JPH1090845A - Development processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate unevenness in drying and developing and to enhance processing stability by raising pH in the surface of the photosensitive material to a specified value or more and replenishing the developing agent in a concentration higher than the initial developing solution. SOLUTION: The pH in the surface layer of the silver halide photosensitive material is set to >=7.5, preferably, >=8.0 and the developing agent is replenished in a concentration higher than that of the initiation solution, and in this case an antifoggant or a hardener to be consumed by the processing of the photosensitive material is replenished by the same amount as the consumption or less. The pH in the surface layer is adjusted by adding an inorganic or organic alkaline substance into at least one of coating liquids for an emulsion layer or a surface protective layer or another layer. The swelling rate of this photosensitive material is <=250%, preferably, <=200%, further more preferably, <=180%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which is excellent in rapid processing suitability, drying unevenness, development unevenness, and processing stability (oxidation resistance). The present invention relates to a method for developing a material.

[0002]

2. Description of the Related Art Black-and-white photosensitive materials (X-ray, for printing plate making, for micro and for negative) are developed with an alkaline developing solution containing a hydroquinone as a developing agent and a 3-pyrazolidone or aminophenol compound as an auxiliary developing agent. Has been processed. However, hydroquinone has drawbacks in that safety issues are becoming more apparent from a biological and toxicological point of view, and the wastewater treatment load is high. It is known that ethylene diols such as ascorbic acid have no problem in safety and function as a developing agent.However, ascorbic acid-containing developer is hydrolyzed in higher alkalinity compared to hydroquinone developer to convert acid. It forms and lowers the pH, losing development activity more and more. Furthermore, in the recent low replenishment processing, the development activity is further reduced due to air oxidation of the developing agent and processing fatigue. Further, in a process in which the development activity must be increased by high-speed processing or the like, development unevenness or the like is likely to occur, which is a serious problem.

[0003] Sulfite is generally known as an antioxidant (preservative) of a developing agent, and is present in a large amount in a black-and-white developer. On the other hand, sulfite is a silver halide salt. It cannot be added more than necessary because it is dissolved in a developing solution and is reduced in the developing solution to cause silver contamination (silver sludge). Silver dirt is further degraded with low replenishment.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to develop a silver halide photographic material which has rapid processing suitability, has no drying unevenness and development unevenness, and has excellent processing stability (oxidation resistance). It is to provide a processing method.

[0005]

The above objects of the present invention have been attained by the following constitutions.

(1) A method for developing a silver halide photographic light-sensitive material comprising a support provided with a hydrophilic colloid layer including a light-sensitive silver halide light-sensitive layer. A method for developing a silver halide photographic material, wherein the developing agent is replenished with a solution having a pH of 7.5 or higher and a developing agent concentration higher than the starting solution.

(2) The method according to (1), wherein the antifoggant or the hardening agent consumed in the processing of the silver halide photographic light-sensitive material is replenished in the same amount as or less than the consumed amount, respectively. A method for developing a silver halide photographic material.

(3) The method for developing a silver halide photographic light-sensitive material as described in (1) or (2) above, wherein a solid processing agent containing a developing agent and tableted by compression molding is replenished.

(4) A method for developing a silver halide photographic light-sensitive material comprising a support provided with a hydrophilic colloid layer including a light-sensitive silver halide light-sensitive layer. Is 250% or less, and the developing agent is replenished with a liquid having a higher developing agent concentration than the starting solution.

(5) The method according to the above (4), wherein the antifoggant or the hardening agent consumed in the processing of the silver halide photographic light-sensitive material is replenished in the same amount as or less than the consumed amount, respectively. A method for developing a silver halide photographic material.

(6) The method for developing a silver halide photographic material as described in (4) or (5) above, wherein a solid processing agent containing a developing agent and tableted by compression molding is replenished.

The present invention will be described in more detail. 1 of the present invention
As an embodiment, the pH of the film surface of the silver halide photographic light-sensitive material is 7.5 or more, and particularly preferably pH 8.0 or more. As a means for adjusting the pH of the film surface, an inorganic or organic alkali substance may be added to at least one of the coating solution for the emulsion layer, the coating solution for the surface protective layer, and the other coating solution for the photographic layer. Good. The method for measuring the pH of the film surface of a silver halide photographic light-sensitive material is as follows: temperature 25 ° C .;
% In an air atmosphere for 30 minutes. Then, a glass electrode type hydrogen ion concentration meter (H
M.12A), apply the sensor part to the part where pure water (adjusted to pH 7.0) was applied to the surface of the sample, read the display for 3 minutes, and read it for the film surface pH of the silver halide photographic material. Value.

In another embodiment of the present invention, the swelling ratio of the silver halide photographic material of the present invention is 250% or less, preferably 200% or less, more preferably 180% or less. The swelling ratio is a ratio of the swelling ratio to the film thickness (the thickness of the entire hydrophilic colloid layer) expressed as a percentage. The swelling thickness is an increase in the swelling thickness measured by dropping distilled water at 25 ° C. onto a photosensitive material and then allowing the photographic material to stand at 25 ° C. for 5 minutes.

The developing solution used in the developing method of the present invention preferably contains, as a developing agent, a compound represented by the following general formula (1) which is generally known as reductones. Further, it is preferable to use a solid processing agent for the developer of the present invention.

[0015]

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Wherein R ₁ and R ₂ are each a hydroxy group,
Amino group (as a substituent, an ethyl group, an n-butyl group,
A hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms, an acylamino group (acetylamino group, benzoylamino group, etc.), an alkylsulfonylamino group (methanesulfonylamino group, etc.), an arylsulfonylamino group (benzenesulfonylamino group, represents a p-toluenesulfonylamino group, an alkoxycarbonylamino group (such as a methoxycarbonylamino group), a mercapto group, or an alkylthio group (such as a methylthio group or an ethylthio group). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group. X is 5
A group of atoms necessary for forming a 6-membered ring, preferably consisting of a carbon atom, an oxygen atom or a nitrogen atom;
₁ , _Two vinyl carbon atoms and the carbonyl carbon atoms substituted by R2 form a 5- to 6-membered ring together. As a configuration example of a X -O -, - C- (R 3) (R 4) -, - C
_{(R 5) =, - C} (= O) -, - N (R 6) -, - formed by combining the N =.

However, R ₃ , R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy, carboxy or sulfo group can be mentioned as a substituent). ), A hydroxy group and a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring.

Examples of the 5- or 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring,
Examples include an azacyclohexenone ring and a uracil ring. Preferred examples of the 5- to 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

The compound represented by the general formula (1) may form a salt with lithium, sodium, potassium, ammonium and the like.

Specific examples of the compound represented by the general formula (1) are shown below.

[0021]

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[0022]

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[0023]

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Preferred among the above specific examples are ascorbic acid or erythorbic acid (stereoisomer) (1-1)
It is. In the present invention, it is preferably at least 30%, more preferably at least 50% of the total weight of the solid treating agent of the compound represented by the general formula (1). The amount added to the treatment liquid is not particularly limited, but is practically 0.1 to 1 liter per treatment liquid.
A value within the range of 100 g, preferably 0.5 to 60 g is desirable for obtaining the effect of suppressing the formation of white precipitate. The treatment liquid of the present invention may contain only one kind of the compound represented by the general formula (1), or may contain two or more kinds thereof.

The developer of the present invention may contain the following developing agents in addition to the reductones. Examples of black-and-white developing agents include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, etc. 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1- Phenyl-4-methyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1
-Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), 1-allyl-
3-aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p
-Amino-m-methylphenyl) -3-aminopyrazoline, pyrazolones (eg, 4-aminopyrazolone), and the like, or a mixture thereof.

The developer of the present invention containing the compound represented by the general formula (1) contains a sulfite. The amount of sulfite in the developing solution of the present invention is 0.05 mol / l or more and 0.3 mol / l.
It is preferably less than 0.1 mol / l and less than 0.3 mol / l.

In the development processing method of the present invention, when the developing solution contains an antifoggant and / or a hardener, the antifoggant (for example, an azole organic antifoggant, that is, an indazole type, an imidazole type, Benzimidazole, triazole, benztriazole, tetrazole, thiadiazole, etc.) or hardener (for example, dialdehydes such as glutaraldehyde) is the same amount as the consumption amount during the running process, or Replenish less than consumed.

In addition, the developing solution of the present invention may be used as a buffer (for example, carbonate, boric acid, borate, alkanolamine, etc.), an alkaline agent (for example, carbonate), a solubilizing agent (polyethylene glycols, and the like). Esters, etc.), pH adjusters (eg, organic acids such as citric acid), sensitizers (eg, quaternary ammonium salts), development accelerators, surfactants, and calcium mixed in tap water used in the processing solution. A masking agent for masking ions, such as sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate may be contained. In the present invention,
Furthermore, silver stain inhibitors, for example, compounds described in JP-A-56-24347 can be used.

The fixing solution according to the present invention is preferably prepared by preparing a solid processing agent and dissolving it. The fixing agent preferably contains a thiosulfate. The thiosulfate is specifically used as a salt of lithium, potassium, sodium, or ammonium. Preferably, a fixing solution having a high fixing speed can be obtained by using ammonium thiosulfate and sodium thiosulfate.

In addition, iodide salts and thiocyanates can also be used as fixing agents. The fixing solution used in the present invention contains a sulfite. As sulfites,
Solid lithium, potassium, sodium, ammonium salts and the like are used.

The fixing solution used in the present invention may contain a water-soluble chromium salt or a water-soluble aluminum salt.
Examples of the water-soluble chromium salt include chrome alum and the like.
Examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride.

The fixing solution used in the present invention contains acetate ions. The type of acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution.However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used. Sodium salts and ammonium salts are preferred.

Further, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof may be contained.

These salts include, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium bitartrate, sodium tartrate, ammonium bitartrate, ammonium bitartrate Potassium, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate,
Preferred examples include lithium, potassium, sodium, and ammonium salts represented by ammonium succinate and the like.

Among the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. Examples of other acids include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid, and malic acid. Acids and salts such as carboxylic acids.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of the fixing accelerator include thiourea derivatives, alcohols having a triple bond in the molecule, thioethers and the like.

The fixing solution has a pH of 3.8 or more, preferably 4.
2 to 5.5.

Further, the replenishment amount during the processing according to the present invention is important in the sense that the amount of waste liquid is reduced to 15 ml / 4 or less for both the developing solution and the fixing solution. Also increases the effect.

Next, the solidification (solidification) of the photographic processing agent will be described. In order to solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. Or any other means such as forming a coating layer (see JP-A-4-29136 and JP-A-4-8136).
No. 5535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341).

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. Compared to a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet, there is an advantage that solubility and storage stability are improved, and as a result, photographic performance is stabilized.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

The method for producing a tablet processing agent is described, for example, in JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent No. 1,213,808 and the like.
For example, Japanese Unexamined Patent Publication Nos.
No. 3, 3-39735 and 3-39939 can be produced. Further, the powder treating agent can be prepared by the method described in, for example, JP-A-54-133332, British Patent Nos. 725,892 and 729,862 and German Patent 3,733,861. Can be manufactured.

The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0g
/ Cm ³ in terms of the strength of the resulting solid,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

Although the solid processing agent used in the present invention may fall within the scope of the present invention, it is within the scope of the present invention that only one part of a certain processing agent is solidified, but it is preferable that all the components of the processing agent be solidified. is there. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine, and the built-in water tank is preferable in terms of space saving and the like.

When the developer is solidified, all of the alkali agent, reducing agent, etc. are converted into solid processing agents, and in the case of tablets, at least three agents can be used, that is, one agent can be used. When divided into solid processing agents, it is preferable that these tablets and granules are packaged in the same manner.

In the present invention, as the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783 and 63-975.
No. 22, Japanese Utility Model Laid-Open No. 1-85732, etc., but any method may be used as long as the function of supplying the tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powders, see JP-A-62-81964, 6
3-84151, JP-A-1-292375, and the gravity drop method described in JP-A-63-105159 and JP-A-63-105159.
There is a known method using a screw or a screw described in 195345 or the like, but the method is not limited thereto.

However, in a preferred method, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent weighed in advance and divided and packaged is opened according to the processing amount of the photosensitive material. There is a way to take it out. Specifically, the solid processing agent is sandwiched and stored in a predetermined amount, preferably in a single replenishment amount, in a package composed of at least two packaging materials, and the package is separated in two directions or the package is separated. A part is opened to make it ready for removal. The solid processing agent in a removable state can be easily supplied to a processing tank having a filtering means by natural fall. Since a predetermined amount of the solid processing agent is stored in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is shut off, the moisture proof is guaranteed unless opened.

As an embodiment, a configuration is conceivable in which a package made of at least two packaging materials is adhered or adhered to each other so as to sandwich the solid processing agent so as to be able to separate the periphery of the solid processing agent. . By pulling each packaging material sandwiching the solid processing agent in a different direction, the contact surfaces adhered or adhered are separated, and the solid processing agent can be taken out.

As another embodiment, a configuration is conceivable in which at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term “opening” as used herein refers to a cut or break that leaves a part of the packaging material. As an opening method, the solid processing agent is forcibly extruded by applying a compressive force from the non-opening side package to the openable package through the solid processing agent, or the package is opened. It is conceivable that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting information on the processing amount. The supply stop signal is obtained by detecting information indicating that a predetermined amount of supply has been completed. In addition, when the processing agent is packaged and opening is required, a driving unit for separating or opening based on the obtained supply start signal operates, and a driving unit for separating or opening based on the supply stop signal is provided. Can be controlled to stop.

In the developing process, the developing agent is replenished with a developing agent having a higher developing agent concentration than the starting solution. As a result, it is possible to prevent consumption due to processing and deterioration in developability due to air oxidation.

The place where the solid processing agent of the present invention is charged may be in a processing tank, but is preferably in communication with a processing section for processing a photographic material, and a processing liquid flows between the processing section and the processing section. And a structure in which there is a constant processing solution circulation amount with the processing unit and the dissolved components move to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

Generally, the temperature of an automatic developing machine is controlled by an electric heater so that the processing solution is controlled. As a general method, a heat exchange unit is provided in the auxiliary tank connected to the processing layer, a heater is installed, and a pump is arranged in this replenishment tank so that the liquid is sent from the processing tank at a constant circulation amount and the temperature is kept constant. I have.

Usually, a filter is disposed for the purpose of removing foreign substances that are mixed in the processing liquid or generated by crystallization, and play a role of removing foreign substances.

It is the most preferable method to supply the solid processing agent to a place where the temperature is controlled, such as the auxiliary tank, which is in communication with the processing section. This is because the insoluble components of the input processing agent are blocked from the processing unit by the filter unit, so that the solid content can be prevented from flowing into the processing unit and adhering to the photosensitive material, etc., and the solubility of the solid processing agent is very high. It will be good.

In the case where a processing agent charging section is provided together with the processing section in the processing tank, it is preferable to devise a shield or the like so that the insoluble portion does not directly contact the film or the like.

As the materials of the filter and the filtration device, those used in general automatic developing machines can be used in the present invention, and the special structure and material do not influence the effects of the present invention.

In the present invention, the circulation frequency of the treatment liquid circulated by the circulation means is preferably 0.5 to 2.0 times / min, particularly 0.8 to 2.0 times / min, and more preferably 1.0 to 2.0 times / min.
2.0 times / min is preferable. As a result, the dissolution of the solid processing agent is promoted, and the occurrence of clusters of the high-concentration liquid can be prevented, the occurrence of uneven density of the processed photosensitive material can be prevented, and the occurrence of insufficiently processed photosensitive material can be prevented. Can be prevented. Here, the number of circulations indicates the flow rate of the circulated liquid, and the time when the liquid amount corresponding to the total liquid amount in the processing tank flows is defined as one time.

In the present invention, the solid treating agent is added to each treatment tank separately from the replenishing water, and the replenishing water is supplied from a refilling tank.

The antifungal means of the water refill tank in this case will be described. If the exchange rate in the rehydration tank is reduced and the residence time of the water is prolonged, scales are generated, and after two to three weeks, there is a problem that the water rots and an odor is generated. Further, if the generated scale is replenished as it is, it adheres to the surface of the photographic light-sensitive material or solid processing agent, and in the case of a developing tank, uneven development, and in the case of a fixing tank, poor fixing, resulting in a significant problem that the commercial value is significantly reduced. There is. Therefore, it is necessary to perform regular cleaning to remove the scale, which is very troublesome. Therefore, the water supply tank of the present invention has a fungicide. This antifungal means can be achieved by at least one means selected from the following group.

(Group) 1) Chelating agent adding means 2) Antifungal agent adding means 3) Deionizing processing means 4) Ultraviolet irradiation means 5) Magnetic processing means 6) Ultrasonic processing means 7) Electrolytic sterilizing means 8) Silver ion Release means 9) Air foaming means 10) Active oxygen release means 11) Means by contact with porous material Means of adding harmless other fungi to prevent harmful bacteria from multiplying These means will be specifically described. . As the chelating agent and the bactericide used as the fungicide in the present invention, known chelating agents and bactericides can be arbitrarily used.

Examples of the chelating agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), 2-hydroxy-4-sulfophenol, 2-hydroxy-3 , 5-disulfophenol is preferred, and bactericides are preferably phenolic compounds, thiazole compounds and benzotriazole compounds. Specifically, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazoline-
Preferred compounds include 3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, sodium o-phenylphenol, and benztriazole.
If these compounds are packaged together, they are preferably in the form of tablets, and if they are divided and weighed in advance, they are preferably individually packaged in an amount to be charged at one time.

The means for adding these may be manually added by the pharmacist, but preferably the solid processing agent supply device of the present invention is installed, and it is more preferable to add the solid processing agent supply device by using the detector. When water is replenished to a certain amount in the tank, it is preferable to automatically add water from the viewpoint of maintenance-free.

The means for modifying water with an ion exchange resin can be carried out based on the means described in JP-A-61-131632.

As the ion exchange resin, various known cation exchange resins (strongly acidic cation exchange resin, weakly acidic cation exchange resin) described in, for example, Published Technical Report, Publication No. 90-473.
And various anion exchange resins (strongly basic anion exchange resins)
And these can be used alone or in combination. Usually, it is preferable to use a strongly acidic H-type cation exchange resin and a weakly basic OH-type anion exchange resin. It may be placed in a water refill tank or the water may be improved elsewhere.

Preferred ion exchange resins for strong acid include DIAION SK1B SK102, SK104, S
K106, SK110, SK112 and SK116 (Mitsubishi Kasei Co., Ltd.). Preferred OH-type strong basic anion exchange resins are DIAION PA406 and PA40.
8, PA412, PA416 and PA418 (Mitsubishi Kasei Co., Ltd.).

Means for irradiating ultraviolet rays is disclosed in
No. 63939 can be implemented. As the ultraviolet irradiation device, a device manufactured by Kindai Bio Research Laboratories (head office Kobe City) is preferably used in a small size. The means for applying a magnetic field according to the present invention can be implemented by the means described in JP-A-60-263939. The means for applying ultrasonic waves can be implemented by the means described in JP-A-60-263940. Means for applying electrolysis is disclosed in
It can be carried out by the means described in Japanese Patent No. 22468.
Further, the means for releasing silver ions include a means for putting silver foil or a silver plate in a water replenishing tank, a means for coating the inner wall with silver, and a means for putting a silver ion releasing compound.

On the other hand, the air foaming means may be a very simple means for blowing air bubbles into the water refill tank, and is appropriately selected according to the size of the water refill tank. Means for preventing the generation of scale and microorganisms are the above 1), 2), 3), 7) and 8) from the viewpoint of compactness and economy, and more preferably 1), 3) and 8). Selected.

The silver ion releasing compound of the means 8) includes silver chloride, silver bromide, silver iodide, silver oxide, silver sulfate, silver nitrate, silver acetate, silver oxalate, silver behenate, silver maleate and the like. Organic acid silver and the like are mentioned as specific examples.

These silver compounds include those having a SiO ₂ —Na ₂ O-based glass body having a network structure as a chemical structure as a base structural component, and a SiO ₄ tetrahedron having a methane type structure and an Al ₄
A zeolite body having a three-dimensional skeleton structure in which O ₄ tetrahedrons share one oxygen atom with each other and containing the silver compound is preferably used.

These silver compounds and zeolite bodies and glass bodies containing the compounds can be obtained as commercial products, such as Bio-Sure SG manufactured by Kinki Pipe Giken Co., Ltd. Opogens (Switzerland)
Tablets) and Zeomic (Zemic) manufactured by Sinanen Zeomic Co., Ltd.
omic) and the like.

Further, the silver compound and the zeolite body and glass body containing the compound can be used in various shapes. For example, it can be in the form of a powder, a sphere, a pellet, a sensation or a filter, or it can be used by being entangled with fibers of cotton, wool, polyester or the like. Specific examples of these include Saniter 30 (manufactured by Kuraray Co., Ltd.).

Further, it is preferable to use the silver compound or the zeolite or glass body containing the silver compound in a water-permeable container such as a plastic case or a tea bag. In addition, clinker 205 manufactured by Nippon Research Institute Co., Ltd., or Pacific Chemical Co., Ltd. can be preferably used.

The photosensitive material used in the present invention is not particularly limited, but preferred examples of elements constituting the photosensitive material will be described below.

The emulsion used in the light-sensitive material of the present invention can be produced by a known method. The silver halide emulsion preferably used includes, for example, monodispersed grains having a high iodine type disclosed in JP-A-2-85846.
The crystal habit of the crystal may be cubic, tetradecahedral, octahedral, and the intervening (111) and (100) planes arbitrarily.

The crystal structure of silver halide may have different silver halide compositions on the inside and outside.

The silver halide emulsion preferably used in the present invention is tabular grains having an average aspect ratio of more than 1. The advantages of such tabular grains are that they can improve spectral sensitization efficiency, improve image graininess and sharpness, and the like. For example, British Patent No. 2,112,157, US Patent No. 4,439,520, and US Pat. 4,433,048
Nos. 4,414,310 and 4,434,226
JP-A-58-113927 and JP-A-58-12792.
No. 1, 63-138342, 63-284272
And JP-A-63-305343, and emulsions can be prepared by the methods described in these publications. In particular, Japanese Patent Application Nos. 6-138568 (pages 1 to 3), JP-A-59-177535 (pages 2 to 5), and JP-A-62-278.
No. 42146 (14-15) are preferably used.

Further preferred silver halide emulsions used in the present invention are silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide and silver chloride of less than 3 mol% of silver iodide. Preferably, it is silver chlorobromide or silver chloride having a silver chloride content of 50% or more. The emulsion described above is a surface latent image type for forming a latent image on the grain surface or an internal latent image type for forming a latent image inside the grain,
Any type of emulsion that forms a latent image on the surface and inside may be used. These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or an aggregating polymer agent exemplified by G3 and G8 described in JP-A-63-158644 may be used. The method used is a particularly preferred desalting method. As the method of chemical ripening of the emulsion used in the light-sensitive material of the present invention, sensitization by a chalcogen compound such as selenium sensitization such as gold sensitization, reduction sensitization and sulfur sensitization, or a combination thereof is preferably used.

The silver halide emulsion of the present invention can be spectrally sensitized. As the spectral sensitizing dye used, cyanine, merocyanine, complex cyanine, complex merocyanine,
Examples include holopolar cyanine, hemicyanine, styryl dyes and hemioxonol dyes.

For example, oxacarbocyanine, benzimidazolocarbocyanine, benzimidazolooxacarbocyanine and the like as described in JP-A-5-113719 are exemplified. Further, dyes having a sensitizing effect in the blue light region described in JP-A-6-332102 are also preferably used. These spectral sensitizing dyes can be used alone or in combination.

The spectral sensitizing dye is preferably added as a solution dissolved in an organic solvent such as methanol. The addition amount of the spectral sensitizing dye is not uniform depending on the type of the dye and the emulsion conditions, but the amount added is 10 mol / mol of silver halide.
It is preferably from 900 to 900 mg, particularly preferably from 60 to 400 mg. The spectral sensitizing dye is preferably added before the completion of the chemical ripening step, and may be added in several portions before the completion of the chemical ripening. More preferably, after the growth step of the silver halide grains and before the completion of the chemical ripening step, particularly preferably before the start of the chemical ripening.

In the present invention, in order to stop the chemical sensitization (chemical ripening), it is preferable to use a chemical ripening terminator in consideration of the stability of the emulsion. Examples of the chemical ripening stopper include halides (eg, potassium bromide, sodium chloride, etc.), and organic compounds (eg, 4-hydroxy-6-methyl-1,3,3) known as antifoggants or stabilizers.
3a, 7-tetrazaindene) and the like. These may be used alone or in combination of a plurality of compounds.

In the emulsion of the light-sensitive material used in the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Examples thereof include a hydrazine compound and a tetrazolium salt.

Examples of the support which can be used in the light-sensitive material of the present invention include those described on page 28 of RD-17643 and page 1009 of RD-308119.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

An emulsion layer may be present on both sides of the support,
Only one side may be used. In the case of both sides, both sides may have the same performance or different performances.

[0092]

【Example】

 Example 1 A solid developer according to the present invention was prepared below.

<Solid developer containing the compound represented by the general formula (1) of the present invention as a main ingredient> [Granulated product (A)] 1-phenyl-3-pyrazolidone is added to 5
70 g, N-acetyl-D, L-penicillamine 10 g,
Glutaraldehyde bisulfite sodium salt 1000
g, potassium carbonate 1008 g, sodium bicarbonate 200
g of DTPA.5Na and 250 g of DTPA.5Na in a commercially available bandam mill until the average becomes 10 μm. 1600 g of sulfite and / or metabisulfite, 4000 g of sodium erysorbate, and D-
Mannit 800g, polyethylene glycol (PE
G) Add 200 g, mix in a mill for 30 minutes, granulate by adding 30 ml of water at room temperature for about 5 minutes in a commercial stirring granulator, then granulate the product with a fluid bed dryer. 40 ℃
And dried for 2 hours to remove almost completely the moisture of the granulated material.
A granulated product (A) was obtained.

[Preparation of Solid Developer] The granules (A) thus obtained were uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. A tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. was subjected to compression tableting at a filling amount of 10 g per tablet, and a developed tablet A was formed into a cylindrical shape having a diameter of 30 mm.

[Granulated product (B)] An average of 570 g of 1-phenyl-3-pyrazolidone was measured in a commercially available bandam mill.
Grind to μm. 4000 g of sodium erythorbate and D-mannitol 8 as sugars were added to the fine powder.
Then, 200 g of polyethylene glycol (PEG) was added, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 5 minutes in a commercial stirring granulator. The granulated product was dried at 40 ° C. for 2 hours with a fluidized bed drier to almost completely remove the water content of the granulated product to obtain a granulated product (B).

[Preparation of Solid Developer] The granules (B) thus obtained were uniformly mixed for 10 minutes by using a mixer in a room conditioned at 25 ° C. and 40% RH or less. A tableting machine modified from Tough Press Collect 1527HU, manufactured by Kikusui Seisakusho Co., Ltd., was subjected to compression tableting at a filling amount of 10 g per tablet, and a refillable developing tablet B was prepared in a cylindrical shape having a diameter of 30 mm. did.

[Granulated product (C)] N-acetyl-D, L-
10 g of penicillamine and 1000 g of glutaraldehyde bisulfite sodium salt are each pulverized in a commercially available bandam mill to an average of 10 μm. This fine powder contains 400 g of D-sorbitol and 400 g of D-mannitol as saccharides, and polyethylene glycol (PEG) 2
After adding 30 g of water in a commercially available stirring granulator at room temperature for about 5 minutes and adding 30 ml of water, the granulated product was added to a fluidized bed dryer at 40 ° C. At 2
After drying for a period of time, the water content of the granules was almost completely removed to obtain granules (C).

[Preparation of Solid Developer] The granules (C) thus obtained were uniformly mixed in a room conditioned at 25 ° C. and 40% RH for 10 minutes using a mixer. A tableting machine modified from Tough Press Collect 1527HU, manufactured by Kikusui Seisakusho Co., Ltd., was subjected to compression tableting at a filling amount of 10 g per tablet, and a refillable developing tablet C was prepared in a cylindrical shape having a diameter of 30 mm. did.

<Preparation of solid fixing agent> [Granulated product (D)] 14580 g of ammonium thiosulfate / sodium thiosulfate (90/10 weight ratio) is pulverized in a commercially available bandam mill until the average becomes 10 μm. To this fine powder, 550 g of sodium sulfite, 750 g of sodium metabisulfite, and 1220 g of pine flow were added, and the amount of water was added to 50 ml, and the mixture was stirred and granulated. The granulated product was dried at 50 ° C. with a fluidized bed dryer to remove water. Almost completely removed.

[Granulated product (E)] 600 g of boric acid, 1480 g of aluminum sulfate / 18-hydrate, 1100 g of succinic acid, and 300 g of tartaric acid are pulverized in a commercially available bandam mill to an average of 10 μm. D-Mannit 250 is added to these fine powders.
g, 50 g of D-Sorbit, and the added amount of water is 30 m.
and agitated granulation.
Dry at ℃ to remove water completely.

[Solid Fixing Agent] β-alanine (3000 g), sodium acetate (4330 g), and CH ₃ (CH ₂ ) ₇ SO ₃ Na (total weight: 1.30 g) were added to the thus obtained granulated product (D).
5%, and 750 g of sodium metabisulfite and CH ₃ (CH ₂ ) ₇ SO ₃ N were added to the granulated product (E).
a to 1.0% of the total weight,
After uniformly mixing for 10 minutes using a mixer in a room humidified at 25 ° C. and 40% RH or less, the obtained mixture was mixed with a tablet machine obtained by modifying a tough press collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. (D) is 10.
2 g and (E) 11.2 g, and compression tableting was performed to prepare a cylindrical fixing tablet having a diameter of 30 mm.

<Preparation of Processing Solution for Automatic Developing Machine> The developing solution in the developing tank was prepared by diluting and dissolving 18 developing tablets (A) with dilution water. The tablets were completely dissolved, and no precipitate was observed. 6. developer prepared at this ratio
8 l was placed in SRX-201 (manufactured by Konica Corporation), a starter described below was added thereto, and the processing was started by filling the developing tank as a start solution. Starter addition amount is 40ml / 1l
Met. 24 fixing tablets (C), 4 fixing tablets (D)
Individuals were diluted with dilution water and dissolved to adjust to 1 liter. The tablets were completely dissolved, and no precipitate was observed. 5.6 liters of the fixing solution prepared in this ratio was put into a fixing processing tank of SRX-201 to be used as a starting solution. In addition, both development and fixing were sampled and stored at 50 ° C. for 3 days, but no precipitate was observed. The pH of the developer when the starter was added was 9.90.

Starter formulation KBr 3.5 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 0.05 g Methyl-β-cyclodextrin 5.0 g Sulfuric acid or potassium hydroxide Finished with water 40ml In addition, the built-in chemical mixer of SRX-201 was modified for solid tablets. The remodeled built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank, and is controlled at 30 ° C. ± 2 ° C. The capacity of each liquid preparation tank is 3.0 liters and the capacity of the spare tank is 3.0 liters. The spare tank is supplied with a replenisher so that the replenisher is not supplied during the stirring and dissolving time (about 25 minutes) even if the replenisher created in the liquid preparation tank runs out during the running processing of the film. A spare tank was provided.

For both development and fixing, a predetermined packaging bag containing each tablet was opened by hand at the modified chemical mixer inlet for each solid agent, and each tablet was set in the built-in chemical mixer. At the same time as dropping, warm water (25 to 30 ° C.) is poured, and the solution is adjusted to 3.0 liters in 25 minutes with stirring and dissolving. This was used as a developing and fixing replenisher. The dissolving pH of the developing solution was adjusted using sulfuric acid or potassium hydroxide to be 10.15, and the dissolving pH of the fixing solution was 4.80.

Processing conditions were a developing temperature of 34 ° C. and a fixing temperature of 34 ° C.
C., a drying temperature of 55.degree. C. and a treatment time of 60 seconds.

<< Preparation of photosensitive material >><Preparation of seed emulsion-1> Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml S-3 (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g water 2825 ml D1 1.75N Potassium bromide aqueous solution The following silver potential control amount: 42 ° C, JP-B-58-58288 and 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. for 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again cooled. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It controlled so that it might be set to 8 mv and +16 mv.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. Diameter (converted to circle diameter)
Was confirmed to be 0.595 μm by an electron microscope. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

<Preparation of Em-1> A tabular silver halide emulsion Em-1 was prepared using Seed Emulsion-1 and the following four kinds of solutions.
Was prepared.

A2 Ossein gelatin 34.03 g S-3 (10% aqueous ethanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3150 ml with water B2 1734 g potassium bromide Equivalent to 3644 ml with water C2 Silver nitrate 2478 g water Fine grain emulsion composed of 3% by weight of D2 gelatin and silver iodide grains (average grain size: 0.05μ) (*) Equivalent to 0.080 mol * 5.0 containing 0.06 mol of potassium iodide To 6.64 liters of a weight percent aqueous gelatin solution, 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the formation of fine particles, the pH was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solutions B2 and C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and the pAg was
It was kept at 8.8 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

Further, the solution D2 was added at a concentration of 0.
Halogen substitution was performed by adding 15 mol%.

After the addition was completed, the emulsion was cooled to 40 ° C.
1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate 90%) was added as an aggregating polymer agent, and the mixture was stirred for 3 minutes. afterwards,
A 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.6. After stirring for 3 minutes, the emulsion was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Thereafter, 9.0 l of distilled water at 40 ° C. was added, and after stirring and standing, the supernatant was drained. Further, 11.25 l of distilled water was added, and after stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% (by weight) aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes and redispersion. After redispersion, the pH was 5.80 at 40 ° C.,
The pAg was adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.1% tabular silver halide grains. The average of the distance between twin planes was 0.020 μm, and the grains having a ratio of the distance between twin planes to the thickness of 5 or more accounted for 97% (number) of all tabular silver halide grains and 10 or more grains. Occupied 49%, and 15% or more of the particles occupied 17%.

Next, after the above emulsion (Em-1) was heated to 60 ° C., a predetermined amount of a spectral sensitizing dye was added as a dispersion in the form of solid fine particles, and 10 minutes after addition, adenine, ammonium thiocyanate, chloroauric acid was added. And a dispersion of triphenylphosphine selenide and a silver iodide fine grain emulsion were further added 30 minutes later.
Aged for hours. At the end of ripening, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above additives and their amounts (AgX1
Per mole) is shown below.

5,5'-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous 400 mg 5,5'-di- (butoxycarbonyl) -3,3 ' -Di- (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt anhydrate 4.0 mg adenine 15 mg potassium thiocyanate 95 mg chloroauric acid 2.5 mg sodium thiosulfate 2.0 mg triphenylphosphine selenide 0.2 mg iodine Silver halide fine particles 280 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg Solid fine particle dispersion of spectral sensitizing dye is disclosed in JP-A-5-297.
It was prepared by a method according to the method described in No. 496. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and 3,500 r.
Obtained by stirring at pm for 30-120 minutes.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of Emulsion Layer Coating Solution) The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² 1,1-dimethylol-1-bromo-1- Nitromethane 70 mg t-butyl-catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound ( H _{^{0.5mg / m 2 n-C 4}} H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Compound (M) 5mg / m ² Compound (N) 5mg / m ² colloidal silica ( Ludox AM: particle size 0.013 μm manufactured by DuPont) 0.5 g / m ² However, 1.5 g / m ² of gelatin is mixed with an emulsion.
Adjusted to be ² .

(Preparation of Coating Solution for Protective Layer) Gelatin 0.8 g / m ² NaOH Amount to be adjusted to pH shown in Table 1 Matting agent made of polymethyl methacrylate 50 mg / m ² (area average particle size 7.0 μm) agents _{(CH 2 = CHSO 2 CH 2} ) 2 O 36mg / m 2 2,4- dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² latex (L) 0.2g / m ² poly Acrylamide (average molecular weight 10,000) 0.2 g / m ² Sodium polyacrylate 30 mg / m ² Polysiloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) ) 7 mg / m ² compound (K) 15mg / m ² compound (O) 50mg / m ² compound (S-2) 5mg / m 2 compound (F-1) 3mg / m 2 compound (F ²⁾ 2mg / m 2 Compound (F-3) 1mg / m 2 It is noted that the amount with the material is one-sided 1 m ² per silver coverage was adjusted to 1.6 g / m ² as a one-sided min.

(Formation of Crossover Cut Layer) Glycidyl methacrylate 50 wt%, methyl acrylate 1
A copolymer dispersion obtained by diluting a copolymer composed of three types of monomers of 0 wt% and 40 wt% of butyl methacrylate so as to have a concentration of 10 wt% was applied as a subbing liquid and was colored in blue with a thickness of 175 μm. on both sides of a polyethylene terephthalate support to prepare a support samples coated with the cross-over cut layer as the coating amount per surface 1 m ² is the following composition.

Solid fine particle dispersion dye (AH) 50 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg Colloidal silica ( Average particle size 0.014 μm) 10 mg Potassium polystyrene sulfonate 50 mg

[0125]

Embedded image

[0126]

Embedded image

(Coating) Using these coating solutions, two slide hopper type coaters were used so that the coating amount per side was 1.6 g / m ² and the gelatin amount was 2.5 g / m ^2. Using 1 per minute
At the speed of 20M, the two-sided simultaneous coating was carried out on the above-mentioned support sample with the following layer constitution, and dried for 2 minutes and 20 seconds. 1 and 2 were made.

Layer position Layer type Layer amount of gelatin per side (g / m ² ) Upper layer Protective layer 0.8 Interlayer Emulsion layer 1.5 Lower layer Filter layer 0.2 Using the coating sample thus obtained, Was evaluated.

<Evaluation of Sensitometric Photographic Performance> The coated sample thus obtained was coated with a fluorescent intensifying screen KO-250 (Konica Corporation).
X-ray irradiation was performed under the conditions of a tube voltage of 90 KVp, a current of 20 mA, and a time of 0.05 second, and a sensitometric curve was created by a distance method to determine the sensitivity. The development process is
Under the processing conditions described above, an SRX-201 modified automatic developing machine was used. The value of the sensitivity is the reciprocal of the X-ray dose required to obtain Fog + 1.0. Table 1 shows the relative values with 1 as 100.

<Evaluation of Drying Unevenness> Using an SRX-201 remodeled automatic developing machine, under the above-mentioned processing conditions, a large-angle size (35.6 × 35.6 cm) was uniformly X-rayed so as to have a density of 1.0. Exposure was performed, and 100 sheets were processed continuously. Thereafter, 10 large-sized samples uniformly exposed to white so that the density became 2.5 were continuously processed. The unevenness seen when the developed sample is reflected by light and observed is divided into the following four stages, evaluated as dry unevenness, and the results are shown in Table 1.

4: No dry unevenness is observed at all. 3: Dry unevenness is observed at the edge (periphery) of the film in a frame shape. 2: About half of the film is observed to have a hazy unevenness from the edge to the center. 1: Film Large uneven drying is observed on the entire surface of the sample.

[0132]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention has high sensitivity and little drying unevenness.

Example 2 The amount of swelling of the film was adjusted to the value shown in Table 2 with a hardener [(CH ₂
= CHSO ₂ CH ₂ ) ₂ O] was changed and the film surface pH was changed.
Is 7.5, and the coated sample film No. 3 and 4 were made. The development unevenness and processing stability were evaluated by the following methods, and each is shown in Table 2.

<Evaluation of Developing Unevenness> Using a SRX-201 remodeled automatic developing machine, under the above-mentioned processing conditions, a large-angle size (35.6 × 35.6 cm) was uniformly X-rayed so as to have a density of 1.0. Exposure was carried out and 50 sheets were processed continuously.
The unevenness observed when the developed sample was observed with a Schaukasten was divided into the following four stages and evaluated as development unevenness.

4: No unevenness was observed at all. 3: Unevenness was slightly observed. 2: Unevenness was considerably observed. 1: Unevenness was observed over the entire surface.

<Processing Stability> An X-ray film SR-G manufactured by Konica Corp. was exposed so that the density after processing became 1.0, and an automatic developing machine modified for SRX-201 was used in the same manner as in Example 1. 2,000 pieces of running processing were performed under the above-described processing conditions. Coated sample film N of the present invention
o. 3 and 4 are the top stage of the running process and 2
The film was developed at the stage after the processing of 000 sheets, and a sensitometric curve was prepared in the same manner as in Example 1 to determine the sensitivity.

[0138]

[Table 2]

From Table 2, it can be seen that the sample of the present invention has excellent processing stability and little development unevenness.

[0140]

According to the present invention, there is provided a method for developing a silver halide photographic light-sensitive material which has rapid processing suitability, has no drying unevenness and development unevenness, and has excellent processing stability (oxidation resistance). Was completed.

Claims (6)

[Claims] 1. A method for developing a silver halide photographic light-sensitive material comprising a support provided with a hydrophilic colloid layer including a light-sensitive silver halide light-sensitive layer, wherein a surface pH of the silver halide photographic light-sensitive material is adjusted. Wherein the developing agent is replenished with a solution having a developing agent concentration higher than 7.5 and a developing agent concentration higher than the starting solution. 2. An antifoggant or a hardener consumed by processing a silver halide photographic light-sensitive material,
2. The method for developing a silver halide photographic light-sensitive material according to claim 1, wherein the replenishment is carried out in an amount equal to or smaller than the consumption amount. 3. The method for developing a silver halide photographic light-sensitive material according to claim 1, wherein a solid processing agent containing a developing agent and tableted by compression molding is replenished. 4. A method for developing a silver halide photographic light-sensitive material comprising a support provided with a hydrophilic colloid layer including a photosensitive silver halide light-sensitive layer, wherein the swelling ratio of the silver halide photographic light-sensitive material is as follows. A developing method for a silver halide photographic material, wherein the developing agent is replenished with a solution having a developing agent concentration of not more than 250% and higher than the starting solution. 5. An antifoggant or hardening agent consumed by processing a silver halide photographic light-sensitive material,
5. The method for developing a silver halide photographic light-sensitive material according to claim 4, wherein the replenishment is carried out in an amount equal to or less than the amount consumed. 6. The method for developing a silver halide photographic light-sensitive material according to claim 4, wherein a solid processing agent containing a developing agent and tableted by compression molding is replenished.