JPS6148701B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing color photographic materials, and particularly to a stabilizing treatment for color photographic materials that does not require washing with water. Generally, when color photographic materials are processed, a color image is obtained by desilvering after color development, but washing with water is always required before and after each processing step. On the other hand, there is a demand for a processing method that does not require a water-washing process, and for black-and-white photographic paper, a stabilization process (that is, a process that stabilizes the image without washing with water; THJames "The Theory of the
There have been patent applications since 1943 for the Photographic Process (see page 444). (British Patent No.
589560; US Patent No. 2453346; US Patent No. 2453347
(No. 2448857, etc.) Furthermore, around 1965, photosensitive materials containing black and white developing agents were treated with a stabilizing solution containing rhodan salt after alkali treatment (stabilization treatment), allowing development that did not require water washing. Processing (such as stabilization of Fuji Kuitsuku sensitive materials) was widely used. Regarding this, a patent (West German Patent No. 1772945) has been submitted that states that color sensitive materials can be stabilized only with a bleach-fix solution containing iron (2)-EDTA and ammonium thiosulfate after color development and termination. However, the method according to this patent not only caused coloring on a white background but also suffered from poor stability of color images, and was not widely available on the market. The above-mentioned stabilization processing solution for black-and-white photosensitive materials specifically performs only image stabilization processing, but does not perform any silver bleaching or fixing processing. It is necessary to perform not only so-called stabilization but also silver bleaching and fixing simultaneously or sequentially. Therefore, it is not possible to transfer the stabilizing treatment liquid used for black and white photographic paper to color photosensitive materials, and it is considered difficult to put stabilization treatment into practical use for such color photosensitive materials. Ta. By the way, in the processing of color photosensitive materials, there is a term "stabilizer" which is similar to the stabilization treatment or stabilization treatment liquid referred to herein. This stabilizing bath is a pH stabilizer used in post-wash processing as a way to increase the stability of processed color images.
This is an addition bath consisting of a buffer solution of 3.5 to 4 and a hardening agent, and is completely different from the stabilization treatment immediately after the bleach-fixing treatment (which does not involve water washing). Furthermore, in recent years, in urban areas, the cost of supplying washing water for photographic processing has become high, and discharging washing wastewater also costs a huge amount of money, so there is a desire to conserve water.
Moreover, due to the rise in the price of oil, there was a problem in that it required a great deal of expense to heat the washing water. Therefore, there is a need for a processing method that increases the stability of color images after processing by stabilizing color sensitive materials and does not necessarily require the conventional washing process that consumes a large amount of water. Ta. Accordingly, a first object of the present invention is to provide a color stabilization processing system that does not necessarily require a water washing step when color developing and bleach-fixing a color photosensitive material. The second object of the present invention is to provide a color development and bleach-fixing processing method for color sensitive materials that provides a more stable color image after processing compared to a conventional processing method using water washing processing. An object of the present invention is to provide a method for stabilizing a photosensitive material. These objects of the present invention are to bleach-fix a chromogenic silver halide color light-sensitive material containing a coupler with a color developer and a bleach-fix solution containing an iron salt of polycarboxylic acid, and then to develop a specific color without washing with water. This was achieved by a new method for processing color photographs, which is characterized by stabilizing a color image by treating it with an aqueous solution of pH 3 to 8 that has a buffering ability and contains a specific amount of phosphoric acid or its salt. In other words, we have challenged the conventional wisdom that stabilizing color photosensitive materials is difficult, and have discovered that the above method is an extremely excellent stabilizing method. The processing method of the present invention increases the stability of color images and eliminates problems such as fogging over time. In addition, conventional processing methods for washing with water consume at least 100% of water per ^m2 of sensitive material and
The processing time of ~5 minutes (at least 2 minutes) was required, but the processing method of the present invention does not necessarily require such washing with water, and requires at most 1 part of water per 1 m ² of sensitive material and a processing time of about 1 minute. Now you can also do it with . In the present invention, at least one selected from orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, and salts thereof.
It is characterized by using an aqueous solution having a buffering capacity and having a pH of 3 to 8 and containing 0.1 to 10 g of each seed compound. Citric acid, tartaric acid, lactic acid, succinic acid, glycine, diethylbarbisolic acid, dimethylglycine, trimethylpyridine, etc. may be added to such aqueous solution as necessary. Moreover, as such an aqueous solution, the following solution containing the above-mentioned specific phosphoric acid or its salt can be used. Namely, Clark-Lubs buffer,
Sprensen's buffer, Kolthoff's buffer,
Michaelis buffer, Palitzsch buffer,
Hasting-Sendroy buffer, Britton-Robinson
buffer solution, etc. can be used. The pH of an aqueous solution having such a buffering ability is 3 to 8, preferably 4 to 6. Various compounds may be contained in the stabilizing bath, which is composed of an aqueous solution containing at least one of the specific phosphoric acids or salts thereof and having a buffering capacity of PH 3 to 8. For example, as various types of mold inhibitors,
Antibiotics (chloramphenicol; kanamycin; erythromycin; leucomycin; tetracycline, etc.) and food additives (sodium benzoate; thiabendazole; salicylic acid; diphenyl; potassium sorbate; dehydroacetic acid; propionic acid; hydroxybenzoic acid, etc.) May be added. Furthermore, if necessary, a hardening agent (such as formalin), a fluorescent whitening agent, a surfactant, etc. may be added. Further, after the treatment with the stabilizing treatment liquid, washing with water, for example, rinsing with water, spray washing, etc., may be performed as necessary. The stabilization treatment in the present invention is usually carried out at a temperature in the range of 10 to 60°C for 30 seconds to 2 minutes. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure Co., Ltd.
Any of the known methods and known dye image-forming processing liquids (color processing liquids) such as those described in Disclosure No. 176, pages 28-30 (RD-17643) can be applied. For example, the negative-positive method (e.g. “Journal of the Society of Motion
61 (1953), pp. 667-701); developed in a developer containing a black and white developing agent to produce a negative silver image and then processed at least once. A color reversal method is used in which a dye-positive image is obtained by carrying out a similar exposure or other suitable fogging process, followed by color development. A special form of development process involves adding a developing agent to the light-sensitive material. For example, a method may be used in which the photosensitive material is contained in an emulsion layer and developed by processing the light-sensitive material in an alkaline aqueous solution.A color developer generally consists of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known one. Primary aromatic amine developers, such as phenylenediamines (e.g. 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N -β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
), pages 226-229, U.S. Patent No. 2193015,
Those described in No. 2592364, JP-A-48-64933, etc. may be used. The color developer may also contain a PH buffer, a development inhibitor or an antifoggant. In addition, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, and antioxidants are added as necessary. , an alkaline agent, a solubilizing agent, a surfactant, an antifoaming agent, and the like. Specific examples of these additives include Research Disclosure (RD-17643) and U.S. Patent No.
It is described in No. 4083723, OLS No. 2622950, etc. The bleach-fix solution used in the present invention uses a ferric salt of polycarboxylic acid as an oxidizing agent. Specific compounds of polycarboxylic acids include oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, and ethylenediamine. -N-(β-oxyethyl)-
N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, alkyliminodiacetic acid, dihydroxyethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid propionic acid, phenylenediaminetetraacetic acid,
1,3-diamino-2-propanoltetraacetic acid, triethylenetetraminehexaacetic acid, hydroxyethyliminoacetic acid, N-hydroxyethylethylenediaminetriacetic acid, oxybis(ethyleneoxynitrilo)tetraacetic acid, malic acid, tartaric acid, citric acid, glutaric acid , adipic acid, lactic acid, crotonic acid, aconitic acid, itaconic acid, diglycolic acid, citraconic acid, etc., and sodium salts and potassium salts of these polycarboxylic acids. Among these compounds, particularly preferred are ethylenediaminetetraacetic acid (EDTA),
Diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',
Examples include aminopolycarboxylic acids such as N'-triacetic acid and propylene diamine tetraacetic acid, and their sodium salts and potassium salts. Further, as the fixing agent, commonly used fixing agents can be used. Specifically, thiosulfate, thiocyanate, potassium iodide, thiourea, etc. are used. Bleach-fix solutions include U.S. Patent No. 3042520;
No. 3241966, Special Publication No. 1973-8506, Special Publication No. 1977-8836
In addition to the bleaching accelerator described in JP-A-53-65732 and the thiol compound described in JP-A-53-65732, various additives can also be added. The photosensitive material used in the present invention is
No. 84636, JP-A-52-119934, JP-A-53-46732
No. 1986-9626, 1974-19741, 1973-37731, Japanese Patent Application No. 1976-76158, Japanese Patent Application No. 54-1976
-76159 and Japanese Patent Application No. 54-102962, the developer may be replenished or maintained. The bleach-fix solution for photosensitive materials used in the present invention is
JP-A-46-781, JP-A No. 48-49437, JP-A No. 48-18191
No. 50-145231, No. 51-18541, No. 51-
It may be recycled by the method described in No. 19535, No. 51-144620, and Japanese Patent Publication No. 51-23178. Any of silver bromide, silver iodobromide, iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halides are silver chlorobromide, silver iodobromide, or silver iodochlorobromide containing 3 mol % or less of silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
(expressed as an average based on projected area) may have a narrow or broad particle size distribution. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubes and octahedrons, or irregular crystal shapes such as spherical and plate shapes. It may be a crystalline substance or a compound of these crystalline forms.
It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a nude water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid) or gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example H. Frieser ed. Die
Grundlagen der Photographischen Prozesse
mit Silberhalogeniden (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization can be found in Research Disclosure, Vol. 176, 17643.
(Published December 1978) Page 23, Section J. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color is formed by oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) during a color development process. It may also contain compounds that can. For example, as a magenta coupler, 5
- Pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR coupling compound that is colorless and releases a development inhibitor. In order to introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl fropionate, 2
butyl alcohol, methyl isobutyl ketone,
After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum,
chromium acetate, etc.), aldehydes (formaldehyde, geryoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1, 3,5-triacryloyl-hexahydro-S-triazine,
1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-
(6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic light-sensitive materials. be done. Useful as flexible supports are films, baryta layers or alpha-olefin polymers of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer) or the like. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. U.S. Patent No. 2681294, U.S. Patent No. 2761791, U.S. Pat.
The method described in No. 3526528 is an advantageous method. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. Example 1 A silver chlorobromide emulsion containing a yellow coupler emulsified dispersion (silver chloride 30 mol %) and a silver chlorobromide emulsion containing a magenta coupler emulsified dispersion (silver chloride) were prepared on a paper support with a resin coating. A color paper was prepared by coating a gelatin layer containing silver chloride (silver chloride 60 mol %), a silver chlorobromide emulsion containing a cyan coupler emulsion dispersion (silver chloride 60 mol %), and a UV absorber. Each coupler emulsion used in this color paper was prepared by dissolving each coupler in a mixture of dibutyl phthalate and tricresyl phosphate, dispersing sorbitan moclarate, funnel oil, and sodium dodecylbenzenesulfonate as dispersing emulsifiers, and dissolving each coupler in a gelatin solution. This is an O/W type distribution. As a coupler, 1-(2′,4′,6′-trichlorophenyl)-3-[3″-(2,4-di-t
-Amylphenoxyacetamide)benzamide]
-5-pyrazolone, 2-(2,4-di-t-amylphenoxyacetamide)-4,6-dichloro-
Three types were used: 5-methylphenol and α-(2-methylbenzoyl)-aceto-(2'-chloro-5'-doderoxycarbonyl) anilide. As the ultraviolet absorber, the one described in Japanese Patent Publication No. 45-9586 was used. Furthermore, the emulsion contains 2,4-
Dichloro-6-hydroxy-1,3,5-triazine sodium salt was added. After exposing the color paper thus produced, it was processed using the following two methods. (33℃ treatment)

[Table] Color developer Benzyl alcohol 10ml Diethylene glycol 3ml Potassium carbonate 25g Sodium chloride 0.1g Sodium bromide 0.2g Anhydrous sodium sulfite 2g Hydroxylamine 2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate
Add 4g water and make 1 using sodium hydroxide.
Adjust to PH/10.0. Bleach-fix ammonium thiosulfate 124.5 g Sodium metabisulfite 13.3 g Anhydrous sodium sulfite 2.7 g EDTA ferric ammonium salt 65 g Add 100 c.c. of a color developer having the above formulation, and add water to make 1. Stabilization treatment liquid phosphoric acid/potassium dihydrogen 4.5g Add water 1 (PH5.0)

[Table] The stability of the samples obtained by the above treatment over time was investigated in the following manner. That is, each sample was dried at 80℃ under a xenon light source (room temperature).
After aging for 3 to 25 days under conditions of 60℃ and 70%RH, fog density and optical density were measured using a densitometer.
The density of the 1.0 (D _1.0 ) portion was measured and each density change (fog density change, color fading rate at D _1.0 ) was evaluated. Regarding changes in fog density, the first
The results are shown in the table. According to the method of the present invention, as can be seen from Table 1, the increase in fog density can be significantly suppressed even though the amount of liquid used is smaller than that of the conventional method (processing method A) in which washing is performed with running water. did it. Also,
The fading rate of the image at D _1.0 was about the same in both Process A and Process B. This is a very surprising fact and means that according to the invention there is no need for washing with water. That is, a highly stable color photographic image could be obtained by simply processing in an aminopolycarboxylic acid bath without washing with water after bleach-fixing. Example 2 0.5g/sodium benzoate was added to the stabilization treatment solution of treatment method B in Examples 1 and 3,
The liquid was tested over time. 3 at 33℃ or 38℃
Although the treatment was continued for several months, there was no generation of moss or off-odor in the stabilization treatment solution, and the same stabilization treatment as in Example 1 could be performed. Example 3 Sodium metaphosphate was used instead of potassium dihydrogen phosphate in the stabilization treatment solution used in Example 1.
When an image retention test was conducted in the same manner as in Example 1 using 3.0 g/or sodium pyrophosphate, excellent image retention was obtained. Example 4 Changes in fog density over time when the amount of potassium dihydrogen phosphate added to the stabilization treatment solution used in Example 1 was changed as shown in Table 2 were investigated in the same manner as in Example 1. I looked it up. The results are summarized in Table 2.

[Table] It can be seen that according to the present invention, the increase in fog density is particularly small in GL and BL.

Claims (1)

[Claims] 1 Color development method After color development, a silver halide color light-sensitive material is subjected to bleach-fixing treatment with a bleach-fixing solution containing an iron salt of polycarboxylic acid, and then, without washing with water, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid and It has a buffering capacity containing 0.1 to 10 g of at least one compound selected from the salts of
A method for processing color photographic materials, characterized by processing with an aqueous solution having a pH of 3 to 8.