JPS58105148A - Color photographic processing method - Google Patents

Abstract

PURPOSE:To prevent desilvering and recoloring defects and to facilitate controlling of solutions by providing a bleach-fixing tank in a counter current system of two tanks and using two kinds of replenishing components. CONSTITUTION:A processing tank 10 consists of a color developing tank 11, the 1st bleach-fixing tank 12, the 2nd bleach-fixing tank 13, and washing tanks 14-16. The 1st and the 2nd bleach-fixing tanks are connected by means of a connecting pipe 12A, in which tanks films are processed while a fixing component (fixer) is replenished through a replenisher supplying pipe 12C from the tank 11 and a bleaching component (an oxidizing agent) is replenished mainly through a replenisher supplying pipe 13A from the tanks 14-16. Since the bleach-fix baths are replenished by a non-regenerating system, the amt. of the replenisher is decreased. The desilvering defects that arise when pH is increased by carrying of the color developing soln. in the bleath-fix baths as well as the recoloring defects that tend to arise when the pH is increased are prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide color photosensitive material (hereinafter simply referred to as "!").
e! ``optical materials.'' ), and particularly relates to a color '4' east processing method that improves the bleach-fixing process.

After exposure, the photosensitive material undergoes the following processing steps: color development, bleach-fixing, and water washing to develop a color photographic image. by the way,
In the bleach-fixing process, various troubles occur because bleaching, which is an oxidation reaction, and fixing, which is a reduction reaction, are carried out in the same bath, and there is a problem that stable processing is strictly prohibited. is.

For example, if the oxidation-reduction potential of the solution is increased in order to improve the bleaching elongation, there is a problem that the fixing component is easily oxidized and sulfurized, or if the fixing speed is increased, there is a restriction on the bleaching speed. As a result, the bleach-fixing process requires a certain amount of time and a long time, and at the same time, it is necessary to finely control the formulation for each type of photosensitive material.

Furthermore, since the bleach-fixing tank is filled with a high pH color developing solution from the previous step, the pH of the bleach constant 59 replenisher is set lower than the pH of the so-called mother liquor.

Therefore, if the amount of color developer brought in and the amount of bleach-fix replenisher refilled are maintained at a constant ratio, the pH of the bleach-fixing solution will be stabilized.In reality, for example, If the amount of color developer brought in changes depending on the condition of the squeegee in the processing equipment, it is likely to change, as the pH of the bleaching stone solution will immediately change, and this can lead to poor desilvering (
This has caused serious troubles such as poor color recovery (when the pH becomes too high) or poor color recovery (when the pH becomes too low).

Furthermore, in recent years, a method for replenishing the bleach-fix solution has been to simply replenish the components that are lacking in the bleach-fix solution when processing photosensitive materials and the components necessary to complex ionize the silver eluted therein. The so-called non-regenerative method (Eastma
fl Kodak's 1NR method. ) has been adopted, and the amount of bleach-fix replenishment has been significantly reduced (to 115 to 1/6 of the conventional amount). The problem is that bleach-fix solutions are becoming more difficult to manage.

The present invention has been made in view of the above circumstances, and its purpose is to provide a color photographic processing method that eliminates all of the above-mentioned problems in conventional color photographic processing methods and facilitates the management of bleach-fix solutions. It is about providing.

The above-mentioned object of the present invention is to provide a color-based processing method that performs color development, bleach-fixing, and water washing, in which at least two white-color fixing processing tanks are used in a countercurrent system. The bleach-fix tank near the image tank mainly contains fixing ingredients.
The bleach-fixing tank located near the relocated washing tank is mainly processed using a color photographic processing method characterized by replenishing each bleaching component.

In the present invention, the bleaching agent liquid refers to a bleaching component (oxidizing agent).
Bleaching components include iron rings of polycarboxylic acids, blush salts, bromate compounds, cobalt hexamine, and other acid preservatives, and fixing components include ammonium thiosulfate and sodium thiosulfate. , ammonium halide, thiourea, and other compounds that have a fixing effect on silver halide.

The polycarboxylic acid referred to here refers to an organic compound containing two carboxyl groups, and specific examples include oxalic acid, succinic acid + malo>#glutaric acid, adipic acid, hexamalic acid, and maleic acid. acid.

7 Talic acid, terephthalic acid, ethylenediamine/tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, gotylenediamine-N-(β-oxyethyl)-N
, N', IJ' -) diacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, anolkyliminodiacetic acid, hydroxyethylglycine, ethyl ether diamine tetraacetic acid m, glycol ether diamine tetraacetic acid, Ethylenediaminetetrabrobin acetic acid, phenylenediaminetetraacetic acid.

1.3-diamino-2-probanolte 1 vinegar ff.

Triethylenetetramine wood acetic acid, hydroxyethyliminoacetic acid PI N-hydroxyJ chitethylenediamine 1-monoacetic acid, oxybis(ethyleneoxy)tetraacetic acid, apple p, :4Q tartaric acid, citric acid, glutaric acid, adipic acid , bolic acid, crotonic acid.

Aconitic acid, itaconic acid, diglycol hundred! , citraconic acid, etc. are depleted by 1 degree.

Among these compounds, particularly preferred is ethylenediaminetetraacetic acid (KDTA).

diethylenetriaminepentaacetic acid, ethylenediamine-
N-(β-oxyethyl) -N, N', N' -
Aminopolycarboxylic acids such as triacetic acid and propylene diamine tetraacetic acid can be mentioned.

For bleach-fix solutions, see US Pat. No. 3,042,520.

In addition to the bleaching accelerators described in Japanese Patent Publication No. 3,244.966, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 4fi-8836, etc., and the thiol compound described in Japanese Patent Publication No. 53-65732, various additives are added. You can also do that. Further, the bleach-fixing solution used in the present invention is
No. 4.9437, No. 48-18191, No. 4.9437, No. 48-18191, No. 4.9437, No. 48-18191, No.
No. 145231, No. 51-18541, No. 51-19
No. 535, No. 51-144620, Special Publication No. 51-23
It may be recycled by the method described in No. 178 or the like.

In addition, "installing the bleach-fixing tank in a two-tank countercurrent system" means:
A method in which the bleach-fix solution is transferred between two separate bleach-fix tanks in the reverse order of the processing of the photosensitive material.

For the perforation treatment of the photosensitive material of the present invention, for example, research disclosure
ure) No. 176, pages 28-30 (RD-17643)
Any known method and known processing solution for forming a dye image, such as those described in , can be applied.

The treatment temperature is usually chosen between 18°C and 50°C, but it may also be below 18°C or above 50°C.

As a special type of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution to effect development.

Color developing solutions generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (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-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.

The color developing solution may also contain a pH buffering agent, a development inhibitor or an antifogging agent.

In addition, if necessary, water softeners, preservatives, organic solvents, development accelerators, one-color patch-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarbonate cross-linking agents, etc. , an acid famine preventive agent, an alkali agent, a solubilizing agent, a surfactant, an antifoaming agent, etc. may all be used.

The photosensitive material used in the present invention is JP-A-51-84-6
No. 36, JP-A-52'-119934, JP-A-53-
No. 46732, JP-A-54-9626, JP-A-54-
No. 19741, JP-A-54-37731, JP-A-56
-1048, JP-A-56-1049, JP-A-56-
It may be processed with a developer that is replenished or maintained in the manner described in No. 27142 Hemorrhoids.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion layer of the light-sensitive material used in the present invention. Preferred silver halides are silver chlorobromide, silver iodobromide, or silver iodobromide containing up to 3 mol % of total silver iodide.

The average grain size of the halogenated grains in the emulsion (
The particle size is defined as the particle diameter for spherical or approximately spherical particles, and the edge length for cubic particles, and is expressed as an average based on the projected area. ) may have a narrow or wide particle size distribution.

The photosensitive dye used in the present invention may be spectrally sensitized with methine-colored violets 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, dye combinations showing supersensitizing 1 and substances showing supersensitizing 1 are listed in the Research Disclosure (R
aaearch Disclosure ) 1 '7
Volume 6 17643 (Published December 1978) Page 23 ■
It is stated in Section 1.

The photographic emulsion layer of the light-sensitive material used in the present invention contains a color-forming coupler, that is, a color-forming image forming agent that forms color by oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative). All compounds that can be used shall be included. For example, magenta couplers include δ-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain azila-7-tonitrile couplers, etc., and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloyl acetanilides, etc.). 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 ions. In addition, colored couplers that have sound effects for color correction or couplers that release all of the development inhibitor during development (
It may also be a so-called DIR coupler).

In addition to DIn couplers, we also use colorless sword craft R, which produces a colorless product of the coupling reaction and releases the development inhibitor.
It may also contain a coupling compound.

Coupler can be introduced into all silver halide emulsion layers by known methods, e.g.
The following methods are used. For example, 7 tar acid alkyl esters (dibutyl phthalate, dioctyl phthalate, phosphoric acid esters (diphenyl phthalate,
triphenyl sulfate, tricresyl 7 osphate, ditributyl 7 osphate Ml;), gostylate citrate (e.g., anatyl tributyl citrate, nisdel ammonium chloride (e.g. λ = octyl benzoate, etc.)
, alkylamides (e.g. diethyl laurylamide, etc.)
.

Fatty acid esters (e.g., dibutoxycetyl succinate, dioctyl azelate, etc.), trimesate (alpha), acid ester furnace (e.g., tributyl trimesate, etc.), or organic solvents with a boiling point of about 30°C to 150°C. ．．
(For example, lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone.

After being dissolved in a hydrophilic colloid (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 mixed and used.

The 4tp optical material used in the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salt (chromium ming (・-r, acid m)
chromium, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydiogysane, etc.), activated vinyl compounds (1 ,3,5-)
lyacryloyl-hexahydro-8-)riazine, 1°3-vinylsulfonyl-2-propatol, etc.).

α2) Active halokene compounds (2,49chloro-6-hydroxy-8-)riazine), mucohalogen acids (mucochlor, mucophenoxychloric acid ItJ), 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 proprietary purposes.

The photographic emulsion of the light-sensitive material used in the present invention contains various compounds for the purpose of preventing capri during the first stage of manufacturing, storage, or image processing of the light-sensitive material, or for stabilizing photographic performance. be able to.

In the light-sensitive material used in 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, which is commonly used in light-sensitive materials. be done. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose vitreous, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and baryta layer-stratified α. -Paper coated or laminated with olefin polymers (eg, polyethylene, polypropylene, ethylene/butene copolymers, etc.).

In the photographic material used in the present invention, the photographic emulsion layer, parent layer, and aqueous colloid layer 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. The methods described in US Pat. No. 2,681,294, US Pat. No. 2,761.791, and US Pat. No. 3,526,528 are effective methods.

Embodiments of the present invention will be described in detail below with reference to the drawings.

Figure 1 is a diagram showing all the essential parts of a color paper processing apparatus which is an embodiment of the present invention. This color paper processing apparatus IO includes a color developing tank 11. First bleach-fix tank 12. The color developer PPj11 consists of a second whitening fixing tank 13 and washing tanks 14 to 16, and the color developer PPj11 has a processing liquid over tube 70-tube 11A, a replenisher supply tube lIB (not shown), stirring means, and liquid temperature control. It has 19 joints. The first bleach-fixing tank 12 is connected to the second bleach-fixing tank 1a1 by a connecting pipe]-2A.
3 is connected to the processing liquid overflow pipe 1.2.
B. In addition to the replenisher supply pipe 120, it is equipped with stirring means, liquid temperature adjustment means, and the like. The second marker fixed tank 13 is
As mentioned above, it is connected to the first bleach-fixing tank 12 by the continuous IT pipe 12A, and the replenisher supply pipe 13A.

It is equipped with stirring means, liquid temperature adjustment means, etc.

In addition, the washing tanks 14 to 16 are connected by connecting pipes 14A and 15A, and the washing tank 16 at the rearmost position is connected to a water supply pipe 16.
A is over 70-pipe 1 in the front washing tank 14.
4n is provided.

For comparison, FIG. 2 shows an example of a conventional color paper processing apparatus. In this installation @20, the color developing tank 11
．． Consisting of a bleach-fix tank 21 and washing tanks 14-16, the same components as shown in FIG. 1 are given the same reference numerals. The present apparatus 120 (5) has a bleach-fixing tank 21 having a 1411 structure, and is equipped with a processing liquid maker 70-pipe 21A, a replenisher supply pipe 21B, a stirring means, a liquid temperature adjusting means, etc. This is different from the device shown in FIG.

The results of a comparative experiment conducted using the apparatus shown in FIG. 1, which is an embodiment of the present invention, and the apparatus shown in FIG. 2 for comparison will be explained in detail as an example below. .

The color paper used in the following experiments consisted of a shoe support 1- with a resin coating, a silver chlorobromide emulsion (30 mol% silver earthide) containing a yellow coupler emulsified dispersion, and a magenta coupler emulsified dispersion. A gelatin layer containing a silver chlorobromide emulsion (silver chloride 60 mol %), a dusty silver bromide emulsion (silver chloride 60 mol %) containing a cyan coupler emulsified dispersion 1, and an ultraviolet absorber is coated. . Each coupler emulsion used in this color paper was dissolved in the respective coupler total dibutyl phthalate tricresyl phosphate mixture, sorbitan moclarate, funnel oil and sodium dodecylbenzene sulfonate Th content as emulsifying agent α6). , which is dispersed in an O/W type in a gelatin solution.

As a coupler, 1-(2,4,6'-)lichloro7
H)-3-(3"-(2,4-t-amylphenoxyacetamide)benzamide)-δ-pyrazolone, 2
- (2,4-di-t-amylphenoxyacetamide)
-4,6-dichloro-5-methylphenol, α-(2
-methylbenzoyl)-aceto-(2'-chloro-5'
-doderoxycarbonyl) anilide were used. In addition, as an ultraviolet absorber, Tokuko Showi 5-9586
The one described in the publication was used. Furthermore, the emulsion contains 2
,4-dichloro-6-hydroxy-1,3,5-) riazine sodium salt was added.

Color paper as described above was processed according to the process shown in FIG. In the bleach-fixing process in the apparatus shown in FIG. 1, the processing times in the two bleach-fixing tanks were made to be approximately the same.

For color developer No. 17, the following formulation was used.

Benzyl alcohol 10ml diethylene glycol 3ml potassium carbonate
25g sodium chloride
0. ] g Sodium bromide 0.2 g Anhydrous sodium sulfite 2 g Hydroxylamine 2 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4 g Add all of the water and make 11 using sodium hydroxide. Adjust the pH to 1,0,0.

As the bleach-fix solution, p”artA as shown below is used.
~Part D divided into four parts was used.

Part A Ammonium thiosulfate (70%) 250+r+/
/2δ0m1Part B Sodium bisulfite 15 g Ammonium sulfite (3%) b Om
/Add water 25QmlPa
rt 0 IDTA FeNH, 2H, O (35%)
18Qm7EDTA ・4H (1.0%)
15m! Ammonium hydroxide (28%
) Add 5ml water
250mjPart D Water 250m/
/250mj The method of using the bleach-fixing solution is as follows.

α) In the case of the device shown in Figure 1, when using it as a so-called mother liquor, the above Part A
/%/ Equal mixture of Part D t- Fill two bleach-fix tanks 1.2.13.

When used as a replenisher, add 13.5 ml of part A and p per l, m of color paper to be processed.
art B to the first bleach-fix tank 12 through the replenisher supply pipe 120', the same < 13.5 ml Part
O and PartDi replenisher supply pipe 13A through the second
α9) respectively to the bleach-fixing tank 13.

2) In the case of the device shown in Figure 2, when using it as a mother liquor, the above Part A-Par
The apparatus is substantially the same as the apparatus shown in FIG. 1 in that the bleach-fix tank 2 is filled with a mixture of all the ingredients. However, when used as a replenisher, 13.5 mj of each of the above Ps per 1 ml of color paper to be processed.
Part A-" Part Df is greatly different from the apparatus shown in Figure @1 in that the same bleach-fix tank 21 is replenished through the replenisher supply pipe 21B.

In addition, the color developer replenishment method is used for both the apparatus shown in FIG. 1 and the apparatus shown in FIG.
,! The replenishment method is exactly the same in that the color developing tank 11 is refilled through the replenisher supply pipe 11Ak. Regarding the water supply for washing, both the apparatus shown in Fig. 1 and the apparatus shown in Fig. 2 supply 5 water per ml of color paper to be processed through the water supply pipe 16A to the washing tank 16 located at the rearmost position. They are completely equivalent in that they are

(2) 0) -L Treatments were carried out using the two types of apparatus under the conditions described above. The treatment was continued until the amount of replenisher supplied to each treatment tank reached 5 times or more the capacity of the respective treatment tank. The results obtained are as follows.

(1) Storage stability of the solution in the bleach-fix tank (room temperature) The solution in the single-cypress bleach-fix tank of the device shown in Figure 2 can be stored for about one month even when not in use, and after that, Although problems such as precipitation occurred, the solution in the two-cypress bleach-fix tank of the apparatus shown in FIG. 1 remained usable for about two months.

(2) Desilvering time was about 30 seconds in the fresh solution state, but in the case of the so-called desilvering solution state, it was 60 to 7 seconds in the case of the apparatus shown in Figure 2.
In contrast, in the case of the apparatus shown in FIG. 1, the time was only 50 to 60 seconds.

(3) Recovery rate of silver The recovery rate of silver from the overflow solution from the bleach-fixing tank 21 of the apparatus shown in Figure 2 was about 60%.
Silver recovery from the overflow liquid from the first bleach-fix tank 12 of the apparatus shown in FIG. 1 reached approximately 90%.

Furthermore, in the apparatus shown in FIG. 2 and the apparatus shown in FIG. -1521
(See Publication No. 35) By providing a silver recovery tank, the silver recovery rate could be improved to about 95% in the apparatus shown in FIG. 2 and to about 99% in the apparatus shown in FIG.

←) Storage stability of processed color paper Comparative results of the so-called photobleaching property show that the color paper processed by the apparatus shown in Figure 1 has a higher degree of yellowing in white areas and a higher degree of fading in cyan. 2. The color paper processed by the apparatus shown in FIG. 2 exhibited clearly superior shelf life 1. This is considered to be because the apparatus shown in FIG. 1 has a bleach-fix tank divided into two, so that the content of color developer components in the latter bleach-fix tank is relatively reduced.

As is clear from the description of the above embodiments, the processing method of the present invention is superior to the conventional processing method in terms of storage stability in the bleach-fix tank, desilvering time, and storage stability of processed color paper. We were able to obtain excellent performance.

In addition, in the treatment by the apparatus shown in FIG. Hit 51
When the amount was reduced from 1 to 1 liter, the same performance as that of the above example was obtained, except that the shelf life of the treated color paper became equivalent to that of the conventional treatment method. This suggests the possibility of reducing the amount of water supplied for washing in the treatment method of the present invention.

Note that the treatment method of the present invention can be used in combination with other yuzu treatment methods. For example, a good example is combining a color developer tank with a color developer regenerating device. Furthermore, it goes without saying that the total amount of water used for washing can be saved by making the washing tank a multi-stage cascade connection tank. Furthermore, the processing method of the present invention is not limited to the processing of color paper as shown in the above embodiments, but can also be applied to the color paper (23) internal fixing tank.

It goes without saying that this method can also be applied to the treatment of other photosensitive forest materials such as moths.

As described above, according to the present invention, color development is possible.

In a color photographic processing method in which all steps of bleach-fixing and water washing are carried out, at least two bleach-fixing processing tanks are provided in a countercurrent system, and the bleach-fixing tank near the color development Sakai image tank in the front stage mainly carries the fixing components, while the latter stage Since the bleach-fixing tank near the water washing tank is mainly replenished with bleaching components, the coexistence of the processing solution in the bleach-fixing tank is completely improved, and the silver rotation rate and the amount of processed light-sensitive material are improved. One remarkable effect is that it is possible to realize a color photographic processing method that can also improve storage stability.

[Brief explanation of drawings]

FIG. 1 is a diagram showing a processing device that is an embodiment of the present invention;
FIG. 2 is a diagram showing a conventional device for comparison, and FIG. 3 is a diagram showing the processing steps. 10.20: color vapor processing device, 11: color developing tank, 12: first bleach-fix tank, 13 = second bleach-fix tank, 14- to 16: washing tank, 21: bleach (24) Patent applicant Fuji Photo Film Co., Ltd. Agent: Masatoshi Isomura, patent attorney:). Figure 1 MA

Claims (1)

[Claims] In a color-based processing method in which a silver halide color photosensitive material is subjected to color development, bleach-fixing, and water washing after exposure, the bleach-fixing process is set up in a countercurrent system with at least two tanks. A color photographic processing power method characterized in that a bleach-fixing tank near the color developing tank is mainly supplemented with a fixing component, and a bleach-fixing tank near a washing tank is mainly supplemented with a bleaching component.