JP2640152B2 - Processing method of silver halide color photographic light-sensitive material for photography - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material for photography, wherein a color developer is processed while being regenerated by ion exchange membrane electrodialysis. The present invention relates to a method for processing a silver halide color photographic light-sensitive material for photography, which is processed while being reproduced by the electrodialysis method, so as not to cause a gradation change or the like in processing.

[Conventional technology]

If the photographic developer waste liquid is allowed to flow into sewage as it is, it deteriorates the quality of rivers and seawater, causing environmental pollution problems.Therefore, the oxidative decomposition method using air blowing, the oxidative decomposition method using ozone, the hypochlorous acid Air decomposition with sodium,
Means for detoxification by treatment with the activated sludge method or the incineration method have been proposed, and some of them have been put to practical use. However, these processing methods have problems such as inefficiency, emission of another harmful substance, and increase in processing cost.

In recent years, it has been desired to reduce the amount of waste photographic processing liquid in order to reduce the environmental pollution load and simplify the processing operation. As a means for reducing the amount of discharged photographic processing waste liquid, there is a method of reducing the discharged liquid by reducing the replenisher of the color developer, and a method of regenerating and reusing the waste liquid of the color developer to reduce the discharged liquid. There are methods.

In the method of reducing the replenisher of the color developing solution, there is a problem that the photographic performance fluctuates due to the accumulation of inhibitory components such as eluates from the emulsion, for example, halogen, and in order to eliminate or reduce such effects, JP-A-61-
No. 251852 and No. 61-261741 disclose a magenta coupler represented by a specific general formula having at least one silver halide emulsion layer containing a core-shell emulsion containing 3 mol% or more of silver iodide, A silver halide color photographic light-sensitive material containing one type of polymer coupler was used, and the color developing process was carried out.
A method has been proposed in which the color developing solution is replenished in an amount of ^-3 mol or less and the color developing replenisher is replenished in an amount of 9 ml or less per 100 cm ^{2 of the} silver halide color photographic light-sensitive material. Japanese Patent Application Laid-Open No. 62-148951 discloses that as a DIR coupler, when it is released from the active position of the coupler by a color development reaction, it becomes a development inhibitor or a development inhibitor precursor, and it flows out into the color developer. Is a coupler having a group having the property of decomposing into a compound that does not substantially affect photographic properties at the coupling active position, and the pH of the development inhibitor is
Used as half-life at 10.0 is less than 4 hours, replenishing amount of developer processing method of the photographic silver halide color light-sensitive material to be developed is shown as below the photosensitive material 1 m ² per 700 ml.

On the other hand, as a method of regenerating and reusing a waste color developing solution, a method of processing using an ion exchange resin, an electrodialysis method using an ion exchange membrane, and the like are known.

As one method of regenerating a color developer using an ion exchange resin, Japanese Patent Application Laid-Open No. 55-144240 discloses a color developer having a higher bromide ion concentration than a conventional color developer. Using a developer containing at least 3 g, preferably 6 g, more preferably 10 g per KBr,
A method of treating a color developing solution in which this is treated with, for example, a styrene-divinylbenzene-based strongly basic anion exchange resin so as to keep the bromide ion concentration in the developing solution constant is disclosed. This is Br by ion exchange resin
^- Since removal capability increases, Br ^{- -} Concentration Br than the higher conventional methods ^- Br in the developer in the removal of requiring less amount of ion exchange resin required to keep the concentration constant. The method for regenerating a color developer using an ion exchange resin is summarized in "SMPTEJ" Vol. 88, pp. 165-167 (1979).

Many studies have been made on a method for regenerating a color developer by an electrodialysis method using an ion exchange membrane.
No. 51-97432, No. 51-85722, Japanese Patent Publication No. 52-36011, No. 5
In addition to JP-A-2-34940, JP-A-53-46732 and JP-A-5-46732 have been proposed in order to carry out the regeneration method more efficiently and maintain the film life long.
As described in JP-A-4-9626 and JP-A-54-19741, there is known a method in which a developer waste solution is contact-treated with a polymer or a resin before or simultaneously with electrodialysis.

In addition, the regeneration method by the electrodialysis method using this ion exchange membrane is improved so that bromine ions and / or
Alternatively, a method of sufficiently removing iodine ions and the like has been proposed (Japanese Patent Publication No. Sho 61-52459).

Further, a method in which the concentration of halogen ions in the photographic processing solution is quantified by adding silver ions during the electrodialysis, and the halogen ion removing means is controlled based on the results (JP-A-54-37741). No.) and, electrodialysis layer connects the desalting chamber developer tank is circulated developer between the desalting developer tank, the developer Br ^- concentration amount of which is controlled to be constant In a method of regenerating a developing waste liquid through an electric current, an amount of water is supplied to an electrolyte solution passing through a concentration chamber of an air dialysis layer according to a developing process to dilute the solution and electrodialysis while maintaining a constant concentration of the electrolyte in the concentrated solution. A method for regenerating a photographic developer as described above (JP-A-56-27142) is known.

[Problems to be solved by the invention]

However, as described above, when the color developing solution is replenished at a low level in order to reduce the discharge amount of the photographic processing waste solution, oxidized decomposition products of the processing solution components and elution products mainly composed of halogen from the photosensitive material are generated. The accumulation in the color developer greatly affects photographic performance. In particular, the effect of suppressing the development due to the accumulation of the leaving group of the DIR coupler used in the color light-sensitive material for photography and the decomposition product thereof is large.
Even if the techniques of -251852, 61-261741, and 62-148951 cannot be used, sufficient low replenishment cannot be achieved.

In addition, the method using an ion exchange resin for regenerating the processing solution requires large-scale equipment, and it is difficult to control the halogen removal rate to a constant value, so that the halogen concentration in the developing solution can be adjusted to a constant value. It is difficult and has drawbacks such as generation of waste liquid due to regeneration of used resin.

When the electrodialysis method using an ion exchange membrane is used, control can be performed in terms of halogen removal, and it is easy to adjust the halogen concentration in the color developer to a constant level, and overflow from the developing tank is prevented. All liquids can be regenerated. However, according to this method, since the halogen is mainly removed, it is considered that the accumulated amount of the other photosensitive material eluted substances is substantially the same as when the replenishment is performed at a level of substantially no discharge. Then, deterioration of the ion-exchange membrane, which is considered to be caused by accumulation of oxides in the composition of the developing solution and accumulation of eluates of the photosensitive material, occurs. In addition, it has been newly found that the repetition of the regeneration of the color developer causes the developer to be fatigued and the development progress speed to decrease. Accordingly, when the photosensitive material is continuously processed, a change in photographic characteristics such as a change in gradation is accompanied.

Techniques for increasing the development progress rate include using a development accelerator (US Pat. Nos. 2,950,970 and 2,515,147),
Incorporating a developing agent into a photosensitive material (US Pat. No. 3,719,49
No. 2) means or a method of increasing the temperature or pH of the color developer can be considered, but it is not sufficient in terms of maintaining stable photographic performance.

The present invention is a method of processing a silver halide color photographic light-sensitive material for photography with a color developer while regenerating the color developer by an ion exchange membrane electrodialysis method, even if the regeneration of the color developer is repeated. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material in which a color developer does not fatigue and a photographic property such as a gradation change does not occur even during continuous processing.

[Means for solving the problem]

In the present invention, when a silver halide color photographic light-sensitive material for photography is processed with a color developing solution, the color developing solution is continuously subjected to ion exchange membrane electrodialysis using an anion exchange membrane and a cation exchange membrane. A method for processing a silver halide color photographic light-sensitive material for photography, wherein the total coated silver amount of the silver halide color photographic light-sensitive material for photography is ^{4 to} 8 g per 1 m ² , and 13 total film thickness
1818 μm, and the bromide ion concentration in the concentrate
The above object has been attained by a method for processing a silver halide color photographic light-sensitive material for photography, wherein the dilution is carried out by diluting with water so as to be maintained at 2 to 20 g / r in terms of r.

In the present invention, the `` total coated silver amount '' of the silver halide color photographic light-sensitive material for photography includes those not directly related to color development, such as black colloidal silver and fine particles of silver iodobromide in a protective layer, “Total film thickness” does not include the thickness of the support.

In the present invention, a remarkable effect is obtained by simultaneously satisfying both the conditions of the total amount of silver applied and the total thickness of the silver halide color photographic light-sensitive material for photography.

When the color developer is regenerated by the ion exchange membrane electrodialysis method, silver eluted from the photosensitive material into the color developer is liable to become a hardly soluble silver salt. Since it is considered that the exchange film is likely to be deteriorated, the amount of silver eluted is reduced by reducing the total coated silver amount of the photosensitive material, and it is considered that at least this is one of the causes and the above-mentioned disadvantage is solved. .

The total coated silver amount of the silver halide color photographic light-sensitive material for photography is 4 to 8 g / m ² , more preferably 4 to 7 g / m ² , and particularly preferably 4 to 4.5 g / m ² . Making the total coated silver amount the above condition relates to the silver amount in the photographic emulsion layer,
The amount of silver in the photographic emulsion layer will be suppressed to some extent. The lower limit of the total amount of coated silver may be a minimum amount necessary for forming an image on the photosensitive material, and since it depends on the type of the photosensitive material, it cannot be unconditionally limited.

The light-sensitive material used in the present invention may be provided as long as at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer is provided on a support. There is no particular limitation on the number and order of the silver emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic material having a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support, The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer in order from the support side,
A green color sensitive layer and a blue color sensitive layer are provided in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, couplers as described in the specification of No. 61-20038, DIR compounds and the like may be included, and as commonly used, a color mixing inhibitor, ultraviolet rays It may contain an absorbent or a stain inhibitor.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62
No. 200350, No. 62-206541, No. 62-206543, a low-speed emulsion layer on the side away from the support as described in
A high-sensitivity emulsion layer may be provided on the side close to the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL is selected from the side farthest from the support.
Can be arranged in this order. JP-A-56-25738
As described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the lower sensitive silver halide emulsion layer, and the lower layer is more than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A No. 59-202464, a medium-speed emulsion layer /
They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Any of these layer arrangements can be used in the color light-sensitive material used in the present invention.

The swelling ratio [(25 ° C., H ₂
Equilibrium swollen film thickness in O-25 ° C, dry film thickness at 55% RH / 25
C. and 55% RH) x 100] is preferably 50 to 200%, more preferably 70 to 150%. If the swelling ratio deviates from the above value, photographic properties are liable to change.

Further, the swelling speed of the light-sensitive material processed in the present invention is 90% of the saturated swelling film thickness in a color-sensitive developer (38 ° C.).
Is defined as the swelling speed T 1/2, and it is preferable that T 1/2 is 15 seconds or less. More preferably, T 1/2 is 9 seconds or less.

The photographic emulsion of the color light-sensitive material used in the present invention is about 80.
Silver iodobromide containing at least mol% of silver bromide. Particularly preferred is silver iodobromide containing from about 100 mole percent to about 90 mole percent bromine.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is described, for example, in Research Disclosure (RD), No. 17643 (1978).
December), pp. 22-23, “I. Emulsion preparat
ion and types) ”and No. 18716 (November 1979
Mon), p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique P
hotographique Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, Focal Press (GFDuffin, Photo)
graphic Emulsion Chemistry (Fcoal Press, 1966)),
"Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikman et al. Making and Coating)
Photographic Emulsion, Fcoal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are provided by Gaft, Photographic Science and Engineerin
g), 14, 248-257 (1970): U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a phase structure.Also, silver halides having different compositions are joined by epitaxial junction. And it may be bonded to a compound other than silver halide such as, for example, silver rhodan and lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the light-sensitive material used in the present invention, and specific examples thereof are described in the aforementioned RD No. 17643.
, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,401,752
No. 4,248,961; Japanese Patent Publication No. 58-10739; British Patent No. 1,
425,020, 1,476,760, U.S. Pat.No. 3,973,968,
Preferred are those described in JP-A-4,314,023 and JP-A-4,511,649 and European Patent No. 249,473A.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,064, RD No. 24220 (June 1984)
), JP-A-60-33552, RD No. 24230 (June 1984)
), JP-A-60-43659, JP-A-61-72238, and JP-A-60-3573.
No. 5, No. 51-118034, No. 60-185951, U.S. Pat.
00,630, 4,540,654, 4,556,630, WO (PCT) 8
What is described in 8/04795 etc. is especially preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and are described in U.S. Pat.No. 4,052,212.
4,146,396, 4,228,233, 4,296,200, 2,36
9,929, 2,801,171, 2,772,162, 2,895,826
No. 3,772,002, No. 3,758,308, No. 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent No. 3,446,622
No. 4,333,999, 4,753,871, 4,451,559,
4,427,767, 4,690,889, 4,254,212, 4,2
Nos. 96,199 and JP-A-61-42658 are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in RD No. 17643, Section VII-G, U.S. Pat.
No., JP-B-57-39413, U.S. Pat.No. 4,004,929,
138,258 and British Patent 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers are U.S. Patent Nos. 3,451,820; 4,080,211; 4,367,282;
No. 4,409,320, No. 4,576,910, UK Patent No. 2,102,173
No. etc.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, U.S. Pat.
Preferred are those described in JP-A-48,962 and JP-A-4,782,012.

As couplers which release an engraving agent or a development accelerator in the form of an image during development, UK Patent Nos. 2,097,140 and 2,13
No. 1,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competing couplers described in U.S. Patent No. 4,130,427 and the like, U.S. Patent Nos. 4,283,472 and 4,338,393.
No. 4,310,618, etc.
0-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, D
IR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after disengagement described in EP 173,302A, RD No. 1144
9, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,553,477, etc., and leuco dyes described in JP-A-63-75747 are released. Couplers and couplers that release a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of high-boiling solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322,027, and specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C or higher used in the oil-in-water dispersion method Examples include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,
4-di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,1
-Diethylpropyl) phthalate), esters of phosphoric or phosphonic acids (triphenyl phosphate,
Tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate,
Tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic esters (2
-Ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate and the like, amides (N, N-diethyldodecaneamide, N, N
-Diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate) , Dioctyl azelate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N
-Dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used,
Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer to form a hydrophilic polymer. It can be emulsified and dispersed in a water-soluble colloid aqueous solution.

Preferably, International Publication No.WO88 / 00723, twelfth
Homopolymers or copolymers described on pages 30 to 30 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

The processing method of the present invention can be applied to various color light-sensitive materials. In particular, it is preferably applied to a color negative film for general use or movies, and a color reversal film for slides or televisions.

Suitable supports that can be used in the present invention include, for example, those described above.
RD. No. 17643, page 28, and RD. No. 18716, page 647, right column, 64
It is described in the left column on page 8.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- [β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p- Phenylenediamine D-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-4-methyl-N-ethyl-N-β-ethoxyethylaniline D-11 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is compound D-5.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine color developing agent used is preferably about 0.1 g / color developing solution.
A concentration of about 20 g, more preferably about 0.5 g to about 10 g.

Further, as a preservative, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as necessary. be able to.

The preferable addition amount of the preservative is 0.
5 g to 10 g, more preferably 1 g to 5 g.

Further, the aromatic primary amine color developing agent directly,
Compounds to be preserved include various hydroxylamines, hydroxamic acids described in JP-A-63-43138, and 63-14604.
No. 1 hydrazines and hydrazides, 63-44657 and 63-58443 described phenols, 63-44656 described α-hydroxyketones and α-aminoketones,
It is preferable to add various sugars described in JP-A-63-36244. Also, in combination with the above compound,
No. 4235, No. 63-24254, No. 63-21647, No. 63-146040
Nos. 63-27841, 63-25654, etc .; 63-30845, 63-14640, 63-4313.
No. 9 diamines, etc., 63-21647 and 63-
No. 26655, polyamines described in JP-A 63-44655, nitroxy radicals described in JP-A 63-53551, alcohols described in JP-A 63-43140, and alcohols described in JP-A 63-53549, JP-A 63-56654. The oximes described above, and 63-23944
It is preferable to use the tertiary amines described in No. 7.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 may be contained as necessary. Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developer used in the present invention is preferably pH 9
To pH 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.

As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphone Acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid.
These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed. However, the color developer according to the present invention has the following characteristics in terms of pollution, liquid preparation and prevention of color contamination.
It is preferable that benzyl alcohol is not substantially contained. Here, “substantially” means that the developer does not contain 2 ml or less, preferably no developer, at all.

Other development accelerators include JP-B-37-16088,
7-5987, 38-7826, 44-12380, 45-9919
Thioether compounds disclosed in U.S. Pat. No. 3,813,247 and US Pat. No. 3,813,247; p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, etc., quaternary ammonium salts, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,23
No. 0,796, 3,253,919, JP-B-41-11431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,346, etc.
No. 01, U.S. Pat.No. 3,128,183, JP-B-41-11431,
Polyalkylene oxides represented by 42-23883 and U.S. Pat.No. 3,532,501, etc., and other 1-phenyl-3-
Pyrazolidones, imidazoles, and the like can be added as needed.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable.
The addition amount is 0 to 5 g / preferably 0.1 g to 4 g /.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer of the present invention is from 20 to 50C, preferably from 30 to 45C. For replenishment of the color developer, a fresh replenisher may be used in addition to the replenisher for the color developer regenerated in the present invention, but the total processing time is 20 seconds to 5 seconds.
Minutes, preferably 1 minute 30 seconds to 4 minutes. It is preferable that the replenishment amount is small. Photosensitive material 1 m ² per 100～2000Ml, preferably
It is 200-1500 ml. More preferably, it is 300 ml to 1000 ml.

Further, the color developing bath may be divided into two or more baths as necessary, and a color developing replenisher may be replenished from the first bath or the last bath to shorten the developing time and reduce the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developing solution used at this time is a so-called black-and-white first developing solution which is generally used for reversal processing of a color photosensitive material. Various well-known additives used in a black-and-white developing solution used in a processing solution for a black-and-white silver halide light-sensitive material are added to a black-and-white primary color reversal photosensitive material.
It can be contained in a developer.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, and accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Examples thereof include inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphate, and a development inhibitor comprising a small amount of iodide or a mercapto compound.

In the present invention, a used color developing solution (overflow solution) is processed by an ion exchange membrane electrodialysis method, and a regenerating agent is contained in the processing solution to be reused as a color developing replenisher.

The regenerating agent is added to a used color developing solution (overflow solution) in principle for the purpose of supplementing the components consumed in the color developing process.

The regenerating agent for a color developing replenisher used in the present invention includes, as a rule, a color developing agent, a pH buffering agent and a chelating agent of the same type as used in the color developing solution, and other components as necessary, such as preservatives. It is preferable to contain an agent, a development accelerator, a fluorescent whitening agent and the like. What is necessary is just to set the amount of these chemical | medical agents to the amount which supplements the consumed component. The amount of each of these regenerants was determined according to the replenisher replenisher 1 obtained.
Per color developing agent is 0.001 to 0.02 mol, pH buffer is
It is preferable that 0.01 to 0.2 mol, the chelating agent is 0.001 to 0.2 mol, and the preservative is 0.01 to 0.03 mol.

In the present invention, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Concentration can be corrected by adding water as needed when preparing a color developing replenisher for the evaporation of the solution in the developing bath, if necessary.

In the present invention, when the developer is treated by the electrodialysis method using an ion exchange membrane, any of the conventionally known electrodialysis methods using ion exchange used in the treatment of photographic waste liquid is used. can do.

It is preferable that the developing waste liquid overflowing from the developing tank is continuously guided to the electrodialysis tank, processed, and the regenerated liquid is returned to the developing tank.

In the electrodialysis tank, the cation exchange membrane K and the anion exchange membrane A are alternately arranged between the electrodes, and the desalting chamber D and the electrode chamber E are arranged between the electrode chambers E.
A structure in which the concentration chambers C are alternately formed can be used.

The cathode and anode are separated alternately by a cation exchange membrane and an anion exchange membrane. From the cathode side to the anode side, a cathode chamber, a plurality of desalination chambers (a cation exchange membrane on the cathode side and a cathode on the anode side) Desalination of an ion exchange membrane electrodialysis tank consisting of a chamber partitioned by an ion exchange membrane), a plurality of concentration chambers (a chamber partitioned by an anion exchange membrane on the cathode side and a cation exchange membrane on the anode side) and an anode chamber A developer waste solution is poured into the chamber, a sodium sulfate solution or sodium carbonate is poured into the concentration chamber, and a direct current is passed through the negative and positive electrodes to perform electrodialysis.

However, in the electrodialysis tank having such a configuration, there arises a problem that the concentration of the electrode solution is reduced or the bromine ion is oxidized in the anode chamber depending on the type of the membrane in contact with the electrode chamber. It is preferable to use an electrodialysis tank having a simple structure.

In this electrodialysis tank, the cathode and the anode are alternately partitioned by a cation exchange membrane and an anion exchange membrane, and an anode chamber extends from the anode side to the cathode side, and then a plurality of desalination chambers (the cathode side has a cation exchange membrane). The same number of concentration chambers as the exchange membrane and the anode side are separated by an anion exchange membrane) and the same number of concentrating chambers as the desalting chambers (the chamber separated by the anion exchange membrane on the cathode side and the cation exchange membrane on the anode side) are the farthest from the anode. The desalination chambers are alternately arranged so that there is a desalination chamber, and both the cathode side and the anode side are separated by a cation exchange membrane adjacent to the cathode side of the desalination chamber arranged farthest from the anode. A concentrating chamber is provided, a cathode chamber is provided adjacent to the concentrating chamber, and a photographic processing solution waste liquid is passed through a desalting chamber of an electrodialyzer in which a common electrolyte solution is supplied and circulated to the cathode chamber and the anode chamber.
A concentrate (also referred to as a concentrate liquid) is passed through the concentration chamber.

Here, the anion exchange membrane and the cation exchange membrane may be any as long as they have an ability to exchange anions or cations, and any exchange membrane is within the scope of the present invention. As the cation exchange membrane, a strongly acidic exchange membrane is preferable.

Electrodes used here include salts such as sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium phosphate, potassium phosphate, sodium nitrate, potassium nitrate, sodium bisulfate, sodium bicarbonate, potassium hydroxide, and hydroxide. Electrolyte solutions such as alkalis such as sodium and acids such as sulfuric acid are suitable. It is sufficient that the concentration of these electrolyte solutions is not less than 0.001 normal, and more preferably 0.01 to 2 normal.

These electrolyte solutions may contain aminopolycarboxylic acids (for example, ethylenediaminetetraacetic acid or its sodium salt, ammonium salt, potassium salt, diethylenetriaminepentaacetic acid or its sodium salt, ethylenediamine-N- (β-oxyethyl- (N , N ′, N ′
-Triacetic acid or its sodium salt, ammonium salt,
Nitrilotriacetic acid or its sodium salt, triethylenetetramine hexaacetic acid or its sodium salt or iminodiacetic acid, etc., aminopolyphosphonic acid (for example,
1,3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,3-propylenediamine-N, N, N', N '-Tetramethylenephosphonic acid or 1-hydroxy-ethane-
1,1-diphosphonic acid, etc.), sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, or 2-phosphoethylimito-N, N-acetic acid.

The concentrated solution used here is an electrolyte solution containing salts such as sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium phosphate, potassium phosphate, sodium nitrate, potassium nitrate, sodium bisulfate, and sodium bicarbonate. ing. It is sufficient if the concentration of these electrolyte solutions is at least 0.001 normal, more preferably 0.01 to 2 normal.

These electrolyte solutions may contain aminopolycarboxylic acids (for example, ethylenediaminetetraacetic acid or its sodium salt, ammonium salt, potassium salt, diethylenetriaminepentaacetic acid or its sodium salt, ethylenediamine-N- (β-oxyethyl- (N , N ′, N ′
Acetic acid or its sodium salt, ammonium salt, nitrilotriacetic acid or its sodium salt, triethylenetetramine hexaacetic acid or its sodium salt or iminodiacetic acid, etc., aminopolyphosphonic acid (for example, 1,
3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,3-propylenediamine-N, N, N', N'- Tetramethylenephosphonic acid or 1-hydroxy-ethane-1,
1-diphosphonic acid, etc.), sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate or 2-phosphoethylimito N, N-diacetate.

Further, a corresponding developer waste liquid may be used for the regeneration of the developer waste liquid as the concentration chamber liquid.

Examples of the material of the cathode of the electrodialyzer and the electrolyzer include iron, nickel, lead, zinc, stainless steel, and the like.
Examples of the material for the anode include platinum, platinum-plated titanium, and graphite.

Also, the current density passed for ion exchange membrane electrodialysis of these developing solution wastes varies depending on the characteristics of the ion exchange membrane and the characteristics of the developing solution, but is generally 0.1 A / dm ^{2 to} 10 A /
dm ² , more preferably 0.2 A / dm ^{2 to} 5 A / dm ² .

In the regeneration of the photographic developer by the ion exchange membrane electrodialysis method of the present invention, immediately before or at the same time as supplying the waste liquid to the desalting chamber of the dialysis tank, JP-A-53-46732, 52-146236, 54-962.
6, 54-19741, 53-132343, etc., polymers, resins, various ion-exchange resins (eg, Diaion SA-10A, SA-20A, PA-316, PA-316, PA-418, WA-
(11, WA-20, CR-10, PK-220, PK-208, Zeolite S-37, Amberlite IR-410) and the like.

Further, by detecting, for example, bromide ions in a photographic processing solution as described in JP-A-54-37731, a constant bromide concentration is maintained while controlling the amount of current supplied to the ion exchange membrane electrodialysis tank. This method also includes a so-called continuous regeneration method in which bromide ions are removed by dialysis, and only the insufficient processing agent component is added to the processing solution waste liquid discharged from the photographic processor and used again as a replenisher.

By diluting the concentrate with water so that the bromide ion concentration in the concentrate is kept constant in the range of 2 g to 20 g / in terms of potassium bromide, the bromide ion in the developer is kept constant, It is more preferable to reduce the fluctuation of the temperature and maintain a high current efficiency for removing the bromide ion from the developer. To replenish the water for diluting this concentrate, for example, synchronize with the replenishment pump that replenishes the replenisher to the developer tank of the automatic developing machine, and replenish it by operating the pump. By replenishing the water according to the above, the bromide ion concentration in the concentrated solution is kept almost constant, and the bromide ion concentration in the developer can be maintained more stable and efficient dialysis can be maintained. preferable.

In the present invention, desilvering is performed after color development. Representative desilvering steps are shown below, but are not limited thereto.

1. (Color development)-Bleaching-Fixing 2. (〃)-Bleaching and fixing 3. (〃)-Bleaching-Bleaching and fixing 4. (〃)-Fixing-Bleaching and fixing 5. (〃)-Bleaching-Bleaching and fixing-Fixing 6. (〃) -Bleaching-fixing-Bleaching 7. (〃) -Bleaching-fixing-fixing If the above desilvering step comprises two or more steps, a washing or rinsing bath may be provided between both steps. Adjustment, washing or a stop bath may be provided between the color developing step and the desilvering step.

In the above-mentioned processing steps, each of the bleaching, bleach-fixing and fixing processing baths may be a single bath, or may be composed of two or more baths. The method of replenishing each processing bath is usually a method of replenishing the replenisher of each processing bath to the corresponding processing bath.However, when the bleach-fix bath comprises a plurality of processing baths, the replenisher is added to the final bath. May be replenished by a so-called countercurrent method of leading the overflow liquid to the pre-bath,
Further, a replenisher may be added to the first bath, and the overflow may be replenished by a so-called forward flow method in which the overflow solution is guided to a subsequent bath. In the steps 3 and 4, the overflow solution of the bleaching bath or the fixing bath, which is the pre-bath, may be introduced into the bleach-fixing bath to replenish the fixing component or the bleaching component in the bleach-fixing bath. In step 5, the overflow solution of the bleaching bath and the overflow solution of the fixing bath may be respectively led to the bleach-fixing bath. In Steps 6 and 7, the components of the subsequent bleaching bath or fixing bath may be led to the bleach-fixing solution.

Examples of the bleaching agent for the bleaching bath or bleach-fixing bath of the present invention include polyvalent transition metal ion compounds such as iron (III), cobalt (IV), chromium (VI), manganese (VII), and copper (II); Substances, quinones, nitrobenzenes and the like are used. For example, ferricyanide, dichromic acid, iron (II
Organic acid chelate compounds of I) or cobalt (IV), ferric chloride, persulfate, hydrogen peroxide, permanganate, benzoquinone, and the like can be used. Among these compounds, it is preferable to use a ferric organic acid complex salt from the viewpoints of pollution, safety and the like, and it is particularly preferable to use a ferric aminopolycarboxylic acid complex salt. These aminopolycarboxylic acids and examples thereof include the following compounds.

1. Ethylenediaminetetraacetic acid 2. Diethylenetriaminepentaacetic acid 3. Cyclohexanediaminetetraacetic acid 4.1,2-propylenediaminetetraacetic acid 5. Ethylenediamine-N- (β-oxyethylel) N,
N ', N'-triacetic acid 6.1,3-diaminopropanetetraacetic acid 7.1,4-diaminobutanetetraacetic acid 8.glycol ether diaminetetraacetic acid 9.iminodiacetic acid 10.N-methyl-iminodiacetic acid 11.ethylenediaminetetrapropion Acid 12.N- (2-acetamido) iminodiacetic acid 13.Dihydroxyethyl glycine 14.Ethylenediamine di-hydroxyphenylacetic acid Ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt or a ferric salt. For example, a ferric ion complex salt may be formed in a solution using an aminopolycarboxylic acid and ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate and the like. . When used in the form of a complex salt, one kind of complex salt may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one or more ferric salts may be used. Further, one or more aminopolycarboxylic acids may be used.
In any case, the aminopolycarboxylic acid may be used in excess of forming a ferric ion complex salt.

Further, the bleaching solution or the bleach-fixing solution containing the above-mentioned ferric ion complex may contain a metal ion complex salt such as cobalt and copper other than iron.

The amount of these bleaching agents added is preferably 0.05 mol to 1 mol per bleaching solution or bleach-fixing solution.
In particular, it is preferably from 0.1 mol to 0.5 mol.

The bleaching solution or bleach-fixing solution of the present invention may contain a rehalogenating agent such as a bromide, for example, potassium bromide, sodium bromide, ammonium bromide, or a chloride, for example, potassium chloride, sodium chloride, ammonium chloride. . In addition, sodium nitrate, nitrates such as ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate,
It may contain one or more inorganic acids, organic acids and salts thereof having pH buffering capacity such as tartaric acid.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831, JP-A-53-37,
No. 418, No. 53-72,623, No. 53-95,630, No. 53-95, 63
No. 1, 53-104,232, 53-124,424, 53-141,6
No. 23, No. 53-28,426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17,129 (July 1978);
No. 129 thiazolidine derivative; JP-B-45-8,506
No., JP-A-52-20832, JP-A-53-32,735, U.S. Pat.
Thiourea derivatives described in 3,706,561; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; No. 49-42,434, No. 49-59,644, No.
No. 53-94,927, No. 54-35,727, No. 55-26,506, No. 58
No. 163,940 can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, US Patent No. 3,893,85
No. 8, West German Patent No. 1,290,812, and JP-A-53-95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent for the bleach-fixing solution include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodides, and thiosulfates are generally used. Ammonium sulfate can be used most widely. As a preservative of the bleach-fix solution, it is preferable to use a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound.

The pH of the bleaching solution or bleach-fixing solution in the present invention is not particularly limited, but is preferably 3.0 to 8.0 when a ferric aminopolyrubonate complex is used as the bleaching agent. The replenishment rate of the bleaching solution or bleach-fixing solution in the present invention, it is necessary to change depending on the amount of coated silver to be processed photographic material, 1000 ml are preferable from the photosensitive material 1 m ² per 10 ml.

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching, bleach-fixing and fixing. here,
After the bleach-fixing or fixing step, processing steps such as washing and stabilization are generally performed. However, after a bath having a fixing ability, a simple stabilization treatment without substantial washing is performed. Processing methods can also be used.

Known additives can be added to the washing water used in the washing step, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants for preventing the growth of various bacteria and algae, and deterrent examples (for example, isothiazolone, organochlorine disinfectants, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LE
West, “Water Quality Criteria”, Phot.Sci.and En
g., vol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As a stabilizing solution used in the stabilizing step, a processing solution for stabilizing a dye image is used. For example, a liquid having a buffer capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), or the like can be used. The stabilizing solution may contain, if necessary, an ammonium compound, a metal compound such as Bi or Al, a fluorescent brightener, a chelating agent (eg, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericide, a deterrent agent, Hardening agents, surfactants, alkanolamines and the like can be used.

In the washing step and the stabilizing step, a multi-stage countercurrent system is preferable, and the number of stages is preferably two to four. The replenishing amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

Water used in these washing or stabilizing steps is not limited to tap water, and may be C
a, It is preferable to use water deionized to a Mg concentration of 5 mg / or less, halogen, and water sterilized by an ultraviolet germicidal lamp.

In the above processing steps of the color light-sensitive material, when continuous processing is performed by an automatic developing machine, the processing solution may be concentrated due to evaporation, particularly when the processing amount is small or when the opening area of the processing solution is large. Will be noticeable. In order to correct such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or a correction solution.

In addition, the amount of waste liquid can also be reduced by using a method in which the overflow solution in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a pre-bath.

(Examples) Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 A sample 103, which is a multilayer color light-sensitive material having the following compositions, was prepared on a cellulose triacetate film support having an undercoat.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer (anti-halation layer) Thickness 1.5 μm Black colloidal silver ……… 0.15 Gelatin ……… 1.5 ExM-8 ……… 0.08 4UV-1 ……… 0.03 UV-2 ……… 0.06 UV-3 …… … 0.07 Solv-2 …… 0.08 Cpd-5 …… 6 × 10 ^-4 Second layer (intermediate layer) Film thickness 1.0 μm Gelatin …… 1.5 UV-1 ……… 0.03 UV-2 …… 0.06 UV -3 ...... 0.07 ExF-1 ...... 0.004 Solv-2 ...... 0.07 Cpd-5 ...... 6 × 10 ^-4 Third layer (first red-sensitive emulsion layer) Thickness 1.4 μm Silver iodobromide Emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin mixed grains, diameter / thickness ratio 2.5) Silver coating amount 0.5 gelatin 0.5 … 0.8 ExS-1 …… 1.0 × 10 ^-4 ExS-2 …… 3.0 × 10 ^-4 ExS-3 ……… 1 × 10 ^-5 ExC-3… 0.22 ExC-4… 0.02 Cpd -5 ......... 3 × 10 ^-4 fourth layer (second red-sensitive emulsion layer) thickness 1.6μm iodobromide emulsion (AgI4 mol%, internal high AgI type, sphere Those diameter 0.55 .mu.m, variation coefficient of 20% of the equivalent spherical diameter, normal crystal, twin crystal mixed grains, diameter / thickness ratio 1) coating silver amount ......... 0.7 Gelatin ......... 1.26 ExS-1 ......... 1 × 10 - ⁴ ExS-2 ... 3 x 10 ^-4 ExS-3 ... 1 x 10 ^-5 ExC-2 ... 0.08 ExC-3 ... 0.33 ExC-4 ... 0.01 ExC-7 ... 0.04 ExY-16 0.01 Solv-1 0.03 Cpd-5 5 × 10 ^-4 5th layer (third red-sensitive emulsion layer) Film thickness 1.4 μm Silver iodobromide emulsion (AgI 10 mol%) , Internal high AgI type, sphere equivalent diameter 0.7 μm, coefficient of variation of sphere equivalent diameter 30%, twin mixed particles, diameter / thickness ratio 2) Silver coating amount ……… 0.7 Gelatin ……… 0.8 ExS-1 ……… 1 × 10 ^-4 ExS-2 …… 3 × 10 ^-4 ExS-3… 1 × 10 ^-5 ExC-5… 0.05 ExC-6… 0.06 Solv-1 ……… 0.15 Solv- 2 ......... 0.08 Cpd-5 ......... 3 × 10 -5 sixth layer (intermediate layer) thickness of 0.8μm gelatin ......... 1.0 Cpd-1 ......... 0.10 Cpd -3 ......... 0.25 Cpd-4 ... ... 1.23 Cpd-5 ......... 4 × 10 -4 Solv-1 ......... 0.05 Seventh layer (first green-sensitive emulsion layer) thickness 0.9μm iodobromide emulsion (AgI2 mol%, internal high AgI type, Equivalent sphere diameter 0.3 μm, Coefficient of variation of equivalent sphere diameter 28%, Normal crystal, twin mixed grains, diameter / thickness ratio 2.5) Silver coating amount 0.30 Gelatin 0.4 ExS-4 5 × 10 ^-4 ExS-5 …… 2 × 10 ^-4 ExS-6 …… 0.3 × 10 ^-4 ExM-8 …… 0.03 ExM-9 …… 0.2 ExY-14 ……… 0.03 Solv-1 …… 0.2 Cpd-5 2 × 10 ^-4 Eighth layer (second green-sensitive emulsion layer) Thickness 1.4 μm Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, sphere) Coefficient of variation of equivalent diameter 20%, normal crystal, twin mixed particles, diameter / thickness ratio 4) Silver coating amount ...... 0.6 Gelatin ... 0.8 ExS-4 ... 5 x 10 ^-4 ExS-5 ... … 2 × 10 ^-4 ExS-6… 0.3 × 10 ^-4 ExM-8… 0.03 ExM-9… 0.25 ExM-10… 0.015 ExY-14… 0.04 Solv-1 ... 0.2 Cpd-5 3 × 10 ^-4 ninth layer (third green-sensitive emulsion layer) Film thickness 1.7 μm Silver iodobromide emulsion (AgI 10 mol%, high internal AgI type, equivalent sphere diameter 0.7 μm) , Coefficient of variation of equivalent sphere diameter 30%, Normal crystal, twin mixed particles, diameter / thickness ratio 2.0) Silver coating amount ……… 0.85 Gelatin ……… 1.0 ExS-4 ……… 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6… 0.2 × 10 ^-4 ExS-7… 3.0 × 10 ^-4 ExM-8… 0.02 ExM-12… 0.06 ExM-13 ……… 0.02 Solv-1 0.20 Solv-2 0.05 Cpd-5 4 × 10 ^-4 10th layer (yellow filter layer) thickness 0.7 μm Gelatin… 0.9 0.9 Yellow colloidal silver… 0.05 Cpd -1 ... 0.2 Solv-1 ... 0.15 Cpd-5 ... 4 x 10 ^-4 11th layer (first blue-sensitive emulsion layer) Film thickness 3.4 µm Silver iodobromide emulsion (4 mol% AgI, internal High AgI type, sphere equivalent diameter 0.5 μm, coefficient of variation of sphere equivalent diameter 15%, octahedral particles) Silver coating amount ……… 0.4 Gelatin ……… 1.0 Ex S-8 2 × 10 ^-4 ExY-14 0.09 ExY-16 0.9 Solv-1 0.3 Cpd-5 4 × 10 ^-4 12th layer (second blue) Sensitive emulsion layer) 0.8 μm thick silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter 1.3 μm, coefficient of variation of equivalent spherical diameter 25%, normal crystal, twin mixed grains, diameter / thickness ratio 4.5) Silver coating amount 0.5 Gelatin 0.6 ExS-8 1 × 10 ^-4 ExY-16 0.12 Solv-1 0.04 Cpd-5 2 × 10 ^-4 Thirteenth layer (first protective layer) Thickness 0.4 µm Fine grain silver iodobromide (average particle size 0.07 µm, AgI 1 mol%) ……… 0.2 Gelatin ……… 0.8 UV-3 ……… 0.1 UV-4 …… 0.1 UV-5 ... 0.2 Solv-3 ... 0.04 Cpd-5 ... 3 x 10 ^-4 14th layer (second protective layer) Film thickness 0.6 µm Gelatin ... 0.9 Polymethyl methacrylate particles ( (Diameter 1.5 μm) ... 0.2 Cpd-5 ... 4 x 10 ^-4 H-1 ... 0.4 In addition to the above components, An activator was added as a coating aid.

A red-sensitive layer (third to fifth layers) of the photosensitive material prepared above,
The film thickness of each layer was changed as shown in Table 1 by changing the amount of silver applied and the amount of gelatin of the green-sensitive layer (7th to 9th layers) and the blue-sensitive layer (11th and 12th layers). did.

Fifth, the chemical structural formulas or names of the compounds used in the present invention are shown below.

Solv-3: Tricresyl phosphate Solv-2: Dibutyl phthalate Solv-3: Bis (2-ethylhexyl) phthalate Samples 101 to 109 prepared as described above were each subjected to imagewise exposure, and were continuously processed in the following processing steps by an automatic developing machine.

Next, the composition of the treatment liquid will be described.

The following color developing solution regeneration method was applied to the above processing.

(Ion exchange membrane electrodialysis method) Ion exchange membrane electrodialysis tank with 10 strongly basic anion exchange membranes, 12 strongly acidic cation exchange membranes (each ² dm ² ), stainless steel cathode and platinum-plated titanium anode Was connected to the above-described color developer tank, and the color developer was circulated. In the concentration room of the electrodialysis tank, the color developer shown above is diluted 4 times with water to make a concentrated solution at the start of running, diluted with water at the time of running, and partially discharged to the outside as waste liquid. The concentrate was circulated while controlling the bromide ion in the concentrate to 2 to 20 g / KBr conversion. In the electrode chamber of the electrodialysis tank, the following electrolyte solution was circulated in the cathode chamber and the anode chamber in common.

(Electrolyte solution) Sodium carbonate 29.3 g Sodium bicarbonate 6.4 g Sodium ethylenediaminetetraacetate 1 g Water is added to 1000 ml (pH 10.20).
By adjusting the concentration within a range of 33 A / ² dm ² , continuous processing was performed while maintaining the potassium bromide concentration in the color developer at 1.4 g ± 0.05 g.

Further, a processing agent necessary for reusing as a replenisher was added to the overflow solution from the color developing tank of the automatic developing machine to make a replenisher, which was used repeatedly.

FIG. 1 shows a conceptual diagram of the electrodialysis tank used, and FIG. 2 shows a conceptual diagram relating to the connection between the color developing tank and the electrodialyzer and the method of reusing the color developing replenisher.
In FIG. 2, N1 represents a color developer and N1-R represents a color replenisher. In the N1 overflow liquid stock tank, when the overflow liquid from the N1 processing tank is stocked and the amount becomes convenient for regeneration, check the pH and specific gravity, confirm that there is no abnormality, and check the next liquid preparation tank. Move to In the liquid preparation tank, add the required amount of chemicals,
While stirring the liquid, add water to the specified volume (liquid adjustment volume). The liquid obtained by the above operation is transferred to the N1-R stock tank as a replenisher N1-R. The necessary amount of replenisher is supplied from the N1-R stock tank to the color developer tank.

According to the above method, the samples 101 to 109 were continuously treated for an average of 5 hours a day for one month. Before and after the continuous processing, each of the samples 101 to 109 was subjected to post-processing by giving gradation exposure for sensitometry.

In the position of the exposure giving the sensitometric yellow density 2.0 tree treated during the continuous processing start, the color developing time yellow density of 1.0 and t _0. Similarly, the color density of yellow at the position of the same exposure in the sensitometry processed at the end of the continuous processing
1.0 to become the color developing time is t _1. Δt = t ₁ −t ₀ (sec) is defined as the difference Δt in the yellow color development speed between before and after the continuous processing. Further, Δγ was calculated as a change in the gradation of yellow, magenta, and cyan before and after the continuous processing.

Note that the gradation here is logE from the point that the density is 0.5.
Is the density change up to the 0.3 density point on the high exposure side. Further, the electrical resistance value of the ion exchange membrane at the end of the continuous treatment (Ω / cm ² )
Was measured. The results are shown in Table 2.

As is apparent from Table 2, even when the total silver amount of the light-sensitive material is within the range of the present invention, when the film thickness is larger than 23 μm, the resistance value of the ion-exchange film is large, and particularly, the developing speed and gradation of yellow. It can be seen that the change increases. (No.1 ~
5) Alternatively, even if the thickness of the photosensitive material falls within the range of the present invention,
It can also be seen that as the amount of silver applied increases, the results worsen.
(No. 3, 8, 9) That is, good results were obtained only when both the amount of applied silver and the film thickness were within the range of the present invention.

Example 2 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multi-layered manner to prepare a multilayer color photosensitive material 202.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 202) First layer: Antihalation layer Black colloidal silver Silver 0.18 Gelatin 0.40 Second layer: Intermediate layer 2,5-Di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U- 1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0) .
6μ, coefficient of variation with respect to particle size 0.15) 0.51 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 Sensitizing dye IV 4.0 × 10 ^-5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 Fourth layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (10 mol% of silver iodide: average grain size of 0.2)
7μ, average aspect ratio 5.5, average thickness 0.2) silver 1.0 sensitizing dye I 5.1 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.3 × 10 ^-4 sensitizing dye IV 3.0 × 10 ^-5 EX -2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide 16 mol%, average grain size 1.1μ)
Silver 1.60 Sensitizing dye IX 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 Sensitizing dye IV 3.1 × 10 ^-5 EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6S layer (intermediate layer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 Gelatin 0.80 7th layer (First green-sensitive emulsion layer) Tabular silver iodobromide emulsion (Silver iodide 6 Mol%, average particle size 0.
6μ, average aspect ratio 6.0, average thickness 0.15) silver 0.40 sensitizing dye V 3.0 × 10 ^-5 sensitizing dye VI 1.0 × 10 ^-4 sensitizing dye VII 3.8 × 10 ^-4 EX-1 0.021 EX-6 0.260 EX- 7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 Eighth layer (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0.1%)
7 μ, variation coefficient 0.18) silver 0.80 sensitizing dye V 2.1 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX-1 0.008 EX-6 0.180 EX-7 0.012 EX-8 0.010 HBS-1 0.160 HBS-4 0.008 Gelatin 1.10 Ninth layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide 12 mol%, average grain size 1.0μ)
Silver 1.2 sensitizing dye V 3.5 × 10 ^-5 sensitizing dye VI 8.0 × 10 ^-5 sensitizing dye VII 3.0 × 10 ^-4 EX-1 0.025 EX-6 0.065 EX-11 0.030 HBS-1 0.25 HBS-2 0.10 gelatin 1.74 10th layer (yellow filter layer) Yellow colloidal silver silver 0.05 EX-5 0.08 HBS-3 0.03 gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (6 mol% silver iodide, Average particle size 0.
6μ, average aspect ratio 5.7, average thickness 0.15) silver 0.24 sensitizing dye VIII 3.5 × 10 ^-4 EX-8 0.12 EX-9 0.85 HBS-1 0.28 gelatin 1.28 12th layer (second blue-sensitive emulsion layer) Monodispersed iodine Silver bromide emulsion (silver iodide 10 mol%, average grain size 0.
8μ, variation coefficient 0.16) silver 0.45 sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 gelatin 0.46 13th layer (3rd blue sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide 14 mol%, average grain size 1.3μ)
Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average particle size 0.07μ)
Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 S-1 0.15 S-2 0.05 Gelatin 0.72 In addition to the above components, a gelatin hardener H-1 and a surfactant were added.

The silver amount and the film thickness of the red-sensitive layer (the third to fifth layers), the green-sensitive layer (the seventh to ninth layers) and the blue-sensitive layer (the eleventh to fourteenth layers) of the photosensitive material prepared above were measured. In the same manner as in Example 1, samples modified as shown in Table 3 were produced.

EX-11: Same as EX-1, but R = H HBS-1; tricresyl phosphate HBS-2; dibutyl phthalate HBS-3; bis (2-ethylhexyl) phthalate Sensitizing dye Samples 201 to 205 prepared as described above were each subjected to imagewise exposure, and processed in the following processing steps by an automatic developing machine.

Washing water is of a countercurrent type from washing (2) to washing (1), and all overflows of washing water were introduced into the fixing bath. The bleach-fix bath is replenished by connecting the top of the bleach tank and the bottom of the bleach-fix tank of the automatic processor and the top of the fix tank with the bottom of the bleach-fix tank by pipes, and supplying replenisher to the bleach tank and the fix tank. All of the generated overflow liquid was allowed to flow into the bleach-fix bath. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of fixing liquid brought into the washing step were 2.5 ml, 2.0 ml, 2.0 ml, 2.0 ml, and 2.0 ml, respectively, per 35 m wide photosensitive material. ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous process.

 The composition of the treatment liquid is shown below.

(Bleaching fixer mother liquor) A mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor in a ratio of 15 to 85. [Adjust with ammonia water and acetic acid] (Washing water) Common for mother liquor and replenisher Tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strong basic anion exchange resin ( Water is passed through a mixed-bed column packed with the same Amberlite IRA-100) to treat the calcium and magnesium ion concentrations to 3 mg / or less, followed by sodium diisocyanurate 20 mg / sodium sulfate 150 mg /
/ Was added. The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common for mother liquor and replenisher (g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononyl 0.3 phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Disodium salt -8.0 For each of the samples 201 to 205, continuous treatment was performed for an average of 5 hours a day for one month while regenerating the color developer using the ion-exchange membrane electrodialysis method in the same manner as in Example-1. Continued for a while. Before and after the continuous treatment, the same evaluation as in Example 1 was performed. The results are shown in Table 4.

As is clear from Table 4, the amount of silver applied to the photosensitive material and
It is understood that good results can be obtained by setting the film thickness within the range of the present invention.

[Effects of the Invention] According to the present invention, while a color developer is regenerated by an ion-exchange membrane electrodialysis method, when the color developer is processed with a silver halide color photographic light-sensitive material for photography, a development process is performed. Even if the development proceeds, the development progress speed does not decrease, and no change in photographic characteristics such as a change in gradation occurs. Therefore, in the present invention, a silver halide color photographic light-sensitive material for photography can be continuously processed by using a regenerated color developing solution as a replenishing solution with almost no addition of a new color developing replenishing solution. In the present invention, the above effects can be obtained by simultaneously satisfying the conditions of the total amount of applied silver and the conditions of the total film thickness.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an electrodialysis tank used in the present invention, and FIG. 2 is a conceptual diagram relating to a connection between a color developing tank and an electrodialyzer and a method of reusing a color developing replenisher. K: Cation exchange membrane, A: Anion exchange membrane D: Desalination chamber, C: Concentration chamber E: Electrode chamber, N1: Color developer N1-R: Color developer replenisher

Claims (1)

(57) [Claims] 1. When a silver halide color photographic light-sensitive material for photography is processed with a color developer, the color developer is continuously subjected to electrodialysis using an ion exchange membrane using an anion exchange membrane and a cation exchange membrane. A method for processing a silver halide color photographic light-sensitive material for photography, wherein the total coated silver amount of the silver halide color photographic light-sensitive material for photography is ^{4 to} 8 g per 1 m ² , And the total film thickness is 13
1818 μm, and the bromide ion concentration in the concentrate
A method for processing a silver halide color photographic light-sensitive material for photography, wherein the dilution is carried out by diluting with water so as to keep it at 2 to 20 g / r.