JPH01156743A - Development processing method - Google Patents

Abstract

PURPOSE:To prevent the variance of the photographic performance of a photosensitive material by detecting the liquid levels of processing tanks of an automatic processor, and by replenishing an amount of water decreased during stand-by period etc., of the processor. CONSTITUTION:The photosensitive material is developed while replenishing a processing solution according to processing amount of the photosensitive material. And the liquid levels of the tanks of a developing solution and/or a fixing solution which decreased by vaporing water during the stand-by period and/or the period of suspension of the automatic processor are automatically detected respectively, and the amount of water equivalent to that of the vaporized water is automatically replenished. The detection of the liquid level is carried out by a level sensor, etc., and a mildew proofing agent such as aminopolycarboxylic acid, etc. may be added to the replenishing water.

Description

Detailed Description of the Invention (Field of use for overtime) The present invention relates to a method for developing silver halide photographic materials using an automatic processor, particularly for processing after a long period of stoppage or standby. The present invention relates to a processing method that can obtain a certain level of photographic properties even when

(Prior Art) After exposure, silver halide black-and-white photographic materials are generally processed through the steps of development, fixing, and washing with water.

Nowadays, most of them use automatic processors (hereinafter referred to as automatic processors) to pump fixed amounts of developer and fixer into the developing tank and fixing tank in proportion to the area of the photosensitive material being processed. It is common for development processing to be carried out while replenishing.

However, in a roller-conveying automatic processor for developing X-ray photographs and photographs in sheet form one by one, such as Graphiferts photosensitive materials, the specific surface area of the processing tank of the automatic processor ( The surface area (-) of the air-adhesive part of the processing liquid in the processing tank divided by the liquid volume <1> in the processing tank) is defined as the value obtained by dividing the surface area (-) of the air-adhesive part of the processing liquid in the processing tank by the liquid volume <1> in the processing tank). Because they can't do that, they have no choice but to grow up.

For this reason, water evaporates from the liquid surface of the processing tank, especially during standby (usually not refilled) or when stopped.
This results in the processing liquid being concentrated.

In particular, concentration of the developer is undesirable as it causes deterioration of photographic properties.
A large specific surface area is undesirable because it causes oxidative deterioration of the developer, but even in the same oxidative deterioration state, the photographic properties are further deteriorated due to the concentration. The reason for the deterioration of photographic properties due to concentration due to water evaporation in the developing solution is that the concentration of inorganic salts such as sulfites, bisulfites, carbonates, phosphates, and borates increases in the composition of the developing solution. It is thought that the developing activity of the main agent changes or the swelling of the photosensitive material is suppressed, resulting in insufficient density.

Furthermore, deterioration of photographic properties occurs in the fixing solution due to evaporation and concentration. Although the mechanism is not clear, the pH of the fixer increases due to evaporation and concentration, and the salt concentration becomes too high. This is the result of not being able to produce enough.

If the salt concentration of the fixer becomes too high, it will also reduce the fixing speed, and may result in poor fixing if the fixing time is fixed as in an automatic processor.

(Object of the Invention) An object of the present invention is to prevent fluctuations in photographic performance due to evaporation of water while the automatic processor is stopped or on standby in the development process of silver halide photographic materials using an automatic processor. It is an object of the present invention to provide a processing method that can be used in black-and-white development processing with a high salt concentration, especially a high sulfite concentration, using an automatic processing machine with a large specific surface area, even when only a small amount of sensitive material is processed, that is, an automatic processing method. To provide a developing processing method capable of obtaining stable photographic performance even when standby or stop time of a developing machine is long.

(Structure of the Invention) The object of the present invention is to provide a method for developing a silver halide photographic light-sensitive material using an automatic processor while replenishing a processing solution according to the amount of processing. Few (
This was achieved by a developing processing method characterized by detecting the liquid level in one processing tank and replenishing the amount of water that evaporates and decreases while waiting and/or stopping the developing process.

In the present invention, at least one of the processing tanks, for example a developer tank and/or a fixer tank, is stopped and/or
Or, during standby, a drop in the liquid level due to water evaporation is automatically detected, and the amount of water that has evaporated is automatically replenished.

A commonly used electrical detection method (level sensor) may be used to detect the liquid level.

A preferred method is to detect the liquid level and replenish the amount of water corresponding to the drop in the liquid level in synchronization with a solenoid valve.

Alternatively, a so-called one-type chicken feeder may be used, and when the liquid level drops, water may be replenished from a water container to compensate for the amount of air that has entered.

In a typical automatic processing machine, each processing tank is provided with an overflow outlet. During processing of the photosensitive material, each processing tank is replenished with a processing solution replenisher according to the area of the photosensitive material. The amount of replenisher is normally set to be larger than the amount of liquid taken out of the processing tank by the photosensitive material, so during processing of the photosensitive material, the processing solution overflows from the overflow outlet and the liquid level is maintained at the level of the overflow outlet. ing.

It is convenient to measure the amount of water that evaporates while the photosensitive material is stopped and/or on standby other than when it is being processed, using the height of the overflow outlet as a reference.

The method of the present invention is useful for roller conveyance type automatic processors having a large specific surface area. It is particularly useful in automatic processors having a specific surface area (surface area (cd) of the air contacting portion of the processing liquid in the processing tank, amount of liquid in the processing tank (1)) of 30 or more. Here, the surface area of the air interface of the liquid in the processing tank is not included in the calculation if the liquid surface is completely covered by a floating pig or the like. Or, if a part of the transport roller is immersed in the processing liquid, or if a part of the transport roller protrudes from the liquid surface, the calculation of the processing liquid surface area above requires a smooth exposed surface. It is considered as the liquid surface and is included in the calculation. In the present invention, the specific surface area is more preferably 50 or more, and even more preferably 80 or more.

Furthermore, even in automatic processors with the same specific surface area, the smaller the ratio of the amount of replenisher to the amount of liquid in the developer tank, the greater the concentration due to water evaporation in the developer. The effect will be greater.

That is, the effect of the present invention is large when the average amount of replenisher per week is 20% or less of the capacity of the developing tank, particularly preferably when it is 10% or less.

It is preferable to replenish the evaporated water of the processing solution of the present invention while the automatic processor is on standby or stopped. It is also preferable that when the automatic processor is turned on, a level sensor detects the amount of evaporation during stoppage, replenishes the amount, and then starts the periodic operation to perform the development process.

Furthermore, water equivalent to the amount of water that evaporated during standby and/or stoppage may be replenished immediately before processing the sensitive material, or the liquid level may be maintained at a predetermined level during standby and/or stoppage. Each time a certain amount is exceeded, the amount of water necessary to restore the liquid level to the original level may be added.

In the present invention, the amount of evaporated water may be replenished in any one of the developing tank, the fixing tank, and the washing tank, but it is preferable to replenish water in the developing and fixing tanks, especially in all the tanks. I do.

As long as the water used here is essentially water, it can be replenished with tap water, or depending on the size of the machine and how it is used, it can be stored in a bottle or tank of an appropriate capacity and treated with anti-mold water. It may also be preferable to use

The above-mentioned anti-mildew measures include ultraviolet irradiation, magnetic field irradiation, ion exchange, and addition of specific compounds or combinations thereof. Preferably, a specific compound is added.

Passing the water through a magnetic field as one of the ways to apply the anti-mold effect means passing the water of the present invention through a magnetic field generated between the positive and negative poles of the magnetic field.

The magnetic field used in the present invention is obtained by using a permanent magnet made of ferromagnetic materials such as iron, cobalt, and nickel.
Alternatively, it can be obtained by passing a direct current through a coil or the like, but there is no particular limitation, and any means capable of forming a magnetic field can be used. Note that the magnetic field may be formed by using one magnet to form lines of magnetic force, or by opposing two magnetic forces (a positive pole and a negative pole) to form lines of magnetic force between opposing magnets.

The method of passing the water used in the present invention through a magnetic field is to use a permanent magnet that forms a magnetic field and move (including rotation) the permanent magnet installed inside the water stock tank or bottle and/or outside the liquid. Alternatively, there are methods such as moving the water by stirring or circulating the water.

A particularly desirable method is to fix a permanent magnet to a part or all of the inside or outside of a circulation system pipe and circulate water.

In the present invention, the method of irradiating water with ultraviolet rays is carried out using a generally commercially available ultraviolet lamp or ultraviolet irradiation device, and preferably the output of the ultraviolet lamp is 5W to 8.
00W (tube output), but is not limited thereto.According to a preferred embodiment of the present invention, the wavelength of ultraviolet rays is in the range of 220 nm to 35'Onm.

In the present invention, the ion exchange resin treatment method involves passing water through a mixed-bed column filled with a commercially available H-type strongly acidic cation exchange resin and an OH-type strongly basic exchange resin to remove calcium and magnesium ions in the water. This is a method that significantly removes A method having the same meaning as this also includes using distilled water as the water in the present invention.

Regarding the method using ultraviolet rays, for example, see Japanese Patent Application Laid-Open No. 60-26
3939, for example, Japanese Patent Application Laid-Open No. 60-263940 for a method using a magnetic field, and Japanese Patent Application No. 61-13 for a method using an ion exchange resin.
It is described in detail in the specification of No. 1632.

In the method of adding a specific compound as one of the anti-mildew measures in the present invention, there are aminopolycarboxylic acids as anti-mildew compounds.
), diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N-N', N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, alkyliminodiacetic acid, dihydroxy Ethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diamino-2-propatoltetraacetic acid, triethylenetetraminehexaacetic acid, hydroxyethyliminoacetic acid, oxybis (ethyleneoxynitrilo)tetraacetic acid, malic acid, and the sodium and potassium salts of these polycarboxylic acids.

Specific examples of compounds as the phosphones M in the present invention include compounds represented by the following general formulas (1) to (IV).

General formula (1) General formula (II) m=o, 1.2 General formula (Ill) % formula %) General formula (rV) 1=0. 1, 2 In the formula, R1-R4 represents a hydrogen atom, a hydroxyl group, an alkyl group (having 1 to 3 carbon atoms, e.g. methyl group, ethyl group, propyl group, etc.), an amino group, an alkoxy group (having 1 to 3 carbon atoms),
3), for example, methoxy group, ethoxy group, etc.), alkylamino group (preferably having 1 to 3 carbon atoms), ori-ruamino group (preferably having 6 to 8 carbon atoms), aryloxy group (preferably having 6 to 8 carbon atoms), 6 to 8).

R, ~R13 are hydrogen atoms, hydroxyl groups, -COO
M-1P 03 Mt, alkyl group (1 to 3 carbon atoms,
For example, it represents a methyl group, an ethyl group, a propyl group, etc.).

RI4 represents a hydrogen atom or an alkyl group (having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc.), and M represents an alkali metal such as a sodium atom or a potassium atom.

Specific compounds represented by the general formulas (1) to -general formula N) include the following.

compound +11 Compound (2) Compound (3) Compound (4) CHZ COON a ■ HC-CH.

CHs CCOONa de P　O,N　a.

Compound (5) CHlCOOH ■ CH.

HOOCCH2CCOOH 0sHz Compound (6) CHlCOOH Compound (n CH, -COOH HOOCCPOsHt CH.

CHICOOH Compound (8) Compound (9) Compound OI Compound αυ Compound Surface Compound 0 CHzPOslb These compounds are preferably added in the form of sodium and/or potassium salts.

Particularly preferred among these compounds are ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, and ethylenediamine-N-hydroxyethyl-
N, N', N'-triacetic acid, propylene diamine tetraacetic acid,
Examples include aminopolycarboxylic acids such as triethylenetetraminehexaacetic acid, ethylenediaminetetramethylenephosphonic acid, and sodium salts, potassium salts, and ammonium salts of 1-hydroxyethylidene-1,1-diphosphonic acid.

Although it is sufficient to use one type of the above-mentioned compound group for the water used in the present invention, two or more types may be used in combination.

The above compound is preferably 0.02 g to 11 g of water.
It is contained within the range of 20g, but more preferably 0.05g.
g to 5 g.

The water treated with the specific anti-mildew means of the present invention is used as washing water or stabilizing liquid in the developing process, and a part of the washing water or stabilizing liquid is stored in the developer tank. Divert to dilution water. Preferably, the water treated with the present anti-mildew means can also be used as dilution water for the developer and/or fixer concentrate in the development process, as described in Japanese Patent Application No. 61-233295.

Furthermore, this water can also be used for washing a crossover rack as described in Japanese Patent Application No. 18636/1983.

Most preferably, all of the water for replenishing evaporated water, the washing water (or stabilizing solution), the dilution water for developing and/or fixing solution, and the washing water of the cross-over rack are shared by the water treated with the above-mentioned anti-mold means. This makes it possible to store these waters in only one stock tank.

The specific anti-mildew means of the present invention does not adversely affect development or fixing.

In the case of the method of adding the specific compound of the present invention to provide antifungal measures, the following methods can be used, for example, for adding the compound.

1) Water to which a certain amount of the compound of the present invention has been added is placed in a fixed container and fed to the developing tank using a chicken feeder.

2) The compound of the present invention is added to a tank of water used for washing water or rinsing water (or stabilizing liquid) and dissolved to provide the solution.

3) While mixing a concentrated liquid in which the compound of the present invention is dissolved and tap water at a constant ratio, supply the evaporated water as make-up water, washing water, or washing water (or stabilizing liquid).

4) Tap water is first supplied to the crossover rack cleaning device and/or washing or stabilization tank, and then a certain amount of the concentrated solution of the compound of the present invention is added.

The developing agent used in the developer of the present invention is mainly composed of hydroquinones, but since it is easy to obtain good performance, a combination of hydroquinones and 1-phenyl-3-pyrazolidones,
Alternatively, a combination of hydroquinones and p-aminophenols is preferable.

Hydroquinone-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isoprohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2, Examples include 5-dimethylhydroquinone, and hydroquinone is particularly preferred.

The p-aminophenol developing agent used in the present invention includes N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl) Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-
Aminophenols are preferred.

The 3-pyrazolidone developing agent used in the present invention is 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,
1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-)dyl-4,4-dimethyl-3-pyrazolidone, 1-p-)dyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone, etc.

Hydroquinone-based developing agents are usually 0.01 mol/1 to 1
．． It is used in an amount of 5 mol/l, preferably 0.05 mol/1 to 1.2 mol/l.

In addition to this, the p-aminophenol developing agent or 3-pyrazolidone developing agent is usually 0.0005 mol/
1 to 0.2 mol/1, preferably 0.001 mol/1 to
It is used in an amount of 0.1 mol/l.

Sulfites used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite, etc. The sulfite is 0.2 mol/1 or more, especially 0.
．． The amount is preferably 3 mol/1 or more, and the upper limit is preferably 2.5 mol/1 in the developer concentrate.

The pH of the developer used in the development process of the present invention is preferably in the range of 9 to 13, more preferably in the range of 10 to 12.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains Hli moderator.

JP-A-62-186259 (Borate), JP-A-60
Buffers such as No.-93433 (eg, sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

In the present invention, the developer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions.

Here, the Keed stability constants are L, G, 5illen・
^.

Written by E. Marte11, H″5tability C
on5tants of Metal-ion Co
5plexes', The Chess+1cal
5ociety, London (1964)
, S, Chaberek-A,t! , Marte
Written by ll.

Organic 5equ'stering Age
nts”+11i1ey (1959) 0, etc. means a constant generally known.

In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe'').

In the present invention, specific examples of compounds of the chelating agent having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds: ethylenediaminediorthohydroxyphenyl Acetic acid, triethylenetetraminehexaacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1 .3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-N,N,N',N'tetrakismethylenephosphonic acid, nitrilo-N,N, N-
trimethylenephosphonic acid, ■-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonethane-2
-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-
Examples include 1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate.

Further, dialdehyde-based hardeners or bisulfite adducts thereof are used in the developer, and specific examples thereof include gel tar aldehyde and bisulfite adducts thereof.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol; l-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may also contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole.
Development accelerators described in Disclosure Vol. 176, No. 17643, Section A (December issue, 1978), and if necessary, colorants, surfactants, antifoaming agents,
It may also contain a water softener, an amino compound described in JP-A-56-106244, and the like.

In the development process of the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

The developer of the present invention includes European Patent Publication No. 136582
No. 958,678, U.S. Pat. No. 32,327
Amino compounds such as alkanolamines described in No. 61, JP-A-56-106244, and European Patent No. 0136582 can be used for the purpose of accelerating development, increasing contrast, and other purposes.

In addition, 'Photographic Photography' by 'F, A Mason
"Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent No. 2,1
No. 93,015, No. 2,592゜364, Japanese Unexamined Patent Publication No. 1973
-64933 etc. may be used.

The fixer is an aqueous solution containing thiosulfate, I) H3,8
Above, preferably 4.2 to 7.0.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, but ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol/l. It is.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like.

In the fixing solution, tartaric acid, citric acid, glyconic acid, or derivatives thereof can be used alone or in combination of two or more. These compounds contain 0.0.
Those containing 0.005 mol or more are effective, especially 0.01 mol/
1 to 0.03 mol/l is particularly effective.

The fixer may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid), pi(
It may contain a J additive (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in JP-A-62-78551.

- In the development processing method of the present invention, after the development and fixing steps, a replenishment amount of 31 or less (
It can also be treated with rinsing water or a stabilizing solution, including 0 (i.e., rinsing with reservoir water). In other words, not only can water be saved, but also piping for installing an automatic processor can be eliminated.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multistage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done.

For the above-mentioned water-saving treatment or piping-free treatment, it is preferable to apply anti-mold means to the washing water or the stabilizing liquid.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, JP-A-62-
No. 115154, No. 62-153952, Patent Application No. 1983
The method using the antibacterial agent described in No. 63030 and No. 61-51396 can be used.

Furthermore, L,! ! ]est, “l1ater Qual
ity Cr1teria'Photo, Sci,
& Bng, Vol. 9 Na6 (1965
), M, L Beach, “Microbiolo
gical Growths inMotion-Pi
ture Processing”SMPTE Jo
Urnal Vol.

85, (1976), R.O., Deegan.
Photo.

Processing Wash l1ater Bi
ocides”J, ImagingTech 1
0. N16 (1984) and JP-A-57-8542
No. 57-58143, No. 58-105145,
No. 57-132146, No. 58-18631, No. 5
Antibacterial agents, antifungal agents, surfactants, etc. described in No. 7-97530 and No. 57-157/244 can also be used in combination.

Additionally, R, T, and Krei minerals are added to the washing bath or stabilizing bath.
Author, J. Fage, Tech 10. +612
Isothiazoline compounds described on page 42 (1984), Re5earch Disclosure 5th year
Isothiazoline compounds described in chDisclosure 1981, May issue), Volume 228, No. 2284
5 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides.

In addition, "Chemistry of anti-bacterial and anti-mildew" by Hiroshi Horiguchi, Sankyo Publishing (Showa 5)
7), "Handbook of Antibacterial and Antifungal Technology," Japanese Society of Antibacterial and Antifungal Research, Hakuhodo (1988) may also be included.

When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank as described in Japanese Patent Application No. 163217/1982.
It is also preferable to adopt a water washing step configuration as in No. 290619.

Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water according to the treatment according to the method of the present invention, is used in Japanese Patent Application Laid-Open No. 1986-1999. As described in Japanese Patent Application No. 235133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that.

In the present invention, "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution. , is the time from immersion in the fixing tank solution to the next immersion in the washing tank solution (stabilizing solution).
This refers to the time spent immersed in the washing tank liquid.

In addition, "drying time" is usually 35℃ to 10℃ for automatic processors.
A drying zone is installed in which hot air of 0°C, preferably 40°C to 80°C is blown, and refers to the time spent in the drying zone.

In the development process of the present invention, the development time is 5 seconds to 3 minutes, preferably 10 seconds to 2 minutes, and the development temperature is preferably 25°C to 50°C, more preferably 25°C to 40°C.

The fixing temperature and time are preferably about 0° C. to about 50° C. and 5 seconds to 3 minutes, and more preferably 25° C. to 40° C. and 10 seconds to 2 minutes.

Water washing or stabilization bath temperature and time are 0 to 50℃ for 5 seconds to 3
minutes is preferred, and 10 seconds to 2 minutes at 15°C to 40°C is more preferred.

According to the method of the invention, the developed, fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is carried out at a temperature of about 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 2 minutes, particularly preferably about 5 seconds at 40°C to 80°C. ~1 minute.

The photographic material used in the developing method of the photosensitive material of the present invention is not particularly limited, and general black and white photosensitive materials are mainly used, as well as color photosensitive materials to be subjected to reversal processing, such as color reversal film or black and white paper. It can also be used as a developer.

In particular, photographic materials for laser printers for medical images, scanner materials for printing, medical direct photography X-ray materials, medical articulation X-ray materials, CR7 image recording materials, and microphotosensitive materials. It is preferable to use it for general black and white negative film, black and white photographic paper, etc.

A silver halide photographic material to which the processing method of the present invention can be applied comprises a support and at least one silver halide emulsion coated thereon. Further, the silver halide emulsion layer can be coated not only on one side of the support but also on both sides.

Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary. A silver halide emulsion is one in which silver halides such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide are dispersed in a hydrophilic colloid. Silver halide emulsions are typically prepared using a water-soluble silver salt (e.g., IN nitrate) by methods well known in the art (e.g., single jet method, double jet method, controlled jet method, etc.).
and a water-soluble halogen salt in the presence of water and a hydrophilic colloid, and are produced through physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization. The emulsion thus obtained has cubic, octahedral, spherical, and other shapes.
hDisclosure 22534 (January
y 1983) can be used, and internal latent image type silver halide grains and surface latent image type halogen particles described in Japanese Patent Publication No. 41-2068 can be used. It can also be used in combination with silver oxide particles.

During the manufacturing process or just before coating, the silver halide emulsion is
Spectral sensitizers (e.g. cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g. 4-hydroxy-
6-methyl-1,3,3a.

7-titrazaindene), sensitizers (e.g., compounds described in U.S. Pat. No. 3,619,198), antifoggants (e.g., benzotriazole, 5-nitrobenzimidazole, polyethylene oxide, hardeners, Coating aids (eg, saponin, sodium lauryl alphaate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide), etc. can be added.

The silver halide emulsion thus produced is coated and dried on a support such as a cellulose acetate film or a polyethylene terephthalate film by a dip method, an air knife method, a bead method, an extrusion doctor method, a double-sided coating method, or the like.

Next, the method of the present invention will be explained with examples, but the present invention is not limited thereto.

Preferred embodiments a of the present invention are listed below.

1) Claim (11) is a roller conveyance type automatic developing machine in which the specific surface area of the processing tank of the automatic developing machine is 30 cd/7! or more.

2. Claims (11) The developer must contain a total of 0.2 mol/1 or more of sulfite and sulfate.

3) Claim (11) Subjecting the replenishing water to at least one of the methods of adding ultraviolet rays, magnetic field irradiation, ion exchange, and adding aminopolycarboxylic acids or phosphonic acids as a fungicidal means.

4) In claim (4), the anti-mold means adds aminopolycarboxylic acids to the water to be replenished.

5) In claim (1), to replenish the amount of water that decreases due to evaporation in the developer tank and fixer tank of an automatic processor.

Example 1 A gelatin silver iodobromide emulsion layer coated with silver halide at a silver content of 3.2 g/rd on each side of a polyethylene terephthalate film (1112 mol % iodide gelatin content 70 g/mol Ag, potato-like grains) An X-ray photographic material comprising a gelatin protective layer coated with gelatin at a ratio of 1 g/rd was developed using a roller transmission type automatic processor.

The development processing conditions and specific surface area of each tank of the automatic processor used are shown below.

Total processing time: 3 minutes 40 seconds (Developer prescription) (Developer and replenisher 11 formulations) Add B agent to A agent (pH 10,00) to make a developer solution, put it in the developing tank of an automatic processor, and use the same composition. developer solution as a replenisher, the above-mentioned photosensitive material opening size (101nchX 121nch)
ch) 50d per sheet was automatically replenished.

Fixer formulation> (Fixer and replenisher 11 formulations) - With water 45 - Add agent B to the agent (
A fixing solution (pH 4, 25) was prepared and used as a fixing tank solution and replenisher for an automatic processor. Replenishment fluid amount is 50-/4 size 1
It is one piece.

Washing water (stabilizing liquid) Ethylenediaminetetraacetic acid, disodium salt, dihydrate salt 0.
4 g/l was added to the washing tank liquid and replenishment liquid of the automatic processing machine. The amount of replenisher is one 50-/4-size sheet.

Turn it on at 9am, put it on standby, and turn it on at 4pm in the evening.
5 sheets of the above-mentioned photosensitive material per day (
Development rate: 40%) Continuous processing was performed. From the 28th onwards, after turning on the machine in the morning, the levels of the liquid in the developing tank, fixing tank, and washing tank are detected, and water with the same composition as the washing water is added to the developing tank and fixing tank according to the evaporation loss. A similar running experiment was carried out by replenishing water into the water washing tank.

As a result, the photographic properties are as follows.

In the method of the present invention, the decrease in D and B is small despite the oxidative deterioration of the liquid, and good performance can be maintained.

It also has excellent water washability.

Example 2 In the automatic processing machine of Example 1, the depths of the developing tank and fixing tank were changed to change the tank liquid capacity. A similar experiment was conducted by changing the specific surface area. However, in the developer formulation of Example 1, instead of DTPA, a developer was used in which 2 g of ethylenediaminetetramethylenephosphonic acid and 30 g of triethanolamine were added to adjust the pH to 10.00. The results after two weeks of running are as follows.

Example 3 1. Add 30 g of gelatin and 6 g of potassium bromide to dish water 11 at 60°C.
A silver nitrate aqueous solution (5 g as silver nitrate) and a potassium bromide aqueous solution containing 0.15 g of potassium iodide were added by double jet method over a period of 1 minute into a container maintained at a temperature of 1.5 g with stirring. Furthermore, silver nitrate aqueous solution (145 g as silver nitrate) and potassium iodide 4.
An aqueous solution of potassium bromide containing 2 g was added by double jet method. At this time, the addition flow rate was accelerated so that the flow rate at the end of addition was five times that at the start of addition. After the addition was completed, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 75 g of gelatin was continuously added, and the pH was adjusted to 6.
．． Adjusted to 7. The resulting emulsion has a projected area diameter of 0.9
The grains were tabular grains of 8 μm and average thickness of 0.138 μm, and the silver iodide content was 3 mol %. This emulsion was chemically sensitized using gold and sulfur enhancement.

2. In addition to gelatin, an average molecular weight of 8000 was added as a temporary surface protective layer.
Polyacrylamide, polystyrene sulfonate soda, polymethyl methacrylate fine particles (average particle size 3)
．． An aqueous gelatin solution containing 0 μm), polyethylene oxide, and a hardening agent was used.

Anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was added to the above emulsion as a sensitizing dye at a ratio of 500 μ/1 mol Ag. , potassium iodide 20
It was added at a ratio of 0/1 mole Ag. Furthermore, as stabilizers, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene and 2,6-bis(hydroxyamino)-
A coating solution was prepared by adding 4-diethylamino-1,3,5-) riazine and nitrone, trimethylolpropane as a dry anti-capri agent, a coating aid, and a hardening agent, and a surface protective layer was formed on both sides of the polyethylene terephthalate support. A photographic material was prepared by coating and drying at the same time. The amount of silver coated on this photographic material is 2 g/rtr per side.

This window material was subjected to stepwise exposure using an optical wedge using a sensitometer, and developed using the following developer, fixer and washing solution formulations.

3.11 Sputum ■ Potassium hydroxide 17g Sodium sulfite 31g Potassium sulfite
50g triethylenetetramine hexaacetic acid vinegar 2g boric acid 9g hydroquinone 25g 4-hydroxymethyl-
4-Methyl-1-phenyl-3-pyrazolidone 3.3 g Jetanolamine 15 g 5-Methylbenzotriazole 0.60 g Potassium bromide 3 g Dilute to 11 with water (adjust to pH 10.50) This developer Pour into the developing tank of an automatic processing machine, and as a developer replenisher, use a developer with the above composition, excluding potassium bromide, at pH 10.6.
I used a solution adjusted to 5.

4. Ammonium thiosulfate 175g Sodium sulfite 15g Ethylenediaminetetraacetic acid disodium dihydrate 0.025g Sodium hydroxide 6g Adjust to 11 with water (adjust to pH 4.95 with acetic acid) This fixer was placed in the fixing tank of an automatic processor and used as a fixer replenisher.

Washing tank liquid and water stock tank liquid Ethylenediaminetetraacetic acid disodium salt/dihydrate 0.4 g/l Automatic developing machine Dry to dry processing for 60 seconds Specific surface area developing tank 7.51 35°C x 11.5 seconds 15
cd/1 fixing tank 7,51 35℃X12.
5 seconds〃Water tank 6.0120℃×7.5
Seconds 94d/1 squeeze roller cleaning tank 200m! Water stock tank 251 Drying 50°C However, although a heater was used to maintain the temperature of both the developer and the fixing tank, cooling water was not used.

In the morning, when the system is started, the liquid level in the developer tank is detected, and the same amount of water is automatically replenished from the water stock tank to each of the developing, fixing, and washing tanks.

The above photosensitive material size (10 inches x 12 inches) 1
Every time a sheet is processed, add developer replenisher to the developing tank 40d Fixer replenisher to the fixing tank 45-Replenish the stock tank water (in the opposite direction to the film direction) from the squeeze roller cleaning tank to the washing tank 6 (ld) , the running process was continued for 3 months. At the end of the development work on day 1, the stock tank liquid was supplied to the roller cleaning device of the crossover rack (method described in Japanese Patent Application No. 163217/1983) using an 80-meter pump, and the small holes were cleaned. The rollers were cleaned by blowing air from the
(method described in No. 31338) During this time, if the developer, fixer, or water valve ran out, a new replenisher was added in the same way. During this time, high-performance photographic properties were obtained with easy work that required no maintenance at all other than supplying replenisher fluid.

Patent Applicant: Fuji Film Co., Ltd. Procedural Amendment Date: λ, 1986, λZ, Commissioner of the Patent Office, Mr. X9,'
, :″ 1.Display of the incident 1986 Long-awaited No. 3/l?7/
No. 2, Title of the invention Development processing method 3, Relationship with the case of the person making the amendments Applicant's address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment No. 5 of "Detailed Description of the Invention" in the specification , the statement in the “Detailed Description of the Invention” section of the statement of contents of the amendment? Correct as shown below.

1) 1st page // line "overtime" "industrial" and correct it.

2) Page 2, line 2 "Adhesion" "contact" and correct it.

3) The 3rd line of the page r (cm”) processing tank” “(crIL2)/Processing tank” and correct it.

4) The 7th line of the page "or" Delete all.

5) #Eb page // line "Exposure" "Exposure" and correct it.

6) Page 7, line 7 "time" "stand-by" and correct it.

7) Line 7 on page 7 "evaporate" "Evaporating thoughts" and correct it.

8) Page 73 Compound (2) " "of ” and correct it.

9) Page 17, line lλ After "dilution water" "," Insert.

lo) 2nd line on page 1 "Glycon" "Glucon" and correct it.

11) Insert "l-phenyl--methyl-hydroxymethyl-3-pyrazolidone/fJ" between line 1 and line C on page 31.

12) After the last line of page ≠2, insert "Also, the swelling rate according to the definition of US Patent @≠4c/≠30 is 110%."

13) No. ≦ After the last line of the page “Example μ.

In the same manner as in Example 3, U.S. Camellia No. 4t#/Hiroshi 301
A light-sensitive material having a swelling ratio of t-220 or more according to the definition of No. 1 was prepared and developed using the following automatic processor and processing solution formulation.

Automatic development Dry to pry! Second processing specific surface area developing tank tl, zl 5z0cxl, 5 seconds 11
c! IL2/L fixing tank 10tJko0Cxi3
．． z seconds 1aa"/washing tank 7.rl coz'
CX7 seconds rFcIL2/l <Developer concentrate formulation>
For 3re” Shishi LLL Potassium Tooxide /1079 “Rice Vinegar [
270f How to prepare liquid
Next item above Part A, Part B, Par
tcveIl [Next, add and dissolve while stirring, and finally make a sit with water to make a developer replenisher <pHto, 3o')
.

This developer replenisher was added at the ratio of the above-mentioned starter powder per liter, and the developer was first placed in the developing tank of an automatic processor (pH/(lJ, /j). After that, it was exposed to light. Each time the material was processed, the developer replenisher was replenished at the rate of t-4cjil/1 piece of quarter cut (/O1nchX/01nch).

Fixing concentrate formulation> Part A Jrl-a
rtB Fixer preparation method> Add water λ0tt- to a replenisher stock tank of approximately 200ml,
Next, the above Parts A, B, and F were sequentially added and dissolved while stirring, and the mixture was mixed with water to prepare a fixing solution replenisher.

A fixing solution identical to the brightening solution was initially filled in the fixing processing tank of an automatic processing machine (pHp, volume). Thereafter, each time the photosensitive material is processed, the fixer replenisher is added to tO'ILt/gX1.
Replenish 4jJ/sheet (/O1nchX/2inch) and next.

During this running experiment, the same amount of water was automatically replenished to each of the developing tank, fixing tank, and washing tank by detecting the liquid level of the developing tank during operation of the 10 machines.

After running for three months, I was able to obtain a photographic performance with a rating of 9.

Example! .

A comparison test was conducted using the following method using FGjroA (manufactured by Fuji Photo Film Co., Ltd.) t-2 as an automatic developing machine.
t - Thought to go.

Turn on the switch at 2 o'clock in the morning, put it in standby mode, and turn it on at 7 o'clock.
The photosensitive material used was Fuji Camera Contact Film 0A-10O (manufactured by Fuji Photo Film Co., Ltd.), and 10 pieces of cut size (development rate rots') were processed each day. As a developer, GR-D/(manufactured by Fuji Photo Film Co., Ltd.)'f! , and GR-F was used as the fixer.
/ (manufactured by Fuji Photo Film Co., Ltd.) The rinsing water used was the rinsing water used in Example /. Developer solution, fixer solution, washing water, 1 piece of cut-size film.
Replenished at the rate of

After the first day, after turning on the two automatic processors in the morning,
The automatic developing machine for B/W is used in the conventional manner, and for the automatic developing machine for S-co, the level of the developing tank, fixing tank, and washing tank liquid of the automatic developing machine is detected and water is washed according to the amount lost by evaporation. Next, a similar running experiment was carried out by replenishing the developing tank, fixing tank, and washing tank with water of the same composition as water. As a result, the photographic performance was as follows.

Here, the sensitivity is expressed relatively as the blackening density at the start/the reciprocal of the exposure amount required to obtain jf, t-1OO. Black spots are visually evaluated by magnifying the non-image area 10 times with a microscope. rjJ indicates that there are no black spots at all, and "≠" indicates that there are some black spots, but it is a screen for plate making. This is a practical version as a dot original version. "3""ko""l"
is of an impractical quality.

As is clear from the results in the table, the method of the present invention results in less change in sensitivity and fewer black spots. ” is inserted.

that's all

Claims (1)

[Claims] In a method of developing a silver halide photographic material using an automatic processor while replenishing a processing solution according to the processing amount, the liquid level of at least one processing tank in the automatic processor is detected. A developing processing method characterized by replenishing the amount of water that evaporates and decreases while waiting and/or stopping the developing processing.