JPS6147961A - Treatment of silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To process quickly a silver halide color photosensitive material by bleaching the developed silver of the photosensitive material with a bleaching agent contg. an org. acid ferric complex salt and iodine-contg. substd. org. compd. after exposing and developing process. CONSTITUTION:The bleaching agent contg. the org. acid ferric complex salt, for example, diethylene triamine pentaacetic acid ferric complex salt, diethylene triamine pentaphosphoric acid ferric complex salt, etc. having bleaching power and the iodine-contg. substd. org. compd., for example, the compd. expressed by formula I - formula V is prepd. The core-shell type photosensitive material (the core of silver iodide and the shell of silver chloride, silver bromide, etc.) is processed by such bleaching agent. The bleaching agent has the high bleaching power of the developed silver and therefore the quick bleaching of the core-shell type silver halide photosensitive material which is hardly bleached and has high sensitivity is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials. Y! For more information, please contact us quickly! The present invention relates to a method for processing silver halide color photographic materials that can be bleached.

C. Prior Art] In general, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material, after the color development step, there is a step of treating the produced metallic silver with a processing solution having bleaching ability. is provided.

Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, a step of fixing the silver halide with a fixing agent is usually added next to the bleaching step, but with a bleach-fixing solution, bleaching and fixing are performed in one step.

Inorganic oxidizing agents such as red blood salts and e7A salts are widely used as oxidizing agents for bleaching image silver in processing solutions with bleaching ability for processing silver halide color photographic light-sensitive materials. There is.

However, some serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents that have bleaching ability. However, there is a risk that it will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body.

It has unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers (fixing agents) such as thiosulfates in the same processing solution, and these agents are not used in bleach-fixing baths. It is almost impossible to use oxidizing agents, which makes it difficult to achieve the goal of speeding up and simplifying the process. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment.

On the other hand, metal complex salts of organic acids such as aminopolycarboxylic acid metal complex salts have been used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling recycling of waste liquid. Treatment liquids have come into use. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so they have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow. 0 For example, iron(III) complex salt of ethylenediaminetetraacetate, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleach solution and a bleach-fix solution in some places, but silver bromide , high-sensitivity silver halide color photographic materials based on silver iodobromide emulsions, especially photographic color papers containing silver iodide as silver halide, color negative films for 10 shadows, and bleaching blades for color reversal films. is insufficient, and even after long-term processing, traces of image silver remain, resulting in poor desilvering properties. This tendency is particularly noticeable in a bleach-fix solution in which an oxidizing agent, thiosulfate, and fE salt coexist because the redox potential decreases.

In this way, considering the requirements for pollution prevention, iron ethylenediaminetetraacetate (m) is the best bleaching agent! It is desirable to use a complex metal salt such as a salt, but as mentioned above, this results in insufficient desilvering power.If this point is not solved, high-sensitivity color photographic materials cannot be rapidly processed. unable to achieve the goal.

Conventionally, it has been proposed to add various bleaching accelerators to a bleaching solution or a bleach-fixing solution using a gold H complex salt of an organic acid such as ethylenediaminetetraacetic iron (m) complex as a bleaching agent as a means of increasing the bleaching edge of the solution. ing. Examples of such bleaching accelerators include thiourea derivatives as described in Japanese Patent Publication No. 45-8056, aliphatic amines as described in Japanese Patent Publication No. 46-556, and as described in Japanese Patent Publication No. 46-280. Selenourea visiting conductor, British patent 1,138,8
The S5-membered ring mercapto compound described in No. 42,
Alternatively, there are thiourea derivatives, thiazole derivatives, and thiadiazole derivatives as described in Swiss Patent No. 336,257.

However, many of these bleach accelerators do not always have a satisfactory bleaching accelerating effect, and even if they have an excellent bleaching accelerating effect, they lack stability in the processing solution, which can shorten the working life of the processing solution. Those that have the disadvantage of being short and cannot withstand long-term storage, or those that are used in the process before processing with a bleaching solution or bleach-fixing solution, and when they are included in the 911 pre-bath φ, the bleaching promotion effect cannot be obtained. Many of them have the following drawbacks.

Furthermore, it is proposed in German Patent No. 213,940 that onium compounds can be used as bleaching accelerators. However, although these onium compounds have a bleaching accelerating effect, the effect is still not sufficient, and especially when metal ta salts of organic acids are used as bleaching agents, bleaching accelerating effects are rarely observed. Ta.

On the other hand, the present inventors previously discovered iron ethylenediaminetetraacetate (I
II) In addition to complex salts, diethylenetriaminepentaacetic acid iron (m) complex salt was found as a bleaching agent with relatively high oxidizing power among the 7 minoboricarpon ugly iron (■) complex salts. This iron (m)
Complex salts are characterized by rapid silver bleaching reactions when the pH is high, especially at pH 4 or higher. However, even with this diethylenetriaminepentaacetic acid iron(m) complex, the bleaching speed is insufficient as a bleaching agent for ultra-high sensitivity silver halide color photographic light-sensitive materials, and the required speed cannot be sufficiently achieved. The present inventor added the iodine-substituted organic compound and/or iodide salt of the present invention to a processing solution containing ethylenediaminetetraacetic acid iron (m) complex salt and having bleaching ability, and developed it. We discovered that the bleaching of silver was significantly accelerated and proposed this technology earlier, but as color photographic materials entered the era of ultra-high sensitivity, new λ silver halide emulsions were used. It has been found that the bleaching technique described above results in an insufficient bleaching speed.

[Problems to be Solved by the Invention] A technical object of the present invention is to provide a processing method by which ultra-high sensitivity color negative photographic materials, ultra-high sensitivity reversal color photographic materials, etc. can also be rapidly bleached.

~ [Structure of the Invention] As a result of extensive research, the present inventor developed a silver halide color photographic light-sensitive material after imagewise exposure, and processed it with a processing solution having bleaching ability / Silver halide color photograph In the method for processing a photosensitive material, the processing solution having bleaching ability is at least one organic acid FF12 iron complex salt (A) selected from the following ferric complex salt group as a bleaching agent, or the following criteria for an organic acid ferric complex salt. Organic acid ferric complex salt (B
) and at least one iodine-containing substituted organic compound and/or iodide salt in which at least one iodine atom has been substituted, or a treatment having a bleaching ability or a treatment having a DITI whitening ability. It has been found that the above technical problem (objective) can be solved by using a processing liquid prior to the processing liquid.

[Organic acid ferric acid 25 J1! (A)] (1) diethylenetriaminepentaacetic acid ferric complex salt (2) diethylenetriaminepentaphosphate ferric ta salt (3) cyclohexanediaminetetraphosphate ferric'M salt (0cyclohexanediaminetetraphosphate ttS2 iron complex salt (5 ) Triethylenetetramine hexaacetic acid ferric complex salt (8) Triethylenetetramine hexaphosphate ferric complex salt (7) Glycol ether diamine tetraacetic acid ferric complex salt (8) Glycol ether diamine tetraphosphorus butyferric complex salt (9) 1.2-diaminopropanetetraacetic acid ferric complex salt (
10) 1,2-diaminopropane tetraphosphate ferric complex salt (1
1) Methyliminodiacetic acid P, ferric complex salt (12) Methyliminodiaphosphate ferric complex salt [Reference solution of organic acid ferric complex salt of organic acid such as aminopolycarboxylic acid for redox potential measurement Co-ferric chloride 0.23M aminopolymer Organic acid such as carboxylic acid 0.305) 1,000 osulfate ammonium sulfate 1.0M ammonium sulfite 0.1M Adjust the pH using aqueous ammonia and acetic acid, and measure the redox potential.

Further, in a preferred embodiment of the present invention, the processing solution having bleaching ability is a bleach-fixing solution, and the surface tension of the processing solution having bleaching ability is 55 dyne/cm or less. The inventor has discovered that the object of the invention can be achieved more effectively.

The present invention will be explained in detail below.

In the present invention, when processing with a treatment liquid containing U-Yamauba,
This means processing with a U white solution or a -bath bleach-fix solution, but the effect of the present invention is better achieved when a -bath bleach-fix treatment is performed. The following explanation will mainly be made regarding this one-bath bleach-fixing process.

The bleach-fix solution of the present invention contains an organic acid ferric complex salt (A) or (B) as a bleaching agent.

As the organic acid fiS2 iron complex salt (A), one type can be arbitrarily selected from the above 12 types, and two or more types can also be used in combination as necessary.

Among the above 12 kinds of compounds of the organic acid ferric complex salt (A), the following are particularly preferable.

(I) Diethylenetriaminepentaacetic acid ferric complex salt (II
) Cyclohexanediaminetetraacetic acid ferric complex salt (■) Triethylenetetramine hexaacetic acid ferric complex salt Organic acid ferric complex salt (B) is a complex salt of multiple organic #f regulated by redox potential
It belongs to the group of III2 iron complex salts, and one type can be arbitrarily selected from these and used, and two or more types can also be used in combination if necessary.

In the present invention, the oxidation-reduction potential of a reference solution of a ferric complex salt of an organic acid such as an aminopolycarboxylic acid is measured using a platinum electrode using an ordinary pH meter at 25°C, and the reference electrode is a calomel solution. This was measured using an electrode.

Regarding the relationship between pH and potential of organic acid ferric complex salts such as aminopolycarboxylic acids, data for f:fS2 iron complex salts alone are known. However, it is not at all true that the favorable effect of the present invention is exerted only on organic acids such as aminopolycarboxylic acids, which have a small difference in redox potential over a wide pH range when measured with the bleach-fixing reference solution of the present invention. This was an unknown and highly prized discovery.

Specific examples of organic acid complex salts such as aminopolycarboxylic acids having a redox potential within the scope of the present invention include, but are not limited to, the following.

(1) Diethylenetriaminepentaacetic acid #ferric complex salt (2) diethylenetriaminepentaphosphate i2iron complex salt (3) cyclohexanediaminetetraacetic acid ferric complex salt (4) cyclohexanediaminetetraphosphate ferric complex salt (5) triethylenetetraminehexaacetic acid t52 iron complex salt (B) triethylenetetramine hexaphosphate ferric complex salt water The ferric complex salt of an organic acid according to the invention includes a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, Or ammonium salt,
Alternatively, water-soluble amine salts such as triethanolamine salts are used, and potassium salts, sodium salts, and ammonium salts are preferably used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. Its use J) can be chosen arbitrarily,
The selection must be made depending on the amount of silver and/\\silver halide composition of the photosensitive material to be processed, but generally the oxidizing power is 1. It can also be used in a lower concentration than other 7-minobolycarboxylic acids 341. For example, it can be used in a concentration of 0.01 mol or more per working solution 11, preferably 0.05 to 0.6 mol.

Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

The bleaching solution and bleach-fixing solution of the present invention have a pH of 0.2 to 8.
5, preferably 4 to 8', more preferably 5
．． 5 to 8.5. The treatment temperature is used at 80° C. or lower, preferably 55° C. or lower, most preferably 45° C. or lower to suppress evaporation.

The treatment time is preferably 8 minutes or less, more preferably 6 minutes or less. By setting the heating time to within 8 minutes, the generation of stain due to the organic acid ferric complex salt of the present invention can be significantly suppressed. In other words, failures can be minimized by shortening the processing time. It is difficult to prevent this stain because conventional bleaches are not quick enough.
Met.

Iodine-containing substituted organic compounds and/or iodide salts (sodium iodide, potassium iodide, ammonium iodide, etc.) that can be contained in the treatment solution having bleaching ability of the present invention or the treatment solution (prebath) preceding it. Specifically, the following may be mentioned, but the present invention is not limited thereto.

Margin below [Exemplary compounds] (a) (b) I H2 (p) 02H.

0H20H-OH20H It has been known that the iodine-containing substituted organic compound and/or iodide salt used in the present invention has an excellent bleaching accelerating effect in combination with conventional bleaching agents, but core-shell emulsions, In particular, high-sensitivity color photographic materials consisting of monodisperse core-shell emulsions having silver iodobromide in the core do not have sufficient accelerating effects; It has been found that a significant promoting effect can only be obtained in combination with a bleaching agent that has bleaching ability.

Regarding the core-shell emulsion used in the present invention, JP-A No. 57
As described in detail in No. 154232, a preferred color photographic light-sensitive material has a silver halide composition of 0 silver iodobromide.
．． It is a silver halide containing 1 to 20 mol %, preferably 0.5 to 10 mol %, and the shell is composed of silver bromide, silver chloride, silver iodobromide or silver chlorobromide, or a mixture thereof. Particularly preferably, the shell is a silver halide emulsion comprising silver bromide.

Further, in the present invention, when processing a high-sensitivity color photographic light-sensitive material using a silver halide emulsion in which the core is a monodisperse silver halide grain and the shell thickness is 0.01 to 0.57 zm, It has more favorable effects.

Silver halide color photographic light-sensitive materials suitable for processing according to the present invention consist of silver halide grains containing silver iodide, in particular silver halide grains containing silver iodide are used as cores, silver bromide , by hiding the core of silver halide grains made of silver chloride, silver chlorobromide, silver iodobromide, or a mixture thereof using a shell having the specific thickness,
This method takes advantage of the ability of silver halide grains containing silver iodide to increase sensitivity, while concealing the disadvantageous characteristics of the grains.

More specifically, the core is made of silver halide containing silver iodide, and the thickness range necessary to effectively exhibit only the desirable properties of this core and to shield undesirable behavior is strictly regulated. The present invention is most suitable as a method for processing color photographic materials using an emulsion in which a core is provided with a shell. In addition, the method of covering the core with a shell that has the necessary minimum absolute thickness to effectively demonstrate the qualities possessed by the core can be used to change the purpose, and therefore to change the materials of the core and shell, for example, to improve shelf life. It is also extremely advantageous in that it can be used in a stretched manner for purposes such as improving the adsorption rate of sensitizing dyes.

In high-sensitivity color photographic materials to which the method of the present invention is optimally applied, silver halide grains (cores) are
The silver iodide content in the silver iodide range ranges from 0.1 to 20 mol% solid solution to mixed crystal, preferably 0.5 to 10 mol%.
It is mole%. The silver iodide contained within the core may be distributed unevenly or uniformly, but uniform distribution is preferred.

A silver halide emulsion having silver halide grains having a shell having the above-mentioned specific thickness can be produced by covering a core of silver halide grains contained in a monodisperse emulsion with a shell. In addition, when the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 10 mol % or less.

In order to form the core into monodisperse silver halide grains, grains of a desired size can be obtained by a double jet method while keeping pAg constant. Further, a highly monodisperse silver halide emulsion can be produced by applying the method described in JP-A-54-48521. A preferred embodiment of the method is a method in which an aqueous potassium-gelatin solution and an aqueous ammonium silver nitrate solution are added to an aqueous gelatin solution containing silver halide seed particles while changing the addition rate as a function of time. It is to manufacture. At this time, the time function of the addition rate, p)I, p
By appropriately selecting ag, temperature, etc., a highly monodisperse silver halide emulsion can be obtained.

Since the particle size distribution of a monodisperse emulsion is almost a normal distribution, the standard deviation can be easily determined. From the relational expression Preferably some, more preferably 10
% or less.

Next, the thickness of the shell covering the core must be such that it does not hide the favorable qualities of the core, and on the contrary, it must be thick enough to hide the unfavorable qualities of the core, i.e.
The thickness is limited to a narrow range defined by such upper and lower limits. Such a shell can be formed by depositing a soluble halide solution and a soluble silver solution onto a monodisperse core by double jetting.

For example, an average grain size of 14 m containing 2 mol% silver iodide in the core
According to experiments in which monodisperse silver halide grains were used, and the coating thickness was varied with 0.2 mol % of silver iodobromide as a shell, for example, when a shell with a thickness of 0.85 lm was made, Monodisperse silver halide grains produced by this method had low covering power. This was treated with a physically developing processing solution containing a solvent that dissolves silver halide, and when observed under a scanning electron microscope, it was found that no developed silver filaments were present. This suggests that the optical density and even the covering power are reduced. Therefore, considering the filament form of developed silver, we thinned the thickness of the silver bromide shell on the surface while changing the average grain size of the core.As a result, the thickness of the shell was determined by the absolute thickness regardless of the average grain size of the core. 0.5 m or less (preferably 0
．． 21 Lm or less), a large number of well-developed silver filaments were produced, a sufficient optical density was obtained, and the quality of the core for high sensitivity was not impaired.

On the other hand, if the thickness of the shell is too thin, parts of the core material containing silver iodide will be exposed, and the effect of covering the surface with the shell, that is, the chemical sensitization effect, rapid development, fixing properties, etc. will be lost. be exposed. The limit of its thickness is 0.01 m.

Further confirmed by a highly monodisperse core with a distribution width of 10% or less, the preferred shell thickness is 0.01-0.06J.
Lm Te, most preferred thickness is 0.03 JLta
It is as follows.

The above-mentioned development silver filaments are sufficiently generated to improve the optical density, the high-sensitivity properties of the core are utilized to produce a sensitizing effect, and rapid development and fixing properties are achieved due to the high This is due to the synergistic effect between the shell whose thickness is regulated as described above by the dispersible core, and the silver halide composition of the core and shell.If the thickness regulation of the shell can be satisfied, the halogen constituting the shell As the silver, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used.

Among these, silver bromide, silver iodobromide, or a mixture thereof is most preferred from the viewpoint of compatibility with the core, performance stability, and storage stability.

The photosensitive silver halide emulsion used in the present invention may be doped with various metal salts or metal complex salts during the formation of silver halide precipitates of the core and shell, during grain growth, or after the growth is completed.For example, gold, platinum, etc. Metal salts or complex salts such as palladium, iridium L., rhodium, bismuth, cadmium, copper, and combinations thereof can be applied.

In addition, excess halogen compounds generated during the preparation of the silver halide emulsion or nitrates that are duplicated or become unnecessary,
Salts and compounds such as ammonium may be removed,
As a method for removal, the Tardel water washing method, dialysis method, coagulation precipitation method, etc. commonly used in general emulsions can be used as appropriate.

Furthermore, the emulsion of the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin or the like, either alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular restrictions on the optical sensitization method for the above emulsion. can be sensitized.

Regarding these technologies, see U.S. Patent No. 2,888,545, U.S. Patent No. 2,912,329, U.S. Pat. No. 195,302, 1.242,58
No. 8, No. 1,293,882, West German patent (oLS)
No. 2,030,328, No. 2,121,780,
It is described in Japanese Patent Publications No. 43-4936, No. 44-14030, etc. The selection depends on the wavelength range to be sensitized, sensitivity, etc.
It can be arbitrarily determined depending on the purpose and use of the photosensitive material.

The above-mentioned silver halide emulsion further includes a silver halide emulsion in which the core grains are monodisperse silver halide grains, and the core grains are coated with a shell to form the silver halide grains contained therein. As a result, a monodisperse silver halide emulsion with a substantially uniform shell thickness can be obtained, but even if such a monodisperse silver halide emulsion is used with its grain size distribution unchanged, In addition, two particles with different average particle diameters
More than one type of monodisperse emulsion may be blended at any time after grain formation to obtain a predetermined gradation for use.

The above-mentioned silver halide emulsion has a distribution width (total silver halide grains contained in the emulsion at a ratio equal to or higher than that of an emulsion obtained by coating a monodisperse core with a shell of 20% or less). 7-silver halide grains other than the core-shell grains are preferably contained within a range of 1/1 that does not impede the effects of the present invention. It may contain or be polydisperse.

Silver genide emulsions preferably used in the present invention include those containing tabular silver halogenide grains. The tabular /- Silver halide grains t± JP-A-58-113930, JP-A No. 58-113930
No. 113934, No. 58-127921 and No. 5B-
108532, etc., and in the present invention, from the viewpoint of effects on color staining and image quality, the particle diameter is 5 times or more the particle thickness, preferably 5 to 100 It is preferable to use particles with a particle diameter of 0.5 grrr, particularly preferably 7 to 30 times.
The above is preferable, and 0.8 to 8 pm is particularly preferably used. The effects of the present invention are more preferably achieved when these tabular silver halide grains are contained in at least 50% by weight of at least one layer of silver halide emulsion. Almost all of them may be the tabular silver halide grains described above.

Furthermore, a silver halide emulsion of a high-sensitivity color photographic light-sensitive material suitably used in the method of the present invention is disclosed in Japanese Patent Application Laid-Open No. 53-103725.
It is also preferable to contain epitaxially bonded silver halide grains as described in No.

The silver halide emulsion preferably used in the present invention may contain various commonly used additives depending on the purpose. For example, azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydrocarbon compounds. Stabilizers and antifoggants such as aldehydes, aziridines, inoxazoles, vinylsulfones, acryloyls, albodiimides, maleimides, methanesulfonic acid esters, triazine, etc. High film agents; benzyl alcohol, polyesters, etc. Examples include development accelerators such as oxyethylene compounds; image stabilizers such as chroman, claman, bisphenol, and phosphite esters; lubricants such as waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-7 minobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

Supports for the high-sensitivity color photographic materials prepared as described above include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, such as polyethylene terephthalate. There are polyester films, polystyrene, etc., and these supports are appropriately selected depending on the purpose of use of each silver halide color photographic light-sensitive material.

The silver halide emulsion preferably used in the present invention is color sensitized to red, green and blue in order to be applied to a color photosensitive material, and contains a combination of cyan, putenta and yellow couplers in a yAvl emulsion. The methods and materials used for color photosensitive materials, such as photosensitive materials, may be used.

The iodine-containing substituted organic compound and/or iodide salt of the present invention can be contained in a processing solution having bleaching ability, that is, a bleach bath or a bleach-fix bath, or in a step before a treatment step using a bleach bath or a bleach-fix bath. It may be contained in the bath used, a so-called pre-bath; in this case, the pre-bath means a bath after the development step and before a bleach bath or a bleach-fix bath. The pre-bath is usually used immediately before the processing step with the bleach bath or bleach-fix bath, but it does not necessarily have to be immediately before, and other baths may be interposed between the pre-bath and the bleach bath or bleach-fix bath. However, when a bleaching or bleach-fixing step is performed immediately following the developing step, the iodine-containing substituted organic compound and/or iodide salt of the present invention may be contained in the developing bath which is a prebath of the bleaching bath.

Further, the iodine-containing substituted organic compound and/or iodide salt of the present invention may be contained only in the bleach bath or bleach-fix bath or a pre-bath thereof, or may be contained in both the bleach bath or bleach-fix bath and the pre-bath. It may also be included. In other words, the desired bleaching accelerating effect can be obtained in any of these addition modes.The amount of the iodine-containing substituted organic compound and/or iodide salt of the present invention to be added to these baths depends on the type of bath and treatment. Although it varies depending on the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc., good results are generally obtained in the range of about 0.001 g to 50 g per liquid IQ of the processing bath, preferably in the range of 0.1 g to 10 g. is obtained. 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, so the amount added should be determined individually. It is preferable to appropriately determine the optimum range depending on the case. Note that one or more of these iodine-containing substituted organic compounds and/or iodide salts of the present invention may be used in combination.

When adding the iodine-containing substituted organic compound and/or iodide salt of the present invention to a treatment bath, it is generally dissolved in water, an alkali, or an organic acid beforehand. Even if it is dissolved in an organic solvent and added, the bleaching accelerating effect is not affected in any way.

The bleaching solution of the present invention can contain an organic acid ferric (m) complex salt, an iodine-containing substituted organic compound, and/or an iodide salt as a bleaching agent, and other additives. As additives, it is particularly desirable to contain alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. , pH buffering agents such as oxalate, acetate, carbonate, phosphate, solubilizing agents such as triethanolamine, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, alkyl Those known to be added to ordinary bleaching solutions, such as amines and polyethylene oxides, can be added as appropriate. - The bleach-fix solution of the present invention includes a bleach-fix solution containing a small amount of a halogen compound such as potassium bromide, or conversely, a bleach-fix solution containing a large amount of a halogen compound such as potassium bromide or ammonium bromide. It is also possible to use a bleach-fix solution, as well as a special bleach-fix solution consisting of a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide.

In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. can also be used.

The silver halide fixing agent to be included in the bleach-fixing solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount that can dissolve 5 g/i or more, preferably 50 g/i or more, more preferably 70 g/i or more.

Note that the opening fixing solution of the present invention contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, nylium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and hydroxide. pH buffering agents consisting of various salts such as ammonium may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifoaming agents can be contained. In addition, preservatives such as hydroxyamine, hydrazine, sulfites, isomeric bisulfite S salts, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, and Organic chelating agents such as carboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, dimethyl An organic solvent such as formamide or dimethyl sulfoxide can be appropriately contained.

In the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after color development. It may be processed,
A prebath containing a bleach accelerator may also be used as a processing solution prior to bleaching or bleach-fixing.

After bleaching and fixing (or bleach-fixing), stabilization treatment can be performed without washing with water, or washing with water can be performed.

After that, in addition to the 0 or more steps that may be stabilized,
Typical examples of preferred processing methods include the following steps, in which known auxiliary steps such as neutralization, black-and-white development 1 reversal, and a small amount of washing with water may be added as necessary.

(1) Color development → Bleach fixing → Water washing (2) Color development → Bleach fixing → Small amount of water washing - Water washing (3) Color development → Bleach fixing → Water washing → Stable (4) Color development → Bleach fixing → Stable (5) Color development Development → Bleach-fix → 1st stability → 2nd stability (6)
Color development → washing with water (or stable) → bleach-fixing → washing with water (or stable) (7) Color development stop groaning bleach-fix → washing with water (or stable) (
8) Color development → bleaching → washing → fixing → washing → stabilization (9)
A color development → bleaching → fixation → stable after washing (10) color development →
Bleaching → Fixing + 1st stabilization → 2nd stabilization (11) Color development → Bleaching → Washing with a small amount of water → Fixing → Washing with a small amount of water → Washing with water → Stabilization (12) Color development → Washing with a small amount of water → Bleach → Washing with a little water → Fixing Washing with a small amount of water Washing with water and stabilizing (13) Color development Stopping → Bleach → Washing with a small amount of water → Fixing Washing with a small amount of water → Washing with water → Stable (14) Black and white development → Washing with water (or stable) → Reversal Color development → Bleach → Fixing → Washing with water (or omitted) ) → Stable (15) Pre-hardening → Neutralization → Black and white development → Stopped color development → Bleaching → Stabilization → Washing (or omitted) → Stability Among these processing steps, the effect of the present invention is more noticeable in one of these processing steps. Therefore, (1) , (2) , (3) , (4)
, (5).

Processing steps (8) and (7) that can be used to satisfy the bleach-fixing steps are more preferably used in the present invention.

It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention. It is also preferable to add these inorganic metal salts after forming them into metal complex salts together with various chelating agents.

It is preferable to add a chelating agent and/or a ferric complex salt thereof other than the present invention to the bleach-fixing solution of the present invention. It is preferable to use it in an amount of 0.45 mol% or less when expressed as mol%.

The black-and-white developer used in the processing of the present invention is a so-called black-and-white first developer used in the processing of color photographic light-sensitive materials, or a black-and-white developer used in the processing of black-and-white photographic materials. It can contain various additives added to.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Substantial or organic inhibitors such as potassium bromide, 2-methylenebenzimidazole, methylbenzimidazole, etc.
Examples include water softeners such as polyphosphates, surface overdevelopment inhibitors made of 1M iodide and mercapto compounds, and the like.

The aromatic primary amine color developing agent used in the color developer used before processing with the processing solution having bleaching ability of the present invention may be any of the known aromatic primary amine color developing agents that are widely used in various color photographic processes. Included. These developers include amine phenol and p-phenylene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer ti, more preferably about 1 g to about 15 g per 1 fL.

Examples of amine phenol developers include 0-7 minophenol, P-amine phenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.

A particularly useful aromatic primary amine color developer is X.

It is an N-dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted.Among these, a particularly useful compound is N,N-diethyl-p- Phenylenediamine hydrochloride, tomethyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dotecylamino)-toluene, toethylate β-methanesulfone Amidoethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyroot β-hydroxyethylaminoaniline, 4
-Amyl 3-methyl-N,N-diethylaniline, 4-
Examples include ami1N-(2ridoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.

The paraphenylenediamine color developing agent is.

It is preferable to mix it into the bleach-fix solution of the present invention.

The alkaline color developer used before the treatment with the bleaching processing solution of the present invention contains, in addition to the above-mentioned aromatic primary amine color developer, various kinds of color developers that are usually added to color developers. Ingredients, such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkaline total sulfites, alkali total sulfites, alkali metal thiocyanates, alkali MJffi halides, benzyl alcohol, diethylenetriaminepentaacetic acid, l- Water softeners and thickeners such as hydroxyethylene-1,1-diphosphone # may optionally be contained in α. The pH of this color developer is usually 7 or higher, most commonly about 10 to about 13.

'r of the present invention, 7! The surface tension of the processing liquid with white ability is 5
It is preferably 5 dyne/cm or less, more preferably 50 dyne/am or less, and most preferably 40 dyne/am or less.
dyne/am or less.

The surface tension of the treatment liquid with bleaching ability used in the treatment of the present invention is determined from "Analysis and Testing Methods for Surfactants" (co-authored by Fumio Kitahara, Shigeo Hayano, and Betsu Hara, published March 1, 1982, [Kodansha In the present invention, the value of surface tension is measured by a general measuring method at 20°C.

In the present invention, any method may be used to reduce the surface tension of the treatment liquid having bleaching ability to 55 d7ne/cm or less, and any method may be used, but surfactants are preferably used. The surface tension of these processing solutions with bleaching ability is 5
The surfactant to reduce the concentration to 5 dyne/cm or less may be added to the tank solution from the replenisher, or may be added by adhering to the photosensitive material from the pre-bath. It may also be dissolved and added to the treatment solution having bleaching ability according to the present invention.

Among the surfactants of the present invention, compounds represented by the following general formulas (1) to (4) are preferably used from the viewpoint of achieving the desired effects of the present invention.

General formula (1) In the formula, one of R1 and R2 is a hydrogen atom, and the other is a formula -
9O3MCM represents a hydrogen atom or a -valent cation,
), Al represents an oxygen atom or a group represented by the formula -NRs- (Rs represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), R and R4 each represent a carbon It represents an alkyl group of numbers 4 to 16, provided that the alkyl group represented by R3, R4 or Rs may be substituted with a fluorine atom.

General formula (2) % formula % In the formula, A2 is a monovalent organic group, for example, carbon number is 6 to 20
, preferably a B-12 alkyl group (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, The substituent is preferably an alkyl group having 3 to 12 carbon atoms (for example, propyl, butylpentyl, hexyl, heptyl, octyl,
Examples of the aryl group include phenyl, tolyl, xynyl, biphenyl, and naphthyl, with phenyl or tolyl being preferred. The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta, and para positions, B represents ethylene oxide or propylene oxide, m represents an integer from 4 to 50, xl is a hydrogen atom, SO coY or PO3Yz, where Y and Yz are hydrogen atoms, alkali fully bent atoms (Na,
K or Li? ) or represents an ammonium ion.

General formula (3) % formula % In the formula, R5, R7, R8 and Rs each represent a hydrogen atom, an alkyl group, and a phenyl group, but R6, R? , R8
and Rs t)) The total number of carbon atoms is 3 to 50. x2
is a halogen atom, a hydroxyl group, a sulfur group, a carbonyl group, a nitric acid group, an acetate group, p-toluenesulfone [i, etc.].

General formula (4) In the formula, Rho, Ru, Ru, and Ru each represent a hydrogen atom or an alkyl group, and 1M represents the general formula (1)
is synonymous with n and p each represent 0 or an integer from 1 to 4, and are values satisfying 1≦n+p≦8.

The lower the surface tension, the more quickly the oxidation of the ferrous complex salt occurs even without forced aeration, which is preferable. Even when aeration is performed, the bubble diameter is small and the surface area is large even if the amount of air is extremely low. Therefore, a combination of a bleach or bleach-fix solution in which oxidation is carried out very efficiently and has a low surface tension is most preferable.

The silver halide color photographic light-sensitive material to which the processing solution having bleaching ability of the present invention can be applied is an internal development method in which one color former is contained in the light-sensitive material (U.S. Pat. No. 2,376,679,
2,801,171), as well as an external development method in which a coloring agent is contained in the developer (see U.S. Pat. No. 2,252,
No. 718, No. 2,582,243, No. 2,590,9
For example, the cyan coloring agent is based on a naphthol or phenol structure, and the coloring agent can be any coloring agent generally known in the art. Those that form aniline dyes, magenta color formers that have a 5-virazolone ring with an active methylene group as a skeleton structure, and yellow color formers that include benzoylacedoanilide and pivalyl acetanilide that have active methylene chains. It is possible to use either a compound having a substituent at the coupling position or a compound having a substituent at the coupling position, such as a compound having a single structure such as a cylide or acylacetanilide structure. Thus, as the coloring agent, both so-called 2-equivalent couplers and 4-equivalent couplers can be used.

The bleaching solution and bleach-fixing solution according to the present invention include color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies,
It can be applied to silver halide color photographic materials such as color reversal films for TVs and color reversal papers, but especially silver iodobromide or silver chloroiodobromide containing 0.1 mol% or more of silver iodide. It is most suitable for processing high-sensitivity color photographic materials having a total coating silver amount of 20 mg/drn' or more.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Average grain size of silver iodobromide containing 3 mol% of silver iodide: 1. O
Gold sensitization and sulfur sensitization were carried out using silver iodobromide emulsions obtained by shelling silver bromide with a shell thickness of 0.05 JLm on emulsion grains of pm, and after ripening, 4-hydroxy-6-methyl-1, After adding 3,3a,7-chitrazaindene, a sample was prepared as follows so that the amount of silver was 10 mg/100 cm.

Anhydro-3,3-di(3-
sulfopropyl)-5,5-dichloro-8-ethylthiacarbocyanine hydroxide (dye p-1) 285
mg/1% AgX, 77 human l:I-3.3-
Di(3-sulfopropyl)-4,5,4,5-dibenzothi7carpocyanine hydroxide (dye p-2) 3
8.5 mg/1 mol AgX and anhydro-1,3-
Diethyl-3-(3-sulfopropyl)-5-trichloromethyl-4,5-benzobenzimidazolothiacarboxyanine hydroxide (dye p-3) 118 mg
Optical sensitization was performed using 71 mol AgX. This photographic emulsion contains 2-(α, α, β, β, γ) as a cyan coupler.
, γ, δ, δ-octafluorohexanamide)-5-
AgX
The amount of coupler was added at 0.3 mol per mol.

Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1,
3,3a,? - tetrazaindene, with poly-tovinylpyrrolidone as a physical development inhibitor and a fog inhibitor;
It was coated on a subbed cellulose acetate film.

The sample was exposed to light in a conventional manner and subjected to the following development treatment.

[Development Processing] Color development for 3 minutes and 15 seconds, bleach-fixing for 1 to 20 minutes, washing with water for 2 minutes, and stabilization treatment for 1 minute are carried out in sequence, followed by drying.

Each treatment was carried out at 37.8°C, and each treatment liquid was prepared according to the following formulation.

[Color developer] Potassium charcoal 30g Sodium sulfate 2.0g Hydroxyamine sulfate 2.0g Potassium bromide
1.2g sodium hydroxide
3.48N-ethylene-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate
Add 4.8g of water to make 11, and add p with sodium hydroxide.
Adjusted to H10.1.

[Bleach-fix solution] Iron (m) complex salt (shown in Table 1) 150.0g
Ammonium sulfite (50% solution) 10.0g
Ammonium thiosulfate (70% solution) 90.0g
Add water to make one sentence, add ammonium hydroxide to pH 7,
UJ on 2! ! I, ta.

[Stabilizing solution] Formalin (35% aqueous solution)? ,0tJL
Add water to make it to 11.

The bleach-fixing solution was treated by adding 2 g/vert of the compound of the present invention shown in Table 1. For each bleach-fix solution, the time required to complete bleach-fixing of the processed film was compared. At the same time, the film was subjected to bleach-fixing treatment for 8 minutes, and after drying, the maximum density of the film is shown in Table 1 as the neutral maximum density. The neutral maximum density is the white light density of the dye plus unbleached and unfixed silver.

In addition, the iron (m) shown in Table 1! The following salts were used as ammonium salts.

No. Iron (m) complex salt (1) Diethylene 7 l-liaminepentaacetic acid ferric complex salt (2) Diethylenetriamine pentaphosphorus ferric complex salt (3
) Cyclohexanediaminetetravinegar butyferric complex salt (4)
Triethylenetetraminehexaacetic acid ferric complex salt (5) Glycol ether diamine tetraacetic acid fJ, diiron complex salt (6)
Glycol ether diamine tetraphosphate ferric 2a salt (
7) 1,2-diaminopropanetetraacetic acid ferric complex salt (
8) 1.2-diaminopropane tetraphosphorus #ferric complex salt (
9) Methyliminodiacetic acid ft52 iron complex salt mata, ethylenediamine quadruple iron (m)7
It is expressed as A #Fe (m).

As is clear from Table 1, in the processing of high-sensitivity color photographic materials, the iodine-substituted compound, compound, and/or iodide salt of the present invention is used only as a bleaching agent other than the present invention, ethylenediaminetetraacetic acid iron (III). ) It can be seen that the bleaching accelerating effect is significantly greater and better when the organic acid iron (m) complex salt of the present invention is added to a bleach-fixing solution as a bleaching agent than when it is used together with ammonium.

Iron ethylenediaminetetraacetate ([
) (EDTA-Fe (III)) In addition to complex salts, attempts were made to use iron(III) nitrilotriacetate complex, hydroxyethylethylenediaminetetraacetic acid iron(III) complex, etc., but the results were essentially ethylenediaminetetraacetate iron(m) complex. Same result.

Example 2 The bleach-fix solution in Example 1 was replaced with the following bleach solution and fix solution, and the processing was performed for 1 minute to 3 minutes, respectively, and the clearing time was measured.

[Bleach solution Core aminopolycarboxylic acid iron (III) complex salt 0.4 mol Ammonium bromide 150.0 g Water was added to make one part, and the pH was adjusted to 8.2 with ammonium hydroxide.

[Fixer] Ammonium thiosulfate (70% solution) 200 m of ammonium sulfite (50% solution) 30 ra of water was added to make one penny.

The aminopolycarboxylic acid iron (m) complex salt of the bleaching solution and the legal element substituted reduction compound and/or iodide salt of the present invention were treated with substantially the same changes as shown in Table 1.

The results were essentially the same as those in Table 1, but the accelerating effect was slightly inferior to that of the bleach-fix solution.

Example 3 Bleach-fixing treatment prescriptions No. 13 to No. 13 of Example 1.

In the step before the treatment and after the color development treatment, an exemplary compound (b) of the legal element substitution power compound and/or iodide salt of the present invention
) was prepared as an aqueous solution of 1 g/i as a bleach constant M pre-bath and treated for 1 minute, otherwise the treatment was carried out in the same manner as in Example 1.

As a result, the clearing time for prescription No. 1 is 21
The desilvering time for all prescriptions No. 2 to No. 13 was about ten seconds longer than in the case of Table 1.

Claims (1)

Scope of Claims: (1) A method for processing a silver halide color photographic light-sensitive material, in which the silver halide color photographic light-sensitive material is developed after imagewise exposure, and then treated with a processing solution having bleaching ability. The treatment solution has a pH of at least one organic acid ferric complex salt (A) selected from the following ferric complex salt group as a bleaching agent or the following reference solution of an organic acid ferric complex salt of 5.0 to 9.
an iodine-containing substituted organic compound and/or an iodide salt containing at least one organic acid ferric complex salt having a redox potential difference within 100 mV between 1. A method for processing a silver halide color photographic material, which comprises using a processing solution having a bleaching ability containing at least one of the above or a processing solution preceding the processing solution having a bleaching ability. [Organic acid ferric complex salt (A)] (1) Diethylenetriaminepentaacetic acid ferric complex salt (2) Diethylenetriaminepentaphosphate ferric complex salt (3) Cyclohexanediaminetetraacetic acid ferric complex salt (4) Cyclohexanediaminetetraphosphate ferric complex salt Ferric complex salt (5) Ferric triethylenetetramine hexaacetic acid complex salt (6) Ferric triethylenetetramine hexaphosphate complex salt (7) Ferric glycol ether diamine tetraacetic acid complex salt (8) Ferric glycol ether diamine tetraphosphate Complex salt (9) 1,2-diaminopropanetetraacetic acid ferric complex salt (1
0) 1,2-diaminopropane tetraphosphate ferric complex salt (11
) Ferric methyliminodiacetic acid complex salt (12) Ferric methyliminodiaphosphate complex salt [Organic acid ferric complex salt standard solution for redox potential measurement] Ferric chloride 0.23M Organic acid 0.305M Ammonium thiosulfate 1.0M Ammonium sulfite The pH is adjusted using 0.1M ammonia water and acetic acid, and the redox potential is measured. (2) The surface tension of the processing liquid with bleaching ability is 55 dyne.
/cm or less
A method for processing a silver halide color photographic light-sensitive material as described in . (3) Claim 1, wherein the organic acid ferric complex salt is diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid ferric complex salt, or triethylenetetraminehexaacetic acid ferric complex salt. Or the method for processing a silver halide color photographic light-sensitive material according to item 2. (4) The method for processing a silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the processing solution having bleaching ability is a bleach-fix solution. (5) A method for processing a silver halide color photographic light-sensitive material according to claim 4, characterized in that a one-bath bleach-fix treatment using a bleach-fix solution is carried out directly following the color development treatment.