JPS6381343A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain stable photographic performance, even in case of remarkably changing a processing amount per unit time by using specific two kinds of processing replenishers. CONSTITUTION:In continuously processing exposed silver halide photographic sensitive material, a 1st developing replenisher contg. a main developing agent and a 2nd developing replenisher which contains a halogen ion donating compd. and does not contain substantially the main developing agent are replenished to the processing bath, as the processing replenisher which is replenished to the processing bath. The 1st developing replenisher is an aqueous solution contg. the main developing agent as an essential component, and the 2nd developing replenisher is an aqueous solution which contains the halogen ion donating compd. and does not contain the main developing agent. Thus, the change in the photographic performance due to the variation in the composition of the developer is reduced, thereby obtaining a stable photographic performance.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for processing silver halide photosensitive materials.

Specifically, the present invention relates to a processing method that reduces changes in performance due to changes in developer composition and provides stable photographic performance.

[Conventional technology]

Generally, processing of silver halide photosensitive materials includes a development step. In the case of black-and-white light-sensitive materials, a black-and-white developer is used that forms a silver image from exposed silver halide, and in the case of color light-sensitive materials, a color developer is used that forms a color image together with a silver image. In the reversal process for obtaining a positive image, both black-and-white and color photosensitive materials are subjected to black-and-white development to form negative images, and then processed with black-and-white and color developers, respectively.

The black-and-white developer and the color developer contain a developing agent as an essential component as a reducing agent for reducing exposed silver halide to metallic silver, and the former contains polyhydroxybenzene derivatives, aminophenol derivatives, or -phenyl-3-pyrazolidone derivatives, etc. are used, and the latter has a p
-phenylenediamine derivatives, p-aminephenol derivatives, etc. are used. In addition, the developer contains an alkaline agent to increase development activity, a preservative to prevent air oxidation of the developing agent, an antifoggant to increase image discrimination, and a metal salt to prevent sedimentation when using hard water. Contains chelating agents to prevent oxidation and accelerators to promote development and color development.

Generally, when a silver halide photosensitive material is continuously processed with a certain amount of developer, the activity of the developer decreases and the resulting photographic properties change. In other words, it becomes difficult to maintain desirable photographic characteristics.

The causes of this change are consumption of the developing agent during development, accumulation of eluates and products from the photosensitive material during development, oxidation of the developing agent and preservative due to heat and air oxidation over time, and oxidation of the developing agent and preservative due to the passage of time. resulting from concentration by evaporation. Therefore, in order to prevent these changes and maintain stable photographic characteristics, an operation called "replenishment" is generally performed. That is, a solution called a "replenisher" having a composition similar to that of a developer is added to the development bath depending on the amount of photosensitive material to be processed.
It seeks to correct the aforementioned changes. In order to make up for the lack of developing agents and preservatives, which are components that are generally consumed and decrease, and to restore the halogen ions, which are components that accumulate and inhibit development, to their original concentration, The concentration is lower than that of the developer. In addition, the concentrations of other components in the replenisher are set so as to maintain preferred concentrations.

When such a replenisher is used and the photosensitive material is developed more than a certain number of times per unit time, the ratio of the developer components in the developing tank is kept constant, and a certain number of photographs are processed as the photosensitive material being processed. However, in reality, as the amount of development processing increases or decreases, changes such as oxidative deterioration occur in the developing agent in the developer tank due to the stop time of the process, and the composition of the developer fluctuates. It has been difficult to obtain stable photographic performance.

Various improvements have been proposed to solve these problems. JP-A No. 46-5436 discloses a method of monitoring the halide concentration and developing agent concentration of the developer, and selectively using two types of replenisher containing a developing agent and having different halogen ion concentrations as needed. Disclosed. However, this method requires monitoring of component concentrations and would be expensive if automated, and the performance of the two types of replenishers deteriorates over time, so they may have to be discarded before they are used up. Additionally, Japanese Patent Application Laid-Open No. 49-68725 discloses a method for replenishing a replenisher solution prepared from at least two stable solution concentrates. This method separates the developing agent-containing part and the alkali or halide-containing part, and mixes them in a fixed ratio immediately before use to create a replenisher, so the finished replenisher does not deteriorate over time. However, it is not possible to correct the fluctuations in liquid composition and photographic performance caused by the aforementioned fluctuations in the amount of photographic material processed per unit time and the stop time. Japanese Patent Application Laid-Open No. 53-jOO232 discloses a method of using two types of replenishers, one for processing fatigue and one for aging fatigue, but this method also suffers from changes in the two types of replenishers themselves over time, and the above-mentioned problems arise. can't solve the problem. Unexamined Japanese Patent Publication 1973
Publication No. 23631 discloses a method of replenishing a single replenisher in an amount determined from a function equation of rest time and temperature, but it is necessary to appropriately correct both the aforementioned decreasing component and accumulating component. It is not possible. Japanese Unexamined Patent Publication No. 51-83528 discloses a method in which overflow liquid from two developing machines with a large throughput is caused to flow into the other developing machine. However, this is not possible with a single developing machine, and has the drawback that photographic performance is affected by changes in the components of the overflow liquid.

[Problem that the invention seeks to solve]

Accordingly, an object of the present invention is to provide a method for processing silver halide photographic materials that can maintain stable photographic performance even if the amount of development processing per unit time varies considerably.

[Means for solving problems]

The present invention was made based on the knowledge that the above problems can be effectively solved by using two specific types of developer replenishers.

That is, the present invention uses a first developer replenisher containing a developing agent and a halogen ion-releasing compound as a developer replenisher to be refilled in a development processing bath when continuously developing an exposed silver halide photographic light-sensitive material. The second developer replenisher containing substantially no developing agent is used, the developer in the development bath is replenished with the first developer replenisher, and the concentration of halogen ions in the development bath does not fluctuate. The present invention provides a method for processing a silver halide photographic material, which comprises replenishing the processing bath with a second developing replenisher.

The first developer replenisher used in the present invention contains a developing agent as an essential component. Specifically, in the case of a black and white developer, dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used. Contains one type or a mixture of two or more types of known black and white developers such as the following. or,
In the case of a color photographic developer, it contains an aromatic primary amine color developing agent such as an aminophenol compound or a p-phinidine diamine compound.

At this time, p-phinidinediamine type compounds are preferably used, and a typical example thereof is 3-methyl-4-aminodiamine-based compounds.
, N-diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxylethylaniline, 2-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-)luenesulfonates, tetraphenylborates, p-(1-octyl)benzenesulfonates, etc. can be mentioned. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Examples of aminophenol derivatives include 0-aminophenol, p-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (
(1966) (L, F, AlMason.

“Photographic Processing
Chemistry”, FocalPress) 2
Those described in pages 26 to 229, U.S. Pat. No. 2.193.015, U.S. Pat. If necessary, two or more color developing agents may be used in combination.

The first developer replenisher used in the present invention (hereinafter referred to as the first replenisher) contains the above-mentioned developing agent in an amount of O, 1 to 30 g/l or less. ), preferably containing 2.0 to 25 g/f,
It is preferable to use it as an aqueous solution with a pH of 9.5 to 12.5.

Furthermore, various compounds can be added to the first replenisher.

For example, it is preferable to use one type or a mixture of two or more of conventionally used hydroxylamines in order to improve the stability of the color developer. Specifically, the following are exemplified. Among these, the alkyl group of the N,N-dialkylhydroxyamine may be substituted with a hydroxy group or a lower alkoxy group.

11, N0H1CH3NllOH, CF3CHJHOH
, ((:H3)2N Kano, (C1l-CH2)2N mouth 11
, (C)1.0c)12C112)2NDH1(N1
1□CLCL)2NDH, (CF3CH2)JportH1 The above hydroxyamines may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and oxalic acid. Preferred hydroxyamines are N,N-dialkyl substituted, and the alkyl group may be further substituted.

These hydroxyamines are 0 per 11 of the first replenisher.
．． It is preferable to use 0.1 g to 20 g, preferably 0.1 g to 10 g, more preferably 1 g to 8 g.

Further, it is preferable to contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts. The amount of these additions is Og
~20g/jl! The amount is preferably Og to 5 g/l, and the smaller the amount, the better, as long as the stability of the color developer is maintained.

Other preservatives include hydroxyacetones described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176;
α-aminocarbonyl compound described in No. 5, JP-A-57-
Various metals described in No. 44148 and No. 57-53749, various saccharides described in JP-A-52-102727,
Hydroxamic acids described in No. 52-27638, No. 59
α, α′-dicarbonyl compounds described in No. 160141, salinic acids described in No. 59-180588, No. 54
-Alkanolamines described in No. 3532, No. 56-9
Poly(alkyleneimine) described in No. 4349, No. 56
Gluconic acid derivatives described in No.-75647 and the like can be added as necessary. Two or more of these preservatives may be used in combination, if necessary.

In addition, the first replenisher in the present invention may include a pH buffering agent such as an alkali metal carbonate, borate or phosphate; an organic solvent such as diethylene glycol; a dye-forming coupler; a competitive coupler; Nucleating agents such as boron hydride; auxiliary developers such as l-phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediamine Triacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and JP-A-58-195845
Aminopolycarboxylic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, typified by the compounds described in the Research Disclosure + - (Research
Disclosure) No. 18170(1
Aminotris (May 979), an organic phosphonic acid described in
methylene phosphonic acid), ethylenediamine-N, N, N
Aminophosphonic acids such as ',N'-tetramethylenephosphonic acid, JP-A-52-102726, JP-A-53-427
No. 30, No. 54-121127, No. 55-40'24
No. 55-4025, No. 55-126241, No. 55-65955, No. 55-65956, and Research Disclosure (Research Di
sclosure) No, 181'? No. 0 (1
May 1979) may contain a chelating agent such as a phosphonocarboxylic acid.

Furthermore, various compounds can be added as development accelerators. For example, U.S. Patent No. 2.648.604, Japanese Patent Publication No. 44-95
03, U.S. Patent No. 3.171.247, various pyrimidylam compounds and other coloronic compounds, cationic dyes such as phenosafranine, neutral salts such as krylam nitrate and potassium nitrate, and Japanese Patent Publication No. 1983-930.
No. 4, U.S. Patent No. 2.533.990, U.S. Patent No. 2.531.
No. 832, No. 2.950.970, No. 2, 577, 1
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 27, US Patent No. 3
．． Thioether compounds described in No. 201.242, and other JP-A-58-15693.4, JP-A No. 60-220344
Examples include the compounds described in No. 1, benzyl alcohol, and the like. Among these, benzyl alcohol is preferable for promoting development, but it is better not to add it from the viewpoint of ease of solution preparation and pollution load.

Furthermore, organic antifoggants such as benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-
Nitrogen-containing heterocycles such as nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, 4-hydroxy-6-methyl-1,3,38,7-titrazaindene compound and l-phenyl-5
-Mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylmercapto-1,3,4-thiadiazole, 3-mercapto-4-phenyl-1,2,4-
Mercapto-substituted heterocyclic compounds such as triazole, 3-mercapto-5-methyl-4←phenyl-1゜2.4-)IJ azole, and mercapto-substituted aromatic compounds such as thiosalicylic acid can be added. can.

The first replenisher used in the present invention contains 0.5 to 10 g of the preservative/0 to 15 g/L of the organic solvent among the above compounds.
ji', auxiliary developer from 0 to 1.0 g/I! , a chelating agent may be contained in an amount of 0.1 to 5 g/It.

Furthermore, a halogen ion-releasing compound, which is a component of the second developer replenisher, is contained in a range of 0 to 2 x 10-2 mol/l, and optionally 2 x 10-2 mol/l.
It can be included.

The second developer replenisher (hereinafter referred to as second replenisher) used in the present invention is an aqueous solution containing a halogen ion-releasing compound and substantially free of a developing agent. Here, "not substantially containing a developing agent" means that it has no developing activity, and preferably contains no developing agent at all.

The above-mentioned halogen ion-releasing compound refers to a compound that releases halogen ions such as chloride ion, bromide ion, and iodide ion in an aqueous solution, and specifically, potassium bromide, sodium bromide, potassium iodide, sodium chloride, Examples include one or a mixture of two or more of potassium chloride, lithium chloride, and the like.

As the second replenisher, when the halogen ion releasing compound is a chloride ion or bromide ion releasing compound, I
0-3 mol/I! ~2 mol/1, preferably 1x l
Q-'+-ru/R~2X10-'mol/I! ,
For iodide ion releasing compounds, lXl0-'mol/l
-2X 10-' mol/11 preferably I X 10-
5 mol/f! ~2x l Q-'mol/ji! It is preferable to use an aqueous solution containing p)It to 13, preferably pH 3 to 10.

It is preferable to add a ρ■ buffer such as an alkali metal carbonate, borate, or phosphate to the second replenishing solution used in the present invention to maintain the pH of the solution within the above range. Furthermore, the second
The replenisher may contain anti-piping agents, antibacterial agents, and the like.

Note that tap water can be used as the water used in the first and second replenishment solutions, but if stored in a tank, bacteria and mold may grow, and sediment may form, so please do not use these. It is preferable to use water that does not cause problems, such as distilled water, ion-exchanged water using a cation exchange resin and/or anion exchange resin, or water from which dissolved components have been removed using an adsorbent such as activated carbon. It is also preferable to sterilize the water used with ultraviolet light.

In the present invention, the photosensitive material is intermittently processed using the first and second replenishers. In addition, in this process, the first replenisher is used to replenish the consumption of the developing agent in the developing bath, which usually involves fluctuations in the throughput per unit time, and the loss due to oxidative deterioration, and the second replenisher is used to compensate for changes in the halogen ions in the processing bath. Prevent by adding liquid. Specifically, the relationship between the rest time, oxidative deterioration of the developing agent, and the amount of development processing and the consumption amount of the developing agent was determined in advance for each photosensitive material, and the first replenisher was replenished based on the relationship. In this case, the relationship with the amount required to compensate for the decrease in the amount of halogen ions in the development processing bath is also determined in advance, and based on these relationships, the first replenisher and the second replenisher are automatically added to the development processing bath. Refill the bath.

It is preferable to carry out the development process by the above method, but the concentration of the developing agent and halogen ions in the development bath is measured,
Based on this, the replenishment amounts of the first and second replenishers can also be determined. In addition, during steady operation, only the first replenisher is used,
Only when the development process is stopped, it is preferable to adjust the amount of the second replenisher based on the length of the stop time and add it to the development bath together with the first replenisher. Here, “steady” and “
"Stop" refers to the amount of processing per unit time that is above or below a certain value, and is determined depending on the tank capacity.

In the processing method of the present invention, following the above-mentioned development processing, ordinary bleaching processing, fixing processing or bleach-fixing processing, washing and/or stabilizing processing, and drying processing are performed. These steps are shown below.

Bleaching, fixing, and bleach-fixing processing After color development, silver halide color light-sensitive materials are usually subjected to bleaching processing. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (■), and copper (II), peracids, quinones, and nitroso compounds. for example,
Ferricyanide, dichromate, organic complex salts of iron (III) or cobalt (■), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, cyclohexanediaminetetraacetic acid Acetic acid, iminodiacetic acid, methyliminodiacetic acid, 1,3-propylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid, complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, manganates; nitrosophenols, and the like can be used.

Among these, potassium ferricyanide, aminopolycarboxylic acid iron (In) complex salts, and persulfates are particularly useful.

The aminopolycarboxylic acid iron(I) complex salts are also useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, in addition to bromide ion and iodide ion, U.S. Pat.
No. 6, No. 49-26586, JP-A-53-32735
No. 53-1623.

and thiourea compounds as shown in JP-A-53-37016, or JP-A-53-124424, JP-A-53-(15631, JP-A-53-57831, JP-A-53-53)
-32736, 53-65732, 54-52
534 and U.S. Pat. No. 3,893.858, or JP-A No. 4
No. 9-59644, No. 50-140129, No. 53-
No. 28426, No. 53-141623, No. 53-10
Heterocyclic compounds described in No. 4232, No. 54-35727, etc., or JP-A No. 52-20832,
Thioether compounds described in JP-A-55-25064 and JP-A-55-26506, quaternary amines described in JP-A-48-84440, or JP-A-49-42349 Compounds such as the thiocarbamoyls described may also be used.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

Further, a hardening agent such as an aldehyde compound or an aluminum salt may be added to the fixing solution.

In the processing of black-and-white light-sensitive materials, after development, a fixing process is performed after a stop bath or the like, if necessary. The composition of the fixer is the same as described above.

Water washing and stabilization processing The silver halide color photographic light-sensitive material developed according to the present invention is generally subjected to a water washing and/or stabilization process after desilvering processing such as fixing or bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Jo
Urnalof the 5ociety of Mo
tion Picture and Television
n [Engineers) Volume 64, P, 248-2
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this arise. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, chlorine-based disinfectants such as inthiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use disinfectants described in ``Microorganism Sterilization, Disinfection, and Anti-Mildew Techniques'' in Sanitation Techniques, and ``Encyclopedia of Antibacterial and Antifungal Agents'' edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the above treatment is 4-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but in general, 15-
20 seconds = lO min at 45°C, preferably 3 at 25-40°C
The range from 0 seconds to 5 minutes is selected.

Furthermore, in the present invention, instead of the above-mentioned washing with water, direct treatment with a stabilizing solution can be performed. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543, 58-14834, 5
No. 9-184343, No. 60-220345, 60-2
No. 38832, No. 60-239784, No. 60-2397
All known methods described in No. 49, No. 61-4054, No. 61-118749, etc. can be used.

In particular, 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-inthiazoline-3
A stabilizing bath containing -one, bismuth compound, ammonium compound, etc. is preferably used.

Further, following the water washing treatment, a further stabilization treatment is performed.
An example of this is a stabilizing bath containing formalin and a surfactant, which is used as the final bath for color photographic materials.

Processing object The processing method of the present invention can be applied to various color photosensitive materials and black and white photosensitive materials. For example, representative examples of color photosensitive materials include color negative films for general use or movies, color reversal films for slides or televisions, color paper, color positive films, and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
It can also be used in black-and-white light-sensitive materials using a mixture of three color couplers as described in J. Typical examples of black and white photosensitive materials include X-ray photosensitive materials (for indirect X-ray and direct X-ray use), lithographic photosensitive materials, black and white prints, black and white negative films, and auto-positive photosensitive materials. can be mentioned.

〔Effect of the invention〕

According to the present invention, the composition of the developer can be maintained appropriately even if the processing conditions such as the type and amount of photosensitive material to be processed, the amount of processing per unit time, moving time and rest time change. , it becomes possible to maintain stable and favorable photographic characteristics. In addition, since the second liquid used for this purpose is extremely stable, its effect does not change and there is no need to manage the liquid, and the present invention eliminates the need for management to maintain the characteristics of the developer. It becomes possible to do so.

Although the reason why the method of the present invention is able to maintain the photographic performance of the photosensitive material is not fully explained, if the amount of photosensitive material to be processed is reduced and the stop time of the development process becomes longer, The developing agent deteriorates due to air oxidation,
Since the developing ability decreases, when the developing agent is replenished in an amount proportional to the stop time to replenish the deteriorated developing agent, the concentration of halogen ions brought into the developing tank from the photosensitive material decreases, and the ions are Therefore, the excellent effects described above can be obtained by replenishing the developer using a replenisher containing a developing agent and another replenisher for adjusting the halogen ion concentration. It is estimated that

Next, the present invention will be explained with reference to Examples.

Example 1 A multilayer color photosensitive material sample was prepared on a triacetyl cellulose film support, each layer having the composition shown below.

1st layer; antihalation layer; black gelatin layer containing colloidal silver; 2nd layer; intermediate layer 2.3 gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone; low-sensitivity red-sensitive emulsion layer; Silver emulsion (silver iodide: 5 mol%)...silver coating amount 1.6
g/m' Sensitizing dye ■...6 x 10-' mole per mole of silver Sensitizing dye ■...1.5XIO-5 mole coupler EX-1... per mole of silver・Coupler EX-2: 0.04 mol per mol of silver... o, OO per mol of silver
3 mole coupler EX-3...0,000 per mole of silver
6 mol 4th layer; High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 10 mol %)...Silver coating amount 14
g/m' Sensitizing dye ■...3 x 10-5 moles per mole of silver Sensitizing dye ■...1.2810-' moles per mole of silver Coupler EX-4...・Coupler EX-2: 0.02 mol per mol of silver...0.001 mol per mol of silver
6 mol 5th layer: 6th layer same as the 2nd intermediate layer; low-sensitivity green-sensitive emulsion layer Monodispersed silver iodobromide emulsion (silver iodide: 4 mol %)...
.

Silver coating amount 1.2 g/m' sensitizing dye ■... 3 x 10-' mol per 1 mole of silver Sensitizing dye ■... I x 10-5 mol coupler EX per 1 mol of silver -5...0.05 mole per mole of silver Coupler EX-6...0,008 per mole of silver
Molar coupler EX-3...0.001 per mole of silver
5 mol 7th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide = 10 mol %)...Silver coating amount 1.
3g/m' Sensitizing dye■...2.5X10-5 moles per mole of silver Sensitizing dye■...0.8X10-' moles per mole of silver Coupler EX-7...・0,017 per mole of silver
Molar coupler EX-6...0, OO per mole of silver
3 mole coupler EX-8...0.003 per mole of silver
Mol 8th layer: yellow filter layer yellow colloidal silver and 2.5-di-t- in gelatin aqueous solution
Gelatin layer containing emulsified dispersion of octylhydroquinone 9th layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide = 6 mol%)...Silver coating amount 0, 7
g/m' Coupler EX-9: 0.25 mol per mol of silver Coupler EX-3: 0.015 mol per mol of silver
Mole 10th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide (silver iodide: 6 mol%)...Silver coating amount 0, 6
g/m' Coupler EX-9...0.06 mol per mol of silver 11th layer; 1st protective layer silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ).・
...Amount of silver coated: 0.5 g 12th gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1; 2nd protective layer A gelatin layer containing trimethylmethanoacrylate particles (diameter 1.5 μm) was coated.

In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each tube.

The compounds used to prepare the samples are as follows.

Sensitizing dye I: anhydro-5,5'-dichloro-3,3
'-di(T-sulfopropyl)-9-dityruthiacarbocyanine hydroxide pyridinium salt sensitizing dye ■: Anhydro-9-ethyl 3.3'-di(
γ-sulfopropyl)-4,5,4'-5'-dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye ■: Anhydro-9-ethyl-5,5'-dichloro-3,3'-di(T -Sulfopropyl)oxycarbocyanine/sodium salt sensitizing dye ■: Anhydro-
5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-cy(β-[β-(γ-sulfopropyl)ethoxy]ethyl)imidazolocarbocyanine hydroxide sodium salt X-2 NaU3) bUj
NaX-3 X-4 X-5 X-6 EX-7 Shi! EX-8 EX-9 CH2-Ctl SO2CH2[:0NII (C
H2) 2NHCOCH2SO2C11=(:LJV-
1 x/y=7/3 (wt ratio) After cutting the color photosensitive material produced in this way into a width of 35 m/m, a standard subject was photographed outdoors.
The treatments shown in Table 1 were performed using an automatic developing machine. Incidentally, after putting the mother liquor into the development processing bath, development was performed using the first and second replenishers.

Table 1 - Processing process (temperature 38℃) Process Processing time Tank capacity Replenishment amount *Color development 3 minutes 15 seconds 10R Table-1 Bleaching 6
Minute 30 seconds 20β 18m1 fixed
3 minutes 15 seconds 101 33 mjl! Wash with water ■
1 minute 30 seconds 6β -Wash ■ 1 minute 3
0 seconds 6β 27 ml stable 4
0 seconds 642 33+nj2*: Photosensitive material 35 m/m width 1 m length In the above processing steps, water washing (■) and (2) were performed using a countercurrent water washing method from ■ to ■. next,
The composition of each treatment liquid is described.

(Color developer) Mother solution (g) First replenisher (g) Diethylenetriamine 1.0 1.1-1-Hydroxyethyl pentaacetate 2.0 2.2 Sodium sulfite 1,1-diphosphonate 4.3 4 .4 Potassium carbonate 3 (1,032,Q Potassium bromide
1.4 0.7 Potassium iodide 1.3
ff1g -hydroxyamine 2.4
2.64-(N-ethyl-4,55,5 N-β-hydroxyethylamino)-2-methylaniline sulfate was added to 1β 11 pH 10,0
010,05 Color development second replenisher> Diethylene triamine 0.5g Pentaacetic acid Potassium bromide 3.0g Potassium iodide 6.0mg Add water to 11 pH (Bleach solution) Mother liquor (g) Replenisher (g) Ethylenediamine tetra 100 110 acetic acid 2
Iron ammonium salt ethylenediamine 4 1011 Disodium acetate salt Aqueous ammonia ? -+nI! 5ml ammonium nitrate 10.0 12.0g ammonium bromide 150 170 Add water
il IJ pH6,05,8 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediamine tetra 1.0 1.2 Acetate disodium salt Sodium sulfite 4.0 5.0 Sodium bisulfite 4.6 5.8 Ammonium thiosulfate Aqueous solution (70%) 175 ml 200 m
Add I2 water to 1βpH6,
66,6 Aqueous solution> Mother liquor (g) Replenisher (g) Ethylenediamine 4 0,5 0.5 Disodium acetate salt Sodium hydroxide pH adjustment pH 7,07,
0 (Stable liquid) Mother liquid (g) Replenisher liquid axis) Formalin 2.0mj! 3.0mj
! (37%w/v) Polyoxyethylene 0.3 0.45-p-
Monononylphenyl ether (average degree of polymerization 10) 2.2 m of photographed photosensitive material processed into JIS 135 size by adding water and repeating circulation for 10 hours to adjust the temperature of the processing solution and resting for 14 hours. was treated as one unit, and the amounts shown in Table 1 were distributed approximately evenly during the temperature adjustment period. Further, addition of replenisher and the like was carried out every time the treatment of one unit was completed.

At the start of processing and at the end of each process, the color temperature was adjusted to 4800°K using a filter using a tungsten light source, and the color temperature was adjusted to 4800°K using a filter. After processing the color photosensitive material, the density was measured. Shown in Table 2.

All values are shown as differences from the characteristic values when treatment was started with a new solution, and the farther the value is from 0, the greater the change, indicating that the characteristics are less stable.

Dmin indicates the minimum density, and the relative sensitivity and gradation were determined as follows.

Relative sensitivity: 0.2 from the lowest concentration in fresh solution treated samples
The exposure amount at which the density increased was determined, and the difference between the density at this exposure amount and the minimum density for each treated sample was defined as the relative sensitivity.

Gradation: The difference between the density value at the above exposure amount and the density value at the point where the exposure amount having a logarithmic value of 1.5 was added to that exposure amount was defined as the gradation.

Comparative Example (1) shows that good results were obtained when the daily treatment amount was sufficient, and that the replenisher prescription and replenishment amount were appropriate. In Comparative Examples (2) to (8), the daily processing amount was reduced to 1/6. Comparative Examples (2) to (4) in which the amount of replenishment was simply increased did not result in small changes in all three characteristics. On the other hand, the present invention (5) has little change in the three characteristics, indicating that it is superior to the comparative example. The replenishment amount of the second replenisher in Nα5 of the present invention was determined based on the analytical values of potassium bromide and potassium iodide at the end of the treatment in Comparative Examples No. 3, No. 4, and No. 4.

Example 2 Continuous processing was carried out using the photosensitive material mother liquor, first replenisher, and second replenisher used in Example 1 under the following conditions. The tea liquid was replenished by detecting the number of tea leaves to be processed and the number of tea leaves to be processed within a certain period of time using the film insertion part, and replenishing the amount determined based on the following calculation.

Processing conditions: The following number of photographed films (length 1.1 m) were processed. The processing liquid circulation time for daily temperature adjustment was 10 hours.

1st day: 60 pieces, 40 pieces, 20 pieces 2nd day; 40 bottles, 30 pieces, 10 pieces 3rd day: 20 pieces 10 pieces 10 pieces 4th day: 10, 6, 4 Day 5; 6 books 6 books 0 books Day 6; 6 books 6 books 0 books 7th day; rest After the 8th day, the above days 1 to 7 It was repeated.

Replenishment method (present invention) (1) Every time the number of detected films to be processed becomes two,
Replenish 80 ml of replenishment solution by operating the replenishment metering pump for a certain period of time.

(2) Every 5 hours, the cumulative number of detections (
X) into the following equation, the replenishment amounts of the first replenisher and the second replenisher were determined, and each was replenished using a metering pump.

Replenishment amount of the first replenisher (A) = -(4O-x) x ml1 Replenishment amount of the second replenisher (B) = -(40-x) x ml However, in the case of X≧40, I decided not to replenish either of them.

In addition to the method of the present invention described above, for comparison, a method of the present invention in which the second replenisher was not added was also used. The results of the 4-week treatment are shown in Table 3.

Note that the testing method for photographic properties was based on Example 1.

From this result, the method of the present invention shows that the changes in the three characteristic values are small (
It can be seen that the performance is stable. In the comparative example, the amount of replenishment per bottle is increased when the throughput is small, but all three characteristics are significantly increased.

Example 3 A color photographic material was prepared by coating the following layers 1 to 11 in multiple layers on a paper support laminated on both sides with polyethylene. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating weights in g/m'' are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (antihalation layer) Black colloidal silver...0.10 Gelatin...2.0 2nd layer (low sensitivity red sensitive layer) Spectrally sensitized with red sensitizing dyes (*5 and *4) Silver iodobromide emulsion (silver iodide 3.5 mol%, average grain size 0.7μ)
・・Silver 0.15 gelatin
...1.0 cyan coupler (*3-1) ・
・・0.20 cyan coupler (*3-2) ・・
0.11 Anti-fading agent (*2) ...0.15
Coupler solvent (*18 and *1)...0.06 3rd layer (
Highly sensitive red sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (*5 and 4) (silver iodide 8.0 mol%, average grain size 0.7μ)
・・Silver 0.10 gelatin
...0.50 cyan coupler (*3-1)
...0.07 cyan coupler (*3-2) ...
・0.04 anti-fading agent (*2) ...0.0
5 Coupler solvent (*18 and *1)...0.02 4th layer (intermediate layer) Yellow colloidal silver...-0,02 Gelatin...1°00 Color mixing inhibitor (*1'4)...・0.08 Color mixture inhibitor solvent (*13) ...0.16 Polymer latex (*6) ...0.10 5th layer (low sensitivity green sensitive layer) Green sensitizing dye (*12) Silver iodobromide emulsion spectrally sensitized with (silver iodide 2.5 mol%, average grain size 0.4μ)
・・Silver 0.20 gelatin
...0.70 magenta coupler (*11) ・
...0.40 anti-fading agent Δ (*10) ...
0.05 Anti-fading agent B (*9)...0.
05 Anti-fading agent C (*8) ...0.02
Coupler solvent (*7)...0.15 6th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 3.5 mol% , average particle size 0°9μ)
・・Silver 0.20 gelatin
...0.70 magenta coupler (*11)
...0.40 anti-fading agent Δ (*10) ...
・0.05 anti-fading agent B (*9) ...0
．． 05 Anti-fading agent C (*8) ...0.0
2 coupler solvent (*7)...0.15 7th
Layer (yellow filter layer) Yellow colloidal silver...0.20 Gelatin...1.00 Color mixing inhibitor (*14)...0.06 Color mixing inhibitor solvent (*13)...0.24 Eradiation Preventive dye (*21, *22) 8th layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*16) (silver iodide 2.5 mol%, average grain size 0.5μ)
・・Silver 0.15 gelatin
...0.50 yellow coupler (*15)
...0.20 coupler solvent (*18) ...
0.05 9th layer (high sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*16) (silver iodide 2.5 mol%, average grain size 1.4 μ)
・・Silver 0.20 gelatin
...0.50 yellow coupler (*15)
...0.20 coupler solvent (*18) ...
0.05 10th layer (ultraviolet absorption layer) Gelatin...1.50 Ultraviolet absorber (*19)...1.0 Ultraviolet absorber solvent (*18)...0.30 Color mixing prevention agent (* 17)
...0.08 11th layer (protective layer) Fine grain silver chlorobromide (silver chloride 77 mol%, average particle size 0
．． 2μ) ...0.07 gelatin
...1.0 hardener (*20)
...0.17 The compounds used here are as follows: * 1 Dioctyl phthalate * 2 2-(2-Hydroxy-3-sec-butyl-5-t-butylphenyl)benzotriazole * 3 -12-Cα-(2,4-di-t-amylphenoxy)butanamide-4,6-dichloro-5-ethylphenol*3-24-chloro-2-(2-chlorobenzamide)
-5-(α-(4-t-amyl-2-chlorophenoxy)octanamide] Phenol* 4 5.5'-dichloro-3,3'-di(3-sulfobutyl)-9-ethylthiacarbonylcyanine Na Salt* 5 Triethylammonium-3-(2-(2-C
3-(3-sulfopropyl) naphtho(1,2-d)thiazolin-2-ylidenemethyl]-1-butenyl)-3-naphtho(1,2-d)thiazolino]propanesulfonate* 6 polyethyl acrylate* 7 phosphorus Acid trioctyl ester*8 2.4-di-t-hexylhydroquinone*9 Di(2-hydroxy-3-t-butyl-5-
methylphenyl)methane*103.3.3', 3-tetramethyl-5°6.5'
, 6'-tetrapropoxy-1゜1'-bisspiroindane *11 *12 5,5'-diphenyl-9-ethyl-3,3'
-Disulfopropyloxacarbocyanine Na salt *13 Phosphoric acid-〇-cresyl ester *14 2,4
-di-t-octylhydroquinone *15 α-pivaloyl-α-[:(2,4-dioxo-1-benzyl-5-ethoxyhydantoin-3-yl)-2-chloro-5-(α-2,4 -Dioxo-amylphenoxy)butaneaminocoacetanilide*16 Triethylammonium 3-(2-(3-benzylrhodanine-5-4')den)-3-benzoxazolinyl]propanesulfonate*17 2.4 -Di-5ec-octylhydroquinone*181J-acid trinonyl ester*195-chloro-2-(2-hydroxy-3-t-butyl-5-t-octyl> Phenylbenztriazole*20 1.4-bis(vinylsulfonyl) acetamido)ethane *21 *22 bLJ3K 5L1
The silver halide color reversal photographic light-sensitive material prepared as described above was cut into a width of 8.250 m, imagewise exposed, and subjected to the following processing using an automatic processor.

First rinse 40 seconds 33℃ 1000m 1 Reversal exposure 100LLIX 1 second color development 2
Minutes 15 seconds 38℃ 330ml water washing
45 seconds 33℃ l0GO+r+e Bleach fixing 1 minute 38℃ 220mβ 2nd rinse■ 30 seconds 33℃ □Second rinse■
30 seconds 33℃ □Second rinse■ 30
Seconds 33℃ 330m! ! The amount of replenishment during the above steps indicates the amount of replenishment per ml of light-sensitive material. The replenishment method for the second rinsing bath was a so-called countercurrent replenishment method in which the tank was refilled, the overflow from the tank was led to the tank, and the overflow from the tank was led to the tank.

Table 3 shows the replenishment amounts of the first black-and-white developer replenisher and the second black-and-white developer replenisher.

Processing solution composition Black and white developer Tank solution (mother liquor) First replenisher Nitrilo-N, N, N- Trimethylenephosphonic acid, pentatrilam salt 0.6 g 0.6 g Diethylenetriaminepentaacetic acid, pentasodium salt 4.0 g 4.0 g
Potassium sulfite 30.0g 30.0
g Potassium thiocyanate 1.2g 1.2
g Potassium carbonate 35.0g 35.
0g Hydroquinone monosulfonate potassium salt 25.0g 25.0g
Diethylene glycol 15.0ml 15.
0mβ1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0g 2.0g Potassium bromide 0.5g - Potassium iodide 5.0mg - Add water
1β 1β pH 9,709,70 Black and white development second replenisher Nitrilo-N,N,N-1-limethylene 0.6
Hyphosphonic acid pentasodium salt diethylenetriaminepentaacetic acid 4.0 g Pentasodium salt Potassium sulfate 68.0 g Potassium iodide 5.0 mg Potassium bromide 0.4 g Potassium thiocyanate 1.2 g Add water
11pH (KOH)
8.0 First rinse liquid
Both mother liquor and replenisher are monosodium phosphate
2.0g ethylenediaminetetrakis (methylenephosphonic acid) 2.0
g Add water 1000m
12p) I 7.0 Color developer Tank liquid Replenisher benzyl alcohol: 15. Omj! 18.8mJ diethylene glycol 12. Orn 1 15.0m
13.6-Sitia 1. 8-octanediol 0.2g 0.25g
Nitrilo-N,N,N-)rimethylenephosphonic acid pentasodium salt 0.5g 0.63
gDiethylenetriaminepentaacetic acid, pentasodium salt 2.0g 2.5gSodium sulfite 2.0g 2.5g
Potassium carbonate 25.0g 31.3
g Hydroxylamine sulfate 3.0g 3.8g
N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 6.3g Potassium bromide 0.5g -Potassium iodide 1. Omg - add water
1I11j2p H10,2510,4
0 Bleach-fix solution Both tank solution and replenisher are 2-mercapto-1,3°4-triazole 1. Og ethylenediaminetetraacetic acid disodium trihydrate 5.0g ethylenediaminetetraacetic acid Fe(III) ammonium hydrate 80.0g sodium sulfite 15.0g sodium thiosulfate (700g/It liquid) 160. O
m R glacial acetic acid 5. Om
Add water 11p 8
6.50 Add 0.2 g of ethylenediaminetetraacetic acid disodium salt to both the second rinse solution tank solution and the replenisher solution to 11 pH (NaO
)1) 8.0 In order to adjust the temperature of the treatment solution, the treatment was repeated by repeating circulation for 12 hours and stopping at 12 o'clock. The amount of inverted color paper processed per day is as shown in Table 3, and the processing was carried out to be as uniform as possible during the 12-hour temperature adjustment. The total number of processing days is shown in Table 3.

Processing the color photographic material subjected to wedge exposure of 250 CMS at the start of continuous processing and at the end of each processing,
Photographic characteristic values were measured. The results are shown in Table-3.

As shown in Table 4, similar to Example 1, when the daily processing amount is small, black and white developer replenishment was performed only with black and white developer replenisher compared to comparative examples (experiments Nα7 to 9). In the example (No. 10.11) according to the present invention in which the first replenisher and the second black-and-white developing replenisher were replenished, there was little variation in photographic characteristics before and after continuous processing, and stable processing could be performed.

Procedural amendments Commissioner of the Patent Office Black 1) Akio Yu 1, Indication of the case 1985 Patent Application No. 227487 2, Title of the invention Processing method for silver halide photographic light-sensitive materials 3, Person making the amendment Relationship with the case Application Person name (520) Fuji Photo Film Co., Ltd. 4, Agent 6, Subject of amendment Column 1 of the detailed explanation of the invention in the specification, 4th line from the bottom of page 9 of the specification, “(hereinafter abbreviated as %). )".

2. “Disappearance due to oxidative deterioration” on page 58, line 2 of the same book.
is corrected as ``disappearance due to oxidative deterioration''.

3. On page 21 of the same book, line 4 from the bottom, "in the case of thiosulfate" is amended to "in the case of thiosulfate".

4. Adjust the “pH” on page 58, line 7 of the same book to rpH 7.o.”

5. Change “aqueous solution” in the 7th line from the bottom of page 40 of the same book to “
Correct as ``washing liquid''.

6. "Table 3" on page 40, line 3 of the same book is corrected to "Table 4."

7. “Fe(III)” on page 63 of the same book, line 8 from the bottom
・Ammonium-"WorFe(III) ・Ammonium-" is corrected.

8. Change “-3” to “-4” in the 7th line from the bottom of page 64 of the same book.
and correct it.

9. Change “Table-3” from the 5th line from the bottom of page 64 of the same book to “Table-3”.
4”.

10, “Table-31” in the second line from the bottom of page 64 of the same book as “Table-
4”.

11. In Table 4 on page 65 of the same book, the gradation change term of Experiment No. 7, the value of R, “-10,04”, is changed to r+0.04.
Correct it with J.

Date 1, Month, Day 1, 1988, Incident Indication: Patent Application No. 227487, 1986
No. 2, Title of the invention Processing method for silver halide photographic light-sensitive materials 3, Person making the amendment Relationship to the case Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Initiator 6, Subject of amendment Detailed explanation of the invention in the specification (1) "Trimethyl methanoacrylate" in line 5 on page 9 of the specification is corrected to "polymethyl methacrylate."

(2) "(a) 5" in Table 1 on page 44 of the same book is corrected to "5".

(3) The compound of "Formula 21" on page 58 of the same book is corrected as follows.

(4) "Ammonium thiosulfate" on page 63, line 16 of the same book is corrected to "ammonium thiosulfate."

Claims (1)

[Claims] When continuously developing exposed silver halide photographic materials, it is used as a developer replenisher to replenish the development bath.
A silver halide photographic light-sensitive material characterized in that the processing bath is replenished with a first developing replenisher containing a developing agent and a second developing replenisher containing a halide ion-releasing compound but substantially free of a developing agent. Processing method.