JPH0545808A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of fur in a washing tank, etc. CONSTITUTION:A photosensitive material processing device 1 is juxtaposed with a developing tank 2, a fixing tank 3 and the washing tank 4 in this order and is further installed with a squeezing section 8 and a drying machine 9. The water 42 in a water storage part 18A of a stock tank 180 is supplied through a pipe 181 into the washing tank 4. The water 41 of the water storage part 18X is supplied to other processing tanks 2, 3 and crossover rollers 61, 62. A sterilizing agent of an active chlorine system or bromine system and a cheating agent are added to the water 42. The chlorine or bromine concn. in the water 42 is 0.1 to 100ppm in such a case and the amt. of the chelating agent to be added is 0.01 to 10g/liter. Such sterilizing agent and chelating agent can be used by tabletting these sterilizing agent and chelating agent and charging the tablets into a stock tank 180, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material or a light-sensitive material).
The present invention relates to a method for processing a silver halide photographic light-sensitive material, which is processed by using a light-sensitive material processing device such as an automatic processor.

[0002]

2. Description of the Related Art For example, a black-and-white light-sensitive material is subjected to a process of developing-fixing-washing after exposure, and then dried. Such processing is usually carried out by immersing the photosensitive material in each processing solution in a developing tank, a fixing tank and a washing tank using an automatic developing machine, and then drying it in a dryer.

In recent years, in order to protect the environment and save water resources, it has been a subject to reduce the replenishment amount and the drainage amount of the treatment liquid, especially washing water.

By the way, when the processing of the light-sensitive material is stopped for a long time, the washing water stays in the washing tank, and water scales are generated. When such water stains are generated, the suspended matter adheres to the photosensitive material to be processed next, and the photosensitive material is contaminated, and the filters and drain pipes are clogged.

Therefore, in order to remove the water marks, it is necessary to regularly wash the water washing tank. Especially, in the roller transfer system, once the water marks are generated, there are many parts of the transfer mechanism. The cleaning is very difficult work, and such maintenance requires a lot of labor and time.

Therefore, in order to improve such a defect,
Various methods such as the following have been proposed.

Japanese Patent Laid-Open Nos. 57-8542 and 58-105.
No. 145, No. 57-157244, No. 62-2209.
No. 51, etc., describes addition of various antifungal agents of thiazolylbenzimidazole compounds and isothiazolone compounds.

Further, a method for making pure water by using an ion exchange resin described in JP-A-61-131632, JP-A-60-60
A method of irradiating with an ultraviolet ray described in JP-A-263939, a method of applying a magnetic field and a method of applying an ultrasonic wave have been proposed in JP-A-60-263940.

Recently, Japanese Patent Application No. 01-91533
JP-A No. 2004-242242 describes providing Ag ⁺ ion releasing means for eluting Ag ⁺ ions in washing water.

However, each of the above-mentioned techniques does not have a sufficient effect of preventing the formation of scales even if they are used alone, and some of them are not practical in terms of long-term continuity. Regular cleaning management of automatic processors is also 2 weeks or 3
Rather than needing it every week, it has no practical meaning unless it is every two or three months. In addition, some additives have problems with toxicity and are not suitable for use.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art. The object of the present invention is to process a silver halide photographic light-sensitive material having a simple structure and very little generation of water scale. To provide a method.

[0012]

These objects are achieved by the present invention described in (1) to (4) below.

(1) When processing a silver halide photographic light-sensitive material using a light-sensitive material processing device for at least developing, desilvering and washing the silver halide photographic light-sensitive material, active chlorine or bromine sterilization is carried out. Agent, using a chelating agent added water at least in the washing treatment,
The chlorine or bromine concentration in this water is 0.1-100ppm,
A method for processing a silver halide photographic light-sensitive material, wherein the amount of the chelating agent added is 0.01 to 10 g / liter.

(2) The method for processing a silver halide photographic light-sensitive material according to the above (1), wherein the bactericidal agent and / or chelating agent is tableted and used by dissolving it.

(3) The method for processing a silver halide photographic light-sensitive material as described in (1) or (2) above, wherein the water is used to replenish the processing solution for the desilvering processing.

(4) The method for processing a silver halide photographic light-sensitive material as described in any one of the above items (1) to (3), wherein the water is used for cleaning a transfer mechanism part for transferring the silver halide photographic light-sensitive material.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The method for processing a silver halide photographic light-sensitive material of the present invention will be described below in detail with reference to the preferred embodiments shown in the accompanying drawings.

FIG. 1 shows a structural example of a photosensitive material processing apparatus used in the method of the present invention.

The photosensitive material processing apparatus 1 shown in the figure is, for example, a roller-conveying type automatic developing machine which conveys a sheet-shaped photosensitive material by rollers. Hereinafter, these will be sequentially described.

In the present invention, the type, form, etc. of the photosensitive material to be processed are not particularly limited.
It is preferably applied to the processing of black-and-white light-sensitive materials such as ray-sensitive materials and printing light-sensitive materials, and therefore the illustrated apparatus is for processing black-and-white light-sensitive materials.

In the photosensitive material processing apparatus 1 shown in FIG. 1, a developing tank 2, a fixing tank 3 and a rinsing tank 4 in which a developing solution, a fixing solution and washing water are respectively placed in a main body case are arranged in this order from the right side in the figure. They are installed side by side.

In the developing tank 2, a carrying roller 51 for carrying the photosensitive material S along a predetermined path in the tank is arranged. Further, also in the fixing tank 3 and the water washing tank 4, similar conveying rollers 52 and 53 are arranged, respectively.

A crossover roller 6 is provided between each of the processing tanks 2 to 4 and a squeeze portion 8 described later.
1, 62 and 64 are installed. These crossover rollers 61, 62, 64 squeeze out the processing liquid adhering to the surface of the photosensitive material when the photosensitive material S is nipped, and suppress the carry-in of the processing liquid from the previous tank to the next tank.

These crossover rollers are
For example, it is preferable that the roller is cleaned with water from a stock tank 180, which will be described later, to prevent the roller from being contaminated due to the adhesion of the developing solution component and the fixing solution component.
That is, a method of spraying water on the crossover roller after completion of the processing work for one day (Japanese Patent Application No. 62-18636),
Alternatively, it is preferable that a rinse tank is provided and the crossover roller is constantly immersed in the water in the rinse tank.

Guides 7 for guiding the photosensitive material S to the next rollers are provided between the rollers such as near the bottoms of the processing tanks 2 to 4 and on both sides of the crossover rollers 61 and 62.

It is preferable that the transport rollers 51 to 53 and the guide 7 are installed in a rack assembled for each processing tank.

The photosensitive material S introduced into the body case is
The rollers 51 to 53, 61, 62, and 64 sequentially convey the developing tank 2, the fixing tank 3, and the water washing tank 4 in order, and during that time, they are immersed in the respective processing solutions for development, fixing and water washing.

In each of the processing tanks 2 to 4, the processing solution is replenished and drained according to the processing tank, and preferably the processing solution is circulated.

It is preferable to replenish the developing tank 2 and the fixing tank 3 with a concentrated developer (or a plurality of types of parts agents) and a concentrated fixer, respectively, by diluting with water to obtain a replenisher having a desired concentration.

Further, in the developing tank 2 and the fixing tank 3, it is preferable to circulate the processing liquid, and these are circulated by circulation pumps 10 and 11, respectively.

The stock tank 180 supplies the washing water to the washing tank 4 and the water for diluting the concentrated liquid. Water is supplied to the stock tank 180 through a pipe 185 from a water source (water faucet) 187, and its flow rate is adjusted by a valve 186.

A squeeze portion 8 is provided on the upper left side of the washing tank 4 in FIG. In this squeeze portion 8, a plurality of pairs of squeeze rollers 81 are installed along the conveyance path of the photosensitive material S, and the squeeze rollers 81 sandwich and convey the photosensitive material S after washing so that the photosensitive material S is removed from the photosensitive material S. Remove water.

Below the squeeze section 8 in FIG. 1, a drying section 9 is provided.
Is provided. This drying unit 9 has a casing 91.
And a warm air supply means 94 for supplying warm air for drying into the casing 91, and inside the casing 91,
A conveyance roller 92 and a guide 93 are installed along the conveyance path of the photosensitive material S.

The warm air supply means 94 is a blower fan 95.
A warm air heated to preferably about 35 to 100 ° C. (more preferably about 40 to 80 ° C.) is supplied into the casing 91 through a duct 97 which has a heater 96 built therein and communicates with the casing 91. In the casing 91, the photosensitive material S that has passed through the squeeze portion 8 is conveyed by the conveying rollers 92 and comes into contact with the supplied warm air to be dried.

In such a photosensitive material processing apparatus 1,
FIG. 2 shows an example of the configuration of the supply system of the processing liquid (replenisher).

As shown in FIG. 2, the developing tank 2 contains a developing solution, the fixing tank 3 contains a fixing solution, and the washing tank 4 contains washing water. Both ends of the developer in the developing tank 3 communicate with the bottom of the developing tank, and are circulated by a pipe 12 in which a circulation pump 10 is arranged. Further, the fixing solution in the fixing tank 3 is also circulated by a pipe 13 in which a circulation pump 11 is arranged, like the developing solution. Although not shown, such a circulation system for the treatment liquid can be provided in the washing tank 4. In this case, the superior effect of the present invention is exhibited in the washing tank 4.

The washing tank 4 may be provided with a drainage pipe and a valve (not shown) installed in the middle of this pipe.

The temperature of the developing solution, the fixing solution, and the washing water in each of the processing tanks 2 to 4 are adjusted by a heater (not shown) to a temperature as described below.

The exposed photosensitive material S is the photosensitive material processing apparatus 1
After being introduced into the inside, the rollers 51-53, 61, 6
It is sequentially conveyed into the developing tank 2, the fixing tank 3, the water washing tank 4, the squeeze portion 8 and the drying portion 9 by a conveying means composed of 2, 63, etc., and is used for development, fixing (desilvering), water washing, draining and drying. Done.

Next, the replenishing liquid supply system (replenishing device) will be described.

As shown in FIG. 2, the replenisher supply system 200 is provided for replenishing the developer with reservoirs 151, 152 and 153 for storing three types of parts agents A, B and C constituting the developer, respectively. Stock tank 150 and a stock tank 15 for replenishing the fixer that stores a concentrated solution of the fixer
4 are provided.

On the upper part of the stock tank 150, a drug container 14 in which partial containers 141, 142 and 143 respectively containing three kinds of parts agents A, B and C are integrated.
0 is set, and on the upper part of the stock tank 154, a drug container 144 containing a concentrated solution of the fixer is set.

Each partial container 141 to 14 of the medicine container 140
From No. 3, the parts agents A to C are put into the corresponding parts agent storage sections 151 to 153 of the stock tank 150, and from the medicine container 144, the concentrated solution of the fixer is put into the stock tank 154.

From the parts agent storage parts 151 to 153 of the stock tank 150, liquid supply pipes 161 to 163 are respectively supplied.
Is extended to the developing tank 2, and the parts agents A to C are supplied to the developing tank 121 by the operation of pumps 171 to 173 installed in the middle of the liquid supply pipes 161 to 163. Further, a liquid feed pipe 164 is extended from the stock tank 154 to the fixing tank 3, and a pump 17 installed in the middle of the liquid feed pipe 164.
By the operation of 4, the concentrated solution of the fixing solution is supplied to the fixing tank 3.

The fixer may be supplied as a plurality of types (for example, two types) of part agents, and in this case, those having the same configurations as the chemical container 140 and the stock tank 150 are used. Also for the developer,
It may be supplied as two types of parts agents (a parts agent containing a dialdehyde hardener and a parts agent not containing it).

Further, the replenisher supply system 200 is provided with a stock tank 180 of washing water which also serves as a supply source of dilution water.

The wash water stock tank 180 is divided into two water storage portions 18X and 18Y by a partition plate 188, and water 41 and 42 are stored in the respective water storage portions 18X and 18Y. In this stock tank 180, tubes 181, 182, 183 extended to the washing tank 4, the crossover rollers 61 and 62, the fixing tank 3 and the developing tank 2, respectively.
And 184 are provided, and pumps 191, 192, 193 and 194 are provided in the middle of each of these tubes. In this case, the pipe 181 is connected to the water storage section 18Y,
The pipes 182 to 183 are connected so as to communicate with the water storage section 18X.

In the present invention, the partition plate 188 may not be provided and the stock tank 180 may have a single water storage section.

By the operation of the pump 191, the water 42 in the stock tank 180 is supplied to the washing tank 4 through the pipe 181.

By the operation of the pump 192, the water 41 (or 42) in the stock tank 180 passes through the pipe 182, and the crossover roller 6 which is a part of the transfer mechanism of the sensitive material.
1 and 62 are sprayed, for example, in a shower shape to clean these rollers 61 and 62. As described above, when the rinse tank of the crossover rollers 61 and 62 is provided, the water from the stock tank 180 is supplied to this rinse tank.

By the operation of the pump 193, the water 41 (or 42) in the stock tank 180 is supplied to the fixing tank 3 through the pipe 183, and the concentrated solution of the fixing liquid sent through the liquid sending pipe 164 is supplied. Dilute to give a fixer of the desired concentration.
When the concentration of the bactericide described below in the water 42 is relatively high, the water 41 is preferably supplied to the fixing tank 3.

By the operation of the pump 194, the water 41 (or 42) in the stock tank 180 is supplied to the developing tank 2 through the pipe 184 and is sent through the liquid supply pipes 171 to 173, respectively. To C or a mixed solution thereof is diluted to obtain a developing solution having a desired composition and concentration.

The water supply from the stock tank 180 to the washing tank 4 and the like is not limited to the operation of the pump as shown in the figure, and a water supply method by a head may be adopted, for example. In this case, a valve for adjusting the timing and flow rate of the water supply may be provided in the middle of the pipe connecting the stock tank 180 and the washing tank 4 or the like.

In the case of the configuration shown in the figure, tap water from the water source 187 to the water reservoir 18X of the wash water stock tank 180 through the pipe 185 is opened and closed by opening and closing the valve 186 (for example, the amount of liquid in the wash water stock tank 180 is detected). However, when the amount becomes less than or equal to a predetermined amount, it is supplied. Excessive water 41 overflows the partition plate 188 due to overflow to store water 18Y.
Flow into. In the present invention, water may be supplied to each of the water storage units 18X and 18 independently.

The composition of the water 42 in the wash water stock tank 180 will be described below.

To the water 42, an active chlorine type or bromine type germicide and a chelating agent are added. These additives not only have an excellent effect of preventing water stains, but also have no adverse effect on photographic properties, that is, they maintain good drying property, silver image storability, color tone and the like, and stains do not occur. Further, these additives have no problem in toxicity and safety of the compound itself, are excellent in handleability, and are inexpensive.

It has been conventionally known to apply an active chlorine-based bactericide as a scale inhibitor to washing water of an automatic processor (MW Beach, SMPTE Journal March 1976, Vol 85,
P154, RT Kreiman, J. Imaging Technology, Vol 1
0, No. 6 (Dec. 1984) P242). It is also useful for sterilization, as it is also used as a disinfectant for city water.
However, this alone is not enough to prevent water marks. Also, the active chlorine used for disinfecting city water is exhausted by the time it is supplied to the automatic processing machine, and in some cases, it has disappeared. At this time, it is very useful to additionally supply active chlorine as in the present invention. It is also known to use a chelating agent (Japanese Patent Laid-Open No. 62-153952).
No.), even if it is always maintained at a certain constant concentration, it is not sufficient to prevent water marks.

Examples of the active chlorine fungicides include sodium hypochlorite, 1-bromo-3-chloro-5,5-dimethylhydantoin (Great Lakes Chemical Corporation
(Trade name: PhotoBrom), chlorinated isocyanuric acid, sodium dichloroisocyanuric acid, N-chlorosuccinimide, trichloroisocyanuric acid, potassium dichloride cyanuric acid, chloropicrin [(Cl) ₃ CNO.
₂ ], 2-chloro-N- (hydroxymethyl) acetamide [ClCH ₂ CONHCH ₂ OH], 2-chloroacetamide [ClCH ₂ CONH ₂ ], chlorobutanol [(Cl) ₃ -C-C- (CH ₃ ) ₂ OH], the compound shown in the following chemical formula 1 (chloramine T), the compound shown in the following chemical formula 2 (dichloramine T), the compound shown in the following chemical formula 3 (chloramine B), and the like.

[0059]

[Chemical 1]

[0060]

[Chemical 2]

[0061]

[Chemical 3]

Examples of the active bromine-based bactericide include sodium hypobromite and the compounds shown in the following chemical formulas 4 to 15.

[0063]

[Chemical 4]

[0064]

[Chemical 5]

[0065]

[Chemical 6]

[0066]

[Chemical 7]

[0067]

[Chemical 8]

[0068]

[Chemical 9]

[0069]

[Chemical 10]

[0070]

[Chemical 11]

[0071]

[Chemical formula 12]

[0072]

[Chemical 13]

[0073]

[Chemical 14]

[0074]

[Chemical 15]

The amount of such an active chlorine-based or bromine-based bactericide (hereinafter, also simply referred to as a bactericide) added is such that the concentration of chlorine or bromine in the water 42 or the water supplied to the washing tank 4 is 0.1 to 0.1. The amount is set to 100 ppm, preferably 0.1.
The amount is 2 to 20 ppm, more preferably 0.2 to 10 ppm. If the chlorine or bromine concentration is less than 0.1 ppm, the effect of preventing water scale will be insufficient, and 100 ppm
When it exceeds the above value, the photographic property is not affected because the fixing solution is neutralized by the carry-in of the fixing bath into the washing tank 4 during the processing of the light-sensitive material S, but when the processing is stopped, corrosion occurs in each part of the light-sensitive material processing apparatus 1. It becomes easy and not preferable.

In the present invention, both an active chlorine type bactericide and an active bromine type bactericide may be used.

As the chelating agent, Al, Ca, Mg,
Any compound may be used as long as it can chelate a metal such as Fe.

As such a chelating agent, it is preferable to use at least one chelating agent of polyaminocarboxylic acid type or phosphonic acid type.

Specific examples of the polyaminocarboxylic acid type chelating agent include ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTP).
A), ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid, propylenediaminetetraacetic acid,
Nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, alkyliminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diamino-
2-Propanoltetraacetic acid, triethylenetetraminehexaacetic acid, hydroxyethyliminoacetic acid, oxybis (ethyleneoxynitrilo) tetraacetic acid, malic acid and sodium salts and potassium salts of these polycarboxylic acids.

Specific examples of the phosphonic acid-based chelating agent include the following chemical formulas 16, 17 and 18
It is a compound represented by each general formula of Chemical formula 19.

[0081]

[Chemical 16]

[0082]

[Chemical 17]

[0083]

[Chemical 18]

[0084]

[Chemical 19]

In the above formula, R _{1 to} R ₆ are each a hydrogen atom, a hydroxyl group, an alkyl group (having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group), an amino group, an alkoxy group (a carbon atom). Number 1 to 3, for example, a methoxy group,
Ethoxy group), alkylamino group (preferably having 1 to 3 carbon atoms), arylamino group (preferably having 6 to 8 carbon atoms), aryloxy group (preferably having 6 to 8 carbon atoms)
Represents 8).

R _{7 to} R ₁₃ are a hydrogen atom, a hydroxyl group, —COOM—, PO ₃ M ₂ , an alkyl group (having 1 carbon atom).
~ 3, such as methyl, ethyl, propyl, etc.).

R ₁₄ is a hydrogen atom, an alkyl group (having 1 carbon atom).
~ 3, such as methyl, ethyl, propyl, etc.). In addition, M represents an alkali metal such as sodium atom and potassium atom.

Specific compounds represented by the general formulas of Chemical Formulas 16 to 19 include those shown in Chemical Formulas 20 to 32 below.

[0089]

[Chemical 20]

[0090]

[Chemical 21]

[0091]

[Chemical formula 22]

[0092]

[Chemical formula 23]

[0093]

[Chemical formula 24]

[0094]

[Chemical 25]

[0095]

[Chemical formula 26]

[0096]

[Chemical 27]

[0097]

[Chemical 28]

[0098]

[Chemical 29]

[0099]

[Chemical 30]

[0100]

[Chemical 31]

[0101]

[Chemical 32]

These compounds are preferably added in the form of sodium salt and / or potassium salt.

Among these compounds, particularly preferable ones include, as aminopolycarboxylic acids, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-hydroxyethyl-N, N ', N'-.
Triacetic acid, propylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, etc., and phosphonic acid, ethylenediaminetetramethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc., and their sodium salts, potassium salts. It may be an ammonium salt.

Further, as a chelating agent, JP-A-62-1
You may use what is described in 53952 or Unexamined-Japanese-Patent No. 61-2149.

The amount of such a chelating agent added to the water 42 is 0.01 to 10 g / liter, and preferably 0.1.
It is set to 02 to 5 g / liter, more preferably 0.1 to 2 g / liter. If the amount of the chelating agent added is less than 0.01 g / liter, the chelating ability for Ca, Mg, etc. contained in water is insufficient, and if it exceeds 10 g / liter, it may be supplemented in terms of solubility. Difficult, practically meaningless and uneconomical.

In the present invention, the concentration of the bactericidal agent and / or the chelating agent in the water 42 in the washing tank 4 is set to the photosensitive material S.
The configuration may be changed according to the frequency of the processing (for example, daytime and nighttime). Generally, at low treatment frequency at night or on holidays, the flow of washing water in the washing tank 4 is small,
In this case, it is effective to increase the concentration of the above additive in order to enhance the effect of preventing water scale.

The method for adding such a bactericidal agent and a chelating agent is as follows.

First, a solution containing a bactericide and a chelating agent, or a solution containing both a bactericide and a chelating agent is added to the water storage section 18Y of the stock tank 180. The addition of this solution may be continuous or intermittent. Such an addition method has an advantage that the bactericide and the chelating agent are always supplied at a constant ratio.

Second, at least one of the bactericidal agent and the chelating agent is tableted, and this is put into the water storage section 18Y of the stock tank 180 and dissolved. The non-tabletted drug is added as a solution as in the first method above. It should be noted that the tablets are preferably charged at regular intervals or at regular processing amounts of the photosensitive material.

Thirdly, a bactericidal agent and a chelating agent are tableted together, and this is stored in the water storage section 18Y of the stock tank 180.
Add to and dissolve. It should be noted that the tablets are preferably charged at regular intervals or at regular processing amounts of the photosensitive material.

Fourth, in the middle of a water supply pipe such as a pipe (not shown) for supplying the tablets in the first and second methods to a pipe 185 from a water source 187 or a separately provided water reservoir 18Y. The tablet is stored in a tablet storage section (not shown) provided in the above, and the tablet is configured to dissolve by the passage of water in the water supply pipe.

In the method of dissolving and using the tablet of the bactericidal agent and / or the chelating agent as in the second and third methods, the pump for replenishment is not required, and the size and cost of the apparatus can be reduced. There is an advantage that.

In the present invention, the solution and the tablets may be charged directly into the water washing tank 4, and when the tablets are installed in the middle of the water supply pipe, the tablet storage part may be provided in the middle of the pipe 181 or the like. (Not shown) may be provided, and the tablet may be housed therein and dissolved.

The pH of the water 42 in the stock tank 180 and the rinsing water in the rinsing tank 4 is preferably 3 to 10, more preferably 4 to 9, and still more preferably 4 to 8.5.

In the present invention, with the above-mentioned structure, it is of course possible to prevent the generation of water scales in the washing tank 4 and the stock tank 180, and the water in the stock tank 180 can be stored in the developing tank 2 and It is supplied to the fixing tank 3,
Further, since it is used for cleaning the crossover rollers 61, 62, the development tank 2, the fixing tank 3, the crossover rollers 61, 62, and the piping system for water supply to these are also prevented from the generation and adhesion of water scale. .. In particular, with respect to the piping system, clogging of the inside of the pipes and filters due to water stains is prevented, and with respect to the crossover rollers 61 and 62, water stains adhere to the roller surfaces, which adhere to the photosensitive material S and cause stains. That inconvenience is prevented.

The amount of replenishment of the water 42 from the stock tank 180 to the washing tank 4 depends on the type of photosensitive material to be processed and other processing conditions, but is usually 1 per 1 m ^{2 of} photosensitive material to be processed.
It is preferably about 20 liters, more preferably 2-1.
It is about 5 liters.

The replenishment timing of the water 41, 42 is generally made in synchronization with the processing of the photosensitive material S.

In practice, the frequency of processing the photosensitive material S may be small, and in this case, all the washing water in the washing tank 4 is removed every predetermined time (for example, once a day). Alternatively, some of them can be replaced. Further, for example, when the processing amount of the photosensitive material S is 0.5 m ² or less in 1 hour,
10 to 10 times the amount of washing water in the washing tank 4 at each interval
Replace 100% (replenishing new flush water and draining existing flush water). By doing this,
The effect of preventing the formation of water marks is further exerted.

[0119] In the photosensitive material processing apparatus 1, the amount of carryover of the washing tank 4 fixer, type of processing photosensitive material, varies depending on conditions such as the temperature of the treatment liquid, usually, the processing photosensitive material 1 m ² per 5 to 50 ml, especially 7 to 30 ml are preferred.

In order to reduce the carry-in amount of the developing solution into the fixing tank 3 and the carry-in amount of the fixing solution into the water washing tank 4, a preliminary water washing tank between the adjacent processing tanks 2 and 3 and between the processing tanks 3 and 4. It is also possible to provide a preliminary washing with water by providing a water washing shower or the like.

Note that, unlike FIG. 2, in the present invention, the pipe 182 and the pump 192 for supplying water to the crossover rollers 61, 62 may be omitted.

The washing water may be replenished to the washing tank 4 by directly piping from the water source 187 to the washing tank 4. In this case, the solution or tablets are directly charged into the washing tank 4. Or, the tablets are installed in the water supply pipe to the washing tank 4 or the like.

Next, as a processing solution typically used in the present invention, a developing solution, a fixing solution and washing water (stabilizing solution).
Will be described.

In the present invention, the developing agent used in the developing solution is a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones, or dihydroxybenzenes and p-aminophenol, from the viewpoint of easily obtaining good performance. A combination of classes is preferred.

Further, ascorbic acids may be used as a substitute for hydroquinones.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dipromhydroquinone, There are 2,5-dimethylhydroquinone and the like, and hydroquinone is particularly preferable.

As the p-aminophenol type developing agent used in the present invention, N-methyl-p-aminophenol,
p-aminophenol, N- (β-hydroxyethyl)
-P-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p
-Benzylaminophenol, etc., but especially N-
Methyl-p-aminophenol is preferred.

Examples of the 3-pyrazolidone type developing agent used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-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-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone and the like.

The developing agent is preferably used usually in an amount of 0.001 to 1.2 mol / liter.

As the preservative of sulfite used in the development,
Sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, and potassium metabisulfite. The sulfite is preferably 0.2 mol / liter or more, particularly preferably 0.4 mol / liter or more. The upper limit is preferably 2.5 mol / liter.

The pH of the developer used for development is 8.5 to 13
Is preferably in the range of, and more preferably pH 9-12.

The alkaline agent used for setting the pH includes
Sodium hydroxide, potassium hydroxide, sodium carbonate,
It contains a pH adjusting agent such as potassium carbonate, sodium triphosphate and potassium triphosphate.

Using buffers such as JP-A-62-186259 (borate), JP-A-60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate. Good.

A hardener may be used in the developing solution. As the hardener, a dialdehyde hardener or a bisulfite adduct thereof is preferably used. Specific examples thereof include glutaraldehyde, and a bisulfite adduct thereof.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, Organic solvent such as ethanol and methanol: 1-phenyl-5-
Mercapto-tetrazole, 2-mercapto-benzimidazole-5-sulfonic acid sodium salt and other mercapto-based compounds, 5-nitroindazole and other indazole-based compounds, 5-methylbenztriazole and other benztriazole-based compounds such as antifoggants Well, Re
search Disclosure Volume 176, No. 17643, X
Development accelerators described on page XI (December issue, 1978), and if necessary, toning agents, surfactants, defoamers, water softeners, amino compounds described in JP-A-56-106244. May be included.

In the present invention, a silver stain preventing agent such as the compounds described in JP-A-56-24347 can be used in the developing solution.

The developing solution is described in JP-A-56-1062.
Amino compounds such as alkanolamines described in No. 44 and EP-A-0136582 can be used.

The fixing solution is an aqueous solution containing thiosulfate as a fixing agent, preferably pH 3.8 or higher, more preferably pH 4.0 to 7.0, still more preferably pH 4.2 to 5.
It is 5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 3 mol / liter.

The fixing agent may contain a water-soluble aluminum salt which acts as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, and the amount of the compound is 0.1.
01 to 0.03 mol / liter is particularly effective.

If desired, the fixer may contain a preservative (for example,
Sulfites, bisulfites), pH buffers (eg acetic acid, boric acid), pH adjusters (eg sulfuric acid), chelating agents having the ability to soften water, and compounds described in JP-A-62-78551 can be contained. ..

The washing water in the present invention is a concept including not only washing water in a narrow sense but also so-called stabilizing liquid.

In addition to the addition of the bactericidal agent and the chelating agent, the washing water may be optionally provided with the following deterrent means. Such an anti-fungus means plays a role of assisting the effect of preventing the formation of scales by the addition of the bactericidal agent and the chelating agent, and the effect of preventing the formation of scales can be further enhanced.

As an anti-fungus means, Japanese Patent Laid-Open No. 60-263
UV irradiation method described in No. 939, 60-26394
Method using magnetic field described in No. 0, Ibid. 61-13163
A method for producing pure water using the ion exchange resin described in JP-A No. 62-115154 and JP-A No. 62-15395.
No. 2, No. 62-220951, No. 62-209532
The method of using the antibacterial agent described in No. 1 is applicable.

Furthermore, LFWest. "Water Quality C
riteria "Photo. Sci. & Eng. Vol.9 No.6 (1965), MW
Beach, "Microbiological Growths in Motion-picture
Processing "SMPTE Journal Vol.85, (1976), RODeeg
an, "Photo Processing WashWater Biocides" J. Imagi
ng Tech 10, No. 6 (1984) and JP-A-57-8542.
No. 57-58143, No. 58-105145,
57-132146, 58-18631, 5
Antibacterial agents, antifungal agents, surfactants and the like described in 7-97530, 57-157244 and the like can be used in combination as necessary.

If necessary, the washing tank (or stabilizing tank) 4 and the stock tank 180 may be equipped with RTKreiman.
J. Image.Tech 10, (6) p. 242 (1984), isothiazoline compounds, Research Disclosure No. 205.
Vol., No. 20526 (May, 1981, May), isothiazoline compounds, Vol. 228, No. 22845 (1983).
, April issue), the compounds described in JP-A-62-209532, and the like.
It can also be used as a bacteriostatic agent (Microbiocide).

In addition, Hiroshi Horiguchi, "The Chemistry of Antibacterial and Antifungal",
A compound as described in Sankyo Shuppan (Showa 57), "Handbook of Antibacterial and Antibacterial Technology", Japan Society for Antibacterial and Antibacterial Agent, Hakuhodo (Showa 61) may be included.

Needless to say, the additives to the washing water are not limited to those mentioned above.

In the present invention, JP-A-63-1835 is used.
It is also possible to provide a squeeze roller cleaning tank described in No. 0. Further, it is also preferable to adopt a constitution of a water washing step as disclosed in JP-A-63-143548.

Further, as described in JP-A-60-235133, a part or the whole of the overflow liquid from the washing tank produced by supplementing the washing water is treated in the preceding treatment step. It can also be used for certain fixers.

In the present invention, the "developing time" is the time from the dipping of the tip of the photosensitive material to be processed in the developing solution to the dipping in the next fixing solution, and the "fixing time" is the fixing solution. The time from the time of dipping to the time of dipping in the next washing water (stabilizing liquid), "washing time" means the time of dipping in washing water. The "drying time" means the time during which the light-sensitive material is in the drying section.

The developing time is 5 seconds to 3 minutes, preferably 8 seconds to 2 minutes, and the developing temperature is 18 ° C to 50 ° C.
Is preferable, and 20 ° C. to 40 ° C. is more preferable.

The fixing temperature and time are preferably about 18 ° C. to about 50 ° C. for 5 seconds to 3 minutes, and more preferably 20 ° C. to 40 ° C. for 6 seconds to 2 minutes. Within this range, sufficient fixing can be performed, and the sensitizing dye can be eluted to the extent that residual color is not generated.

The temperature and time for washing (stability) with water are 0 to 50 ° C.
Is preferably 6 seconds to 3 minutes, and more preferably 10 ° C. to 40 ° C. and 6 seconds to 2 minutes.

In the present invention, as described above, the photosensitive material which has been developed, fixed and washed with water is dried through the squeeze roller for squeezing the washing water. Drying is preferably performed at about 35 to 100 ° C, and the drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 minutes, more preferably 40 to 80 ° C for about 5 seconds to. 2 minutes.

In the present invention, when dry-to-dry development processing of 100 seconds or less is performed, in order to prevent development unevenness peculiar to rapid processing, a rubber material as described in JP-A-63-151943 is used. Is used as a roller at the outlet of the developing tank, and is disclosed in JP-A-63-151944.
As described in the specification, the discharge flow rate for stirring the developer in the developer tank is set to 10 m / min or more,
Further, as described in JP-A-63-264758, it is more preferable to stir more strongly than during standby at least during the development processing.

In the present invention, the kind of the light-sensitive material to be processed is not particularly limited, and examples thereof include a color negative film, a color reversal film, a color printing paper, a color positive film, a color reversal printing paper, a plate-making photographic light-sensitive material and an X-ray. Examples include various photographic materials such as photographic light-sensitive materials, black-and-white negative films, black-and-white photographic paper, and micro-photosensitive materials.

Among them, black-and-white light-sensitive materials, especially X-ray film for direct shooting and X-ray film C for indirect shooting.
It is suitable for processing medical or industrial X-ray photographic light-sensitive materials such as RT films, X-ray dub photographic light-sensitive materials, and medical CRT image photographic light-sensitive materials.

[0160]

EXAMPLES Specific examples of the present invention will be described below.

(Example 1) Medical X-ray sensitive materials RX, Super HR-S, Super HR-A, Super HR manufactured by Fuji Photo Film Co., Ltd.
-L in terms of treatment amount (area) ratio in order of 30%, 50%, 10%,
A running experiment was performed with 10%.

The average processed amount of the photosensitive material per day is about 200 sheets in terms of the size of quarter cut.

The automatic processor, processing solution and the like used in this experiment are as follows. All of these are manufactured by Fuji Photo Film Co., Ltd.

Developer: FPM-5000 type processing solution: developer / RD-3 starter / RD-3S fixer / Fuji F

The treatment process was as shown in Table 1 below, and tap water was used as the washing water.

[0166]

[Table 1]

The amount of the starter used was 20 ml per liter of the developing replenisher.

22 liters of the developing replenisher was stored in the developing tank of the automatic developing machine. Next, 440 ml of the starter was weighed and added to the developing tank. After that, a developing replenisher was further added just before overflow, and this was used as a developing starter.

On the other hand, the fixing tank was filled with the fixing replenisher just before it overflowed.

The developing replenisher is 45 m per sheet of four-cut size
60 ml of fixing replenisher was replenished.

The rinsing tank was filled with tap water, and during the development process, the rinsing water was 3 liters per minute (0.
4 liters) was replenished.

After the treatment for one day was completed, all the washing water in the washing tank was drained and this was repeated every day.

Water storage unit 1 in the washing tank and in the stock tank
The additives shown in Table 2 below were added to the water in 8Y.

[0174] In such a treatment, the state of generation of scales in the washing tank was examined. The results are shown in Tables 2 and 3 below.
(Continued from Table 2).

There was no problem with the toxicity of the washing water in these ranges.

There was no problem with the stability and photographic properties of the obtained image.

[0177]

[Table 2]

[0178]

[Table 3]

As shown in Table 3, in each of the examples of the present invention, the effect of preventing water stain was excellent, the toxicity was safe, the safety was ensured, and the handling was easy.

At night, the processing amount of the sensitizing material becomes extremely small, so that the total amount of replenishing water for washing decreases, so that the concentrations of the bactericide and the chelating agent become higher than those in the daytime. At night,
The generation of water scales is likely to occur because the flow of water in the washing tank is small. However, since the concentrations of the bactericide and the chelating agent are increased, the generation of water scales can be effectively prevented.

[0181]

As described above, according to the present invention, an extremely excellent effect of preventing the formation of water stains can be obtained in the water washing tank of the light-sensitive material processing apparatus and other places, and the photographic property is not adversely affected. There is no problem with toxicity and safety.

[Brief description of drawings]

FIG. 1 is a cross-sectional side view showing a configuration example of a photosensitive material processing apparatus used in the present invention.

FIG. 2 is a schematic configuration diagram for explaining a processing method of a silver halide photographic light-sensitive material of the present invention.

[Explanation of symbols]

 1 Photosensitive Material Processing Device 2 Developing Tank 3 Fixing Tank 4 Water Washing Tank 41, 42 Water 51, 52, 53 Conveying Rollers 61, 62, 64 Crossover Roller 7 Guide 8 Squeeze Section 81 Squeeze Roller 9 Drying Section 91 Casing 92 Conveying Roller 93 Guide 94 Warm air supply means 95 Blower fan 96 Heater 97 Duct 10, 11 Circulation pump 12, 13 Tube 140, 144 Chemical container 141, 142, 143 Partial container 150, 154 Stock tank 151, 152, 153 Parts agent storage part 161, 162, 163, 164 Liquid feeding pipe 171, 172, 173, 174 Pump 180 Rinsing water stock tank 18X, 18Y Reservoir 181, 182, 183, 184, 185 pipe 186 Valve 187 Water source 188 Partition plate 191, 192, 193, 194 Po Flop 200 replenisher supply system S photosensitive material

Claims (4)

[Claims] 1. An active chlorine-based or bromine-based bactericide for processing a silver halide photographic light-sensitive material by using a light-sensitive material processing apparatus for at least developing, desilvering and washing with a silver halide photographic light-sensitive material. And water containing a chelating agent are used for at least the washing treatment, and the concentration of chlorine or bromine in the water is 0.1 to 100 ppm, and the amount of the chelating agent added is 0.01 to 10 g / liter. A method for processing a silver halide photographic light-sensitive material. 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the bactericidal agent and / or chelating agent is tableted and used by dissolving it. 3. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the water is used to replenish the processing solution for the desilvering processing. 4. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the water is used for cleaning a conveyance mechanism part for conveying the silver halide photographic light-sensitive material.