 2 NTSeH 3 ta N---
-N N N pH with water overnight
8.2 Pre-treatment liquid dish shelf sand 40 evening acid 20 evening HS Ding S
, ``SH 5taN---N pH 1 with water
8.2 Pre-treatment liquid {E} Shelf sand 4
0 Tana acid 20 T Exemplary compound '1' 5 T with water■
ZpH
8.2 Pretreatment liquid [F] Glacial acetic acid
30'sodium hydroxide
2.4 ta exemplified compounds ■
1 kp with 2.0 ta water
H 4
．． 0 pretreatment solution) Sodium bicarbonate
25 ta sodium carbonate 12.
0 ta Exemplary Compound '71 5 ta water 1 night PH
9.7 Pretreatment solution 5) Sodium sulfite 60 t Glacial acetic acid 12.0 t Sodium acetate 10.0 t Sodium thiosulfate 120.0 t Sodium hydroxide 2.0 t Exemplary compound (11
) with 5 t water
1〆PH
4.6 Pretreatment liquid 〇 Exemplary compound (IQ
with 3 tsp water
1soPH
7.9 The pretreatment solution and bleach-fixing were carried out at 38oo, and other treatments were carried out at 29.5°C. The completion time of bleach-fixing of the film in each treatment was measured on the same day after preparation of the processing solution and after storage for one month, and the bleach-fixing performance of the film using the pre-treatment solution was compared. The results are shown in Table 3 below. The bleach-fixing completion time is the time required for all of the silver salt in the unexposed and exposed areas to be desilvered and removed from the system (so-called clearing time). As is clear from Table 3, when a pretreatment solution containing no compound of the present invention is used, bleach-fixing is incomplete with the commonly known bleach-fix solutions for color paper processing. On the other hand, when processing with a pretreatment solution containing the compound of the present invention, bleach-fixing can be completed in a surprisingly short time even with a weak oxidizing bleach-fix solution, and the processing solution remains clear even when stored for a long period of time.・The processing time is almost the same compared to same-day processing, indicating that the bleach-fixing promotion effect is very stable. Furthermore, the dye image obtained by bleach-fixing after treatment with a pretreatment solution containing the compound of the present invention has a lower color density than the dye image obtained by bleaching using a red blood salt bleaching solution. It was confirmed that there was no inferiority in photographic properties such as color balance, and the storage stability of the dye was also good. After the pre-treatment liquid treatment, bleach-fixing treatment was performed via water washing treatment, and the same results as shown in Table 3 were obtained in all cases. Example 4 Each of the following layers was sequentially coated on a support made of cellulose acetate film from the support side to prepare a sample. Layer 1: Antihalation layer Layer 2: Gelatin intermediate layer, Layer 3: 1 as a cyan coupler dissolved in tri-o-cresyl phosphate and dispersed in an aqueous gelatin solution.
-Hydroxy-N- {6-(2.4-t-aminophenoxy)butyl}-2
- Red-sensitive silver halide gelatin emulsion layer containing naphthamide at a ratio of 1.4 mm/day: Gelatin intermediate layer 5: 1 as a magenta coupler dissolved in dibutyl phthalate and dispersed in an aqueous gelatin solution. (2, 4,
6-Trichlorophenyl)-3-{[Q-(2,4-di-t-amylphenoxy)-acetamide]penzamide}-5 Nigirazolone and 1-(2,4,6-trichlorophenyl)-3 -{-Q-(2.4-di-t-amylphenoxy)acetamide]penzamide}-4-(4
-Methoxyphenylazo) -5-pyrazolone at a ratio of 1.8 m/m Green-sensitive halogenated synthetic fiber gelatin emulsion layer Layer 6: Gelatin intermediate layer 7: Filter layer containing yellow colloidal silver 8: Dibutyl phthalate Q-(4-nitrophenoxy)-Q-pivalyl-5-[y-(2,4-di-t-amylphenoxy)butylamide]-2-chloroacetanilide as a yellow coupler dissolved in a gelatin solution and dispersed in an aqueous gelatin solution. A sound-sensitive silver halide gelatin emulsion layer containing 2.4 μm / 2.4 μm/m of a sonic silver halide gelatin emulsion layer Layer 9: Gelatin protective layer This sample was exposed to a certain amount of light using a tungsten light source with the color temperature adjusted to 490 K using a filter. After that, the following treatment was performed. Processing process Processing time Color development 3 minutes pre-treatment 2 minutes bleaching 1 minute to 2 minutes Washing 2 minutes fixation 8 minutes stabilization 1 minute drying Each treatment takes 37 minutes. The same processing solution used in Example 2 was used for color development, fixing, and stabilization, and the same processing solution used in Example 3 was used for pretreatment, but the bleaching solution was prepared using the following formulation. I used something. Bleach solution formula Ammonium ethylenediaminetetraacetate 10 tA Ethylene diamine tetraacetate Iron plate fin salt 35.0 Ammonium bromide 50 t Water
1 So with ammonium hydroxide PH6.
3. Measure the bleaching completion time of the film in each treatment.
Shown in the table. The bleaching completion time refers to the bleaching treatment time required for the amount of residual silver to reach the atmosphere after completion of fixing, and the bleaching accelerating effect of pretreatment was compared. Table 4 As is clear from Table 4, when a pretreatment solution containing no compound of the present invention was used, the bleaching treatment was incomplete during the normal treatment time. On the other hand, when the pretreatment solution containing the compound of the present invention was used for treatment, it was found that even a bleaching solution with weak oxidizing power could be used for sufficient treatment in a short period of time. This allows the treatment solution to be diluted, which is advantageous in terms of pollution control and rapid processing. It was also confirmed that the dye images obtained by pretreatment containing the compound of the present invention, bleaching, and fixing had no problems in photographic properties such as color density and color balance, and the storage stability of the dyes was also good. .

Claims (1)

[Claims] 1. After developing the exposed silver halide color photographic light-sensitive material, in the step of processing it with a processing solution having bleaching ability containing a metal complex salt of an organic acid, the processing solution or the processing solution prior to this processing solution. A method for processing a silver halide color photographic light-sensitive material, which comprises adding a compound which is a dimer of a heterocyclic ring having at least one nitrogen atom and having at least two mercabuto groups in its molecular structure to the material. .