JPH04268554A - Device for processing photosensitive material - Google Patents

Abstract

PURPOSE:To facilitate extremely rapid processing of photosensitive materials with high quality and to reduce the size of the device for wet processing. CONSTITUTION:Processing rollers 18 are immersed at least partly in the processing liquid in processing tanks. The photosensitive material 10 is transported by being engaged with the peripheral surfaces of the processing rollers 18. The processing rollers 18 provided with elastic deformable members 11 on the peripheral surfaces rotate at the absolute value of the circumferential speed of >=1.5 times the absolute value of the transporting speed of the photosensitive material. Processing liquid ejection members 22 are provided near the processing rollers 18 to rapidly supply the fresh processing liquid. Cam mechanisms 25 for sinking the entire part of the processing rollers 18 into the processing liquid at the shutdown of the processing liquid are provided. The processing liquid is rapidly exchanged on the surface of the photosensitive material in spite of the extremely rapid processing and, therefore, the high- efficiency processing is possible and since the volume of the processing liquid is small, the size of the device for processing is reduced. The deposition of the processing liquid components does not arise by the evaporating of the processing liquid stick on the peripheral surfaces of the processing rollers.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a wet processing apparatus for photosensitive materials, and more specifically, to a novel photosensitive material for stable and continuous processing of high quality photosensitive materials with excellent rapid processing properties. It relates to a processing device.

0002

2. Description of the Related Art As a photosensitive material processing apparatus, there is an apparatus that performs processing such as development, bleaching, fixing, washing, stabilization, and drying on a photosensitive material after exposure to form an image on the photosensitive material. Among the treatment steps, water washing and stabilization are also called washing steps. Usually, the processing step consists of a step in which the exposed photosensitive material is immersed in each processing solution while being transported.

As a recent trend, it is desired to simplify and speed up the processing of all photosensitive materials, but in the conventional processing liquid immersion method, when the processing is simplified or downsized, the ratio of immersion time to the total processing time increases. This causes problems such as the inability to secure the necessary processing time in the processing solution. As a means to compensate for this drawback, regarding water washing equipment, as a means other than immersion, Japanese Patent Application Laid-Open No. 62-240967 and No.
As described in Japanese Utility Model Publication No. 40969, there is a device for cleaning the surface of a photosensitive material with running water, and a device for cleaning the surface of a photosensitive material with running water,
As described in Japanese Patent Application No. 1-147442, an apparatus has been proposed in which cleaning is performed by spraying cleaning water onto a photosensitive material.

0004

However, the above-mentioned processing cannot fully demonstrate its performance during rapid processing. One of the reasons for this is that the dirty processing solution near the surface of the photosensitive material is not smoothly replaced with fresh processing solution, and as a result, the processing time in the processing solution is shortened. I can't.

For example, taking the water washing process as an example, when a photosensitive material to which a bleach-fix solution has adhered is dried as it is, processing solution components such as thiosulfate and silver thiosulfate complexes contained in the bleach-fix solution crystallize on the film surface. During storage, the image silver may react with processing solution components, resulting in discoloration or fading of the image. Silver complex salts dissolved in the processing solution may turn into silver sulfide and cause contamination. Therefore, water washing and stabilization are performed to remove the processing solution components on the surface of the light-sensitive material and inside the emulsion film.

In the conventional method of immersing a photosensitive material in washing water and washing it with water, a conveying means is required to transport the photosensitive material within a washing tank containing a large amount of washing water for immersing the photosensitive material. Therefore, the conveyance mechanism is complicated and the device becomes large. Furthermore, since the photosensitive material is immersed in the washing water for a predetermined period of time, the washing time becomes long.

[0007] Furthermore, a device for immersing a photosensitive material in rinsing water in a slit-shaped rinsing tank described in Japanese Patent Application Laid-Open No. 63-216050 can perform efficient rinsing with a small amount of rinsing water, but the device is complicated. It is difficult to maintain.

[0008] Also, JP-A-62-240967, JP-A-62-240967
In the apparatus described in Japanese Patent No. 240969, which cleans the surface of a photosensitive material with running water, sufficient washing cannot be performed only by running down the washing water.

Furthermore, the apparatus described in Japanese Patent Application Laid-Open No. 62-240970, which supplies flowing sewage in substantially multiple stages, is large and complicated, and difficult to maintain.

[0010] Furthermore, Utility Model Application No. 50-947, No. 51-1
In the apparatus described in Japanese Patent No. 47442, which performs washing by spraying washing water onto a photosensitive material, sufficient washing cannot be performed only with a jet of washing water.

[0011] As is clear from what has been stated above,
SUMMARY OF THE INVENTION An object of the present invention is to provide a processing apparatus for a photosensitive material that can efficiently exchange a processing liquid near the surface of a photosensitive material, has high quality, is simple, and can be processed extremely quickly.

0012

Means and Effects for Solving the Problems The above objects of the present invention are achieved by the photosensitive material processing apparatus described in (1) to (3) below.

(1) a processing roller, at least a portion of which is immersed in a processing liquid, rotates, and has an elastically deformable member on its peripheral surface;
a means for transporting the photosensitive material by engaging the photosensitive material with the peripheral surface of the processing roller, the absolute value of the circumferential speed of the processing roller is A photosensitive material processing apparatus characterized in that the photosensitive material is processed by rotating the processing roller at a speed of 1.5 times or more the absolute value of the photosensitive material conveyance speed. (2) The photosensitive material processing apparatus according to (1), further comprising a cleaning means for cleaning the peripheral surface of the processing roller. (3) In an apparatus that processes a photosensitive material by engaging the photosensitive material with the peripheral surface of a rotating processing roller partially immersed in a processing liquid, the processing roller is completely immersed in the processing liquid when the apparatus is not in operation. 1. A photosensitive material processing apparatus comprising a processing roller dipping means for dipping.

According to the present invention, an elastically deformable member is provided on the circumferential surface of the processing roller, which is at least partially immersed in the processing liquid, and the emulsion surface of the photosensitive material is attached to the circumferential surface of the processing roller that is immersed in the processing liquid. The amount of processing liquid supplied to the photosensitive material by rotating the processing roller at an absolute value of the circumferential speed of the processing roller at least 1.5 times the absolute value of the photosensitive material conveyance speed while processing the photosensitive material. The processing liquid near the surface of the photosensitive material can be efficiently exchanged. Furthermore, since the elastically deformable member slides into contact with the photosensitive material, it is possible to reliably destroy and remove the film formed on the emulsion surface.

Moreover, by providing a cleaning means (for example, a cleaning brush, a cleaning nozzle, etc.) for removing processing liquid components adhering to the peripheral surface of the processing roller, the processing liquid after processing on the processing roller can be reused. The photosensitive material is not supplied to the photosensitive material, and the photosensitive material can be processed satisfactorily with a small amount of processing liquid during ultra-rapid processing, and the processing apparatus can be downsized. In particular, the cleaning means is effective for a processing roller that has a concave portion formed on its circumferential surface as a result of having an elastically deformable member on its circumferential surface as in the present invention.

For example, in the cleaning step, processing liquid components adhering to the photosensitive material are removed by the rapidly exchanged cleaning water, making it possible to perform efficient cleaning. Furthermore, in the developing process, the developer in contact with the emulsion surface of the light-sensitive material is quickly replaced with fresh developer, making it possible to speed up the development. Also,
By removing the processing liquid adhering to the part of the processing roller that is in the air, processing liquid components do not precipitate on the processing roller when the device is stopped, and it is possible to prevent the processing roller from becoming dirty.
Photosensitive materials also do not get dirty.

[0017] In this way, processing steps such as cleaning and development can be speeded up, processing can be carried out efficiently with a small amount of processing liquid, and the number of components is small, so the apparatus can be simplified and downsized. This also makes maintenance easier.

In the present invention, the type of processing liquid is not limited as long as the photosensitive material is processed in contact with the processing liquid, but in particular, the photosensitive material wetted with a certain processing liquid may be subjected to other types of processing. Suitable for supplying liquid. Note that the wet photosensitive material refers to the photosensitive material immediately after being removed from the developer, bleach-fix solution, bleaching solution, fixer, or the like.

[0019] As a method for applying liquids such as emulsions used in photosensitive materials, there is a known method in which a coating roller in contact with the liquid is brought into rotational contact with the photosensitive material in order to ensure a constant coating amount. However, such a coating roller is generally driven to rotate in the same direction as the conveyance direction at a circumferential speed approximately equal to the conveyance speed of the photosensitive material. If the circumferential speed of the applicator roller is rotated at a speed higher than the conveyance speed of the photosensitive material, there are problems such as scratches on the surface of the photosensitive material and failure to maintain coating accuracy. Making it faster has not yet been achieved.

However, it has been found that even when processing is carried out by rotating the processing roller at a higher speed than the photosensitive material transport speed as in the present invention, no scratches occur on the surface of the photosensitive material. This is thought to be because a film of processing liquid is formed between the processing roller and the photosensitive material, and the liquid is exchanged continuously and at high speed.

[0021] As described above, rotating the processing roller at a high circumferential speed is important from the viewpoint of liquid exchange, and is a completely new method that cannot be achieved by simply extending the concept of conventional coating means. It's a method.

The absolute value of the peripheral speed of the processing roller is at least 1.5 times the absolute value of the photosensitive material conveyance speed, and 1.
The effects of the present invention have been confirmed up to a speed ratio of 500 times. The speed ratio is preferably 20 to 1000 times, more preferably 30 to 500 times, particularly preferably 60 to 300 times.
It's double. The above speed ratio can be increased within a limit that does not cause splashing of the processing liquid. The peripheral speed of the processing roller is
It is set from the above speed ratio and the photosensitive material conveyance speed. In fact, the effects of the present invention have been confirmed up to a circumferential speed of the processing roller of 150 km/hour. Furthermore, although the direction of rotation of the processing roller is not limited, it is preferable that the processing roller rotates in a direction opposite to the direction in which the photosensitive material is conveyed.

Further, according to the present invention, the processing roller rotates with at least a portion immersed in the processing liquid, by providing a mechanism for submerging the entire processing roller in the processing liquid when the processing apparatus is not in operation. It is possible to prevent the processing liquid adhering to the peripheral surface of the roller from evaporating and the processing liquid components to be deposited on the peripheral surface, thereby eliminating contamination of the surface of the photosensitive material when it comes into contact with the processing roller.

The shape and material of the processing roller and the elastically deformable member used in the present invention are not particularly limited, but the processing roller may be, for example, a roller having recesses or protrusions on its circumferential surface in order to be able to carry the processing liquid. There are also rollers that have water absorption properties. As an elastically deformable member, the Young's modulus is 5 × 105
Natural rubber and the following synthetic rubbers having a density of N/m 2 or less can be used. Diene-based (butadiene rubber, isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber); Olefin-based (isobutylene-isoprene rubber, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, chlorosulfonated polyethylene, Chlorinated polyethylene, ethylene-vinyl acetate copolymer); polysulfide-based (polyalkylene sulfide); organosilicon compound-based (silicon rubber); fluorine-based compound (polychlorotrifluoroethylene, vinylidene fluoride-propylene hexafluoride)・Copolymer); Urethane type (urethane rubber); Ether type (propylenoxide rubber, epichlorohydrin rubber); Vinyl type (acrylic acid ester-acrylonitrile copolymer, acrylic acid ester-2-chloroethyl vinyl ether copolymer)

The usable dimensions of the elastic deformation member are 1 mm to 15 mm in radial height when fixed to the roller;
Preferably 2 mm to 10 mm, thickness 0.02 mm to 1
5mm (the thickness of the tip of the member and the part where it is attached to the roller may be different), and the axial width of the roller is 5mm or more (
The maximum width is up to the width of the photosensitive material that can be processed. Angle at which the elastically deformable member is fixed to the roller surface (angle with respect to the tangent)
is 5° to 90°, and the number is one or more (provided at intervals such that they do not touch adjacent members).

According to the present invention, good processing can be performed even with a small amount of processing liquid. Therefore, even if the capacity of the treatment tank is 450 ml or less, good treatment can be performed. Furthermore, even if the capacity of the processing tank is 45 ml or less, good processing can be performed by using the processing roller of the present invention. The lower limit of the capacity of the treatment tank is not particularly limited, but it is sufficient that it includes an amount that enables treatment.

On the other hand, when the processing tank is made smaller by a method in which the photosensitive material is immersed in the processing solution, the speed at which the photosensitive material is transported is slowed down to obtain a predetermined liquid contact time. If necessary, rapid processing cannot be achieved. Furthermore, if the transport speed is slow, the liquid near the surface of the photosensitive material cannot be exchanged well, and if the processing liquid is stirred to prevent this, the liquid level will not be stabilized and the immersion time will not be constant, resulting in uneven processing. Furthermore, in a configuration in which a photosensitive material is transported or reversed in a processing liquid, there is a limit to miniaturization due to the arrangement of each component.

In particular, under conditions of low replenishment and slow processing, the processing liquid is slow to reach the equilibrium concentration, leading to unstable processing. To improve this, the processing tank should be made smaller and the amount of processing liquid should be reduced. This is effective.

By processing the photosensitive material by engaging it with the peripheral surface of the processing roller, which is at least partially immersed in the processing liquid, as in the present invention, it is possible to achieve good results even when the capacity of the processing tank is small. The treatment tank can be made smaller.

When the processing roller, which is at least partially immersed in the processing liquid, is rotated, there are many opportunities for the processing liquid to come into contact with air.
Evaporation and oxidation of the processing liquid progresses rapidly, resulting in a decline in processing performance. Therefore, when carrying out the present invention, it is preferable to seal the upper part of the processing liquid to prevent evaporation and oxidation of the processing liquid. In particular, in the rapid water washing process, the temperature of the washing liquid is often raised to speed up the process, which tends to accelerate evaporation and oxidation.

[0031] Furthermore, when cleaning is performed using a processing roller,
If the amount of evaporation of the cleaning liquid is large, the liquid level may drop below the processing roller, causing problems such as scratches on the photosensitive material.

[0032] In order to prevent these, it is preferable to substantially seal the upper part of the processing liquid. In order to prevent evaporation and oxidation of the processing liquid, it is preferable to prevent the processing liquid from coming into contact with air completely, but it is sufficient that the processing liquid is not completely sealed, but is substantially sealed.

As one aspect of sealing, there is a structure in which the upper space of the processing liquid is closed with a sealing lid or the like, or a structure in which a floating lid or the like is provided to prevent the liquid surface from coming into contact with air.

[0034] For sealing, it is particularly important to seal the entrance and exit of the photosensitive material and the degree of opening of the liquid surface, but it is described in Japanese Patent Application Laid-Open No. 2-84642 that the material is substantially sealed. As such, the maximum slit width for color developer, bleach-fix, bleach, fix and stabilizer is 1.5 mm;
For cleaning liquid, it is 2.5 mm. Further, an inert gas such as nitrogen gas or argon gas may be sealed inside the sealed device.

Processing solutions that can be used in the present invention include developing solutions, fixing solutions, bleach-fixing solutions, washing solutions, and stabilizing solutions for photosensitive materials. Furthermore, the pH of the processing liquid that can be used is 3 to 13, the viscosity is 500CP or less, and the surface tension is 15 to 75 dyn/c.
m, specific gravity is 0.75 to 1.3, and any of these can be selected and used.

When the present invention is applied to cleaning treatment, cleaning solutions that can be used include ion exchange water, tap water, etc., which contain preservatives, chelating agents, surfactants, pH buffers, and optical brighteners. , an antifungal agent, a hardening agent, and the like. Furthermore, since the cleaning liquid is supplied only to the emulsion surface of the photosensitive material, subsequent drying is facilitated.

Furthermore, in the cleaning process, when multiple cleaning tanks are arranged to perform multi-stage cleaning processing, good cleaning can be achieved by applying the configuration of the present invention to at least one of the multiple tanks. . In this multi-stage cleaning process, a so-called counter-flow system is preferable, in which the last stage tank is replenished with the cleaning liquid, and the cleaning liquid is sequentially replenished from the latter stage tank to the previous stage tank. Further, it is preferable that the amount of cleaning liquid refilled to the last tank is 0.5 to 3 times the amount of cleaning liquid brought in by the photosensitive material from the previous tank. Furthermore, the cleaning process time is 3
Preferably, the time is within 0 seconds.

The light-sensitive material used in the present invention may be any light-sensitive material that uses a processing liquid, such as black and white photographic materials for printing, medical use, and general use, and color photographs such as color negative films, color reversal films, and color papers. There are photosensitive materials. The processing of the present invention can process color prints by taking advantage of speed, and can be applied to intelligent color hard copy processing where speed is more desirable.

In particular, when the present invention is applied to intelligent color hard copies, it is preferable to perform scanning exposure using high-density light such as a laser (for example, a semiconductor laser) or a light emitting diode.

The present invention also provides particularly excellent cleaning when cleaning color photographic materials in an extremely short time as described in the embodiments of the present invention and Japanese Patent Application No. 1-232590. be effective.

Silver halides used in the light-sensitive material according to the present invention include silver chloride, silver bromide, (iod)silver chlorobromide,
Silver iodobromide etc. can be used, but especially for the purpose of rapid processing, silver chloride containing substantially no silver iodide can be used.
It is preferred to use silver chlorobromide or silver chloride emulsions with a mole % or more, more preferably 95% or more, particularly 98% or more.

[0042] In the photosensitive material according to the present invention, in order to improve the sharpness of images, etc., the hydrophilic colloid layer is added to the hydrophilic colloid layer described in European Patent No. 27 of EP 0,337,490A2.
Adding dyes that can be decolorized by processing (especially oxonol dyes) described on pages 76 to 76 so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or improving the water resistance of the support The resin layer contains 12% by weight or more (more preferably 14% by weight) of titanium oxide that has been surface-treated with a di- to tetrahydric alcohol (for example, trimethylolethane), etc.
(above)) is preferably included.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277,589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. The use of a compound that chemically combines with the oxidized form of a group amine color developing agent to form a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, to reduce the amount remaining in the film during storage after processing. This is preferable in order to prevent the generation of stains and other side effects due to the formation of color pigments due to the reaction between the color developing agent or its oxidized product and the coupler.

Furthermore, the photosensitive material according to the present invention has a preventive agent as described in JP-A-63-271247, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration. It is preferable to add a fungicide.

[0046] The support used in the photosensitive material according to the present invention may be a white polyester support for display purposes or a support on the side having a silver halide emulsion layer on which a layer containing a white pigment is provided. A support may also be used. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support. In particular, the transmission density of the support was set to 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferable to set it in the range of 5 to 0.80.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case in particular, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred.

[0048] Also, upon exposure, US Pat. No. 4,88
Preferably, a band stop filter as described in US Pat. No. 0,726 is used. This eliminates optical color mixture and significantly improves color reproducibility.

The exposed photosensitive material may be subjected to a color development process, but for the purpose of rapid processing, it is preferable to carry out a bleach-fixing process after the color development. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of promoting desilvering.

Silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied to process this light-sensitive material As processing additives, the following patent publications, especially European patent EP 0,355,660A2
Preferably, those described in the specification of Japanese Patent Application No. 1-107011.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056] Also, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan coupler described in Publication No. 33144, European Patent EP 0,333,18
3-hydroxypyridine cyan couplers described in the specification of No. 5A2 (among them, the 4-equivalent coupler of coupler (42) listed as a specific example) has a chlorine leaving group.
Equivalent ones, couplers (6) and (9) are particularly preferred) and cyclic active methylene cyan couplers described in JP-A No. 64-32260 (particularly coupler example 3 listed as a specific example, 8,34 are particularly preferred)
It is also preferable to use

The color photographic material used in the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out in one bath or in separate baths.

The color developer used in the present invention contains:
Contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-1 N,N-diethyl-p-phenylenediamine D-2 4-amino-N,N-diethyl-3-methylaniline D-3 4-amino-N-(β-hydroxyethyl)
-N-Methylaniline D-4 4-Amino-N-ethyl-N-(β-hydroxyethyl)aniline D-5 4-Amino-N-ethyl-N-(β-hydroxyethyl)-3-methylaniline D -6 4-Amino-N-ethyl-N-(3-hydroxypropyl)-3-methylaniline D-7 4-amino-N-ethyl-N-(4-hydroxybutyl)-3-methylaniline D-8 4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-3-methylaniline D-9
4-amino-N,N-diethyl-3-(β-hydroxyethyl)aniline D-10 4-amino-N-ethyl-N-(β-methoxyethyl)-3methyl-aniline D-11 4-amino- N-(β-ethoxyethyl)
-N-Ethyl-3-methylaniline D-12 4-Amino-N-(3-carbamoylpropyl-N-n-propyl-3-methylaniline D-13
4-amino-N-(4-carbamoylbutyl-N-
n-propyl-3-methylaniline D-14 N-(
4-Amino-3-methylphenyl)-3-hydroxypyrrolidine D-15 N-(4-amino-3-methylphenyl)
-3-(hydroxymethyl)pyrrolidine D-16 N-(4-amino-3-methylphenyl)
-3-pyrrolidinecarboxamide

Among the above p-phenylenediamine derivatives, exemplified compounds D-5, D-6, D-7, and D are particularly preferred.
-8 and D-12. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid, etc. may also be used. The amount of the aromatic primary amine developing agent used is preferably 0.002 mol to 1 liter of developer solution.
The amount is 0.2 mol, more preferably 0.005 mol to 0.1 mol.

[0061] In carrying out the present invention, it is preferable to use a developer containing substantially no benzyl alcohol. Here, "substantially not containing" preferably means 2
The benzyl alcohol concentration is below ml/liter, more preferably below 0.5 ml/liter, and most preferably contains no benzyl alcohol at all.

[0062] It is more preferable that the developer used in the present invention contains substantially no sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency. This kind of effect is
This is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" means preferably having a sulfite ion concentration of 3.0 x 10-3 mol/liter or less, and most preferably not containing any sulfite ions. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably contains substantially no sulfite ions, and more preferably substantially no hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties. Here, "substantially not containing hydroxylamine" preferably means 5.0 x 10-3
hydroxylamine concentration less than or equal to mol/liter;
Most preferably it does not contain any hydroxylamine.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

[0065] The organic preservative herein refers to any organic compound that reduces the deterioration rate of the aromatic primary amine color developing agent when added to the processing solution for color photographic light-sensitive materials. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals,
Particularly effective organic preservatives include alcohols, oximes, diamide compounds, and fused ring amines. These are JP-A Nos. 63-4235, 63-30845, 63-21647, 63-44655, 63-
No. 53551, No. 63-43140, No. 63-566
No. 54, No. 63-58346, No. 63-43138, No. 63-146041, No. 63-44657, No. 63-44656, U.S. Patent No. 3,615,503
No. 2,494,903, JP-A-52-1430
It is disclosed in various publications or specifications such as No. 20 and Japanese Patent Publication No. 48-30496.

Other preservatives include JP-A-57-441
48 and 57-53749, salicylic acids as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, JP-A-56- Polyethyleneimines described in Publication No. 94349, U.S. Pat. No. 3,746,544
If necessary, aromatic polyhydroxy compounds described in the specification and the like may be contained. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred, and details thereof can be found in JP-A No. 1-97953, JP-A No. 1-186939, and JP-A No. 1-1-1.
It is described in No. 186940, No. 1-187557, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines in terms of improving the stability of the color developer and further improving the stability during continuous processing.

[0069] As the above-mentioned amines, Japanese Patent Application Laid-Open No. 63-2
Cyclic amines such as those described in JP-A No. 39447, amines such as those described in JP-A-63-128340, and other amines such as those described in JP-A-1-186939 and JP-A-1-187.
Examples include amines such as those described in Japanese Patent No. 557.

In the present invention, it is preferable that the color developer contains chlorine ions in an amount of 1.5×10 −1 mol/liter or less. Particularly preferably, it is 1×10 −1 mol/liter or less. In other words, the chloride ion concentration is 1.
If the amount is more than 5×10 −1 mol/liter, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density.

Furthermore, in the present invention, bromine ions are added to the color developer in an amount of 3.0 x 10-5 mol/liter to 1.
It is preferable to contain 0x10-3 mol/liter. More preferably, it is 5.0 x 10-5 to 5 x 10-4 mol/liter. If the bromide ion concentration is more than 1 x 10-3 mol/liter, development will be delayed and the maximum density and sensitivity will be reduced; if it is less than 3.0 x 10-5 mol/liter, fog should be sufficiently prevented. I can't.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the light-sensitive material into the developer during the development process, or may be added to the fluorescence enhancer added to the developer. It may also be supplied from a whitening agent. When added directly to a color developer, chloride ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride.
Among them, preferred are sodium chloride and potassium chloride. In addition, as a supplier of bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, Among these, preferred are potassium bromide and sodium bromide.

[0073] When eluted from the photosensitive material during the development process,
Both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

[0074] The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds. be able to.

[0075] In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate,
Glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-
amino-2-methyl-1,3-propanediol salt,
Valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. Especially carbonates,
Phosphate, tetraborate, and hydroxybenzoate have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher,
It is more preferable since it has advantages such as no adverse effect on photographic performance (fogging, etc.) even when added to a color developer, and is inexpensive.

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

[0077] The amount of the buffer added to the color developer is:
It is preferably 0.1 mol/liter or more, particularly preferably 0.1 mol/liter to 0.4 mol/liter.

In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N
',N'-tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid , 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-
Examples include hydroxybenzyl)ethylenediamine-N,N'-diacetic acid. Two or more of these chelating agents may be used in combination, if necessary. Further, the addition amount may be sufficient as long as it is sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

[0079] Any development accelerator can be added to the color developer if necessary. As a development accelerator,
-16088, 37-5987, 38-782
6, No. 44-12380, No. 45-9019, and U.S. Pat.
p-phenylenediamine compounds disclosed in No. 9829 and No. 50-15554, JP-A-50-137
No. 726, Japanese Patent Publication No. 1973-30074, Japanese Patent Publication No. 1987-1
Quaternary ammonium salts disclosed in No. 56826 and No. 52-43429, U.S. Patent No. 2,494,9
No. 03, No. 3,128,182, No. 4,230,
No. 796, No. 3,253,919, Special Publication No. 1977-
11431, U.S. Pat. No. 2,482,546, U.S. Pat. No. 2,596,926, U.S. Pat. No. 42-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, No. 42-23883, and U.S. Patent No. 3,532,5
Polyalkylene oxides disclosed in publications such as No. 01 or specifications, 1-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary.

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

[0081] Color developers that can be applied to the present invention include:
Preferably, it contains an optical brightener. As the fluorescent brightener, 4,4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 5g/liter or less.
Preferably it is 0.1 g/liter to 4 g/liter. Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer applicable to the present invention is 30°C to 50°C, preferably 35°C to 50°C. The treatment time is 5 seconds to 30 seconds, preferably 5 seconds to 20 seconds, and more preferably 5 seconds to 15 seconds. The smaller the amount of replenishment, the better, but 20ml to 6ml per 1m2 of photosensitive material.
00ml is suitable, preferably 30ml to 100ml
It is l.

When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = contact area between processing liquid and air (cm2)/capacity of processing liquid (cm3)

The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, there is also a method using a movable lid as described in JP-A No. 1-82033. , and the slit development method described in Japanese Patent Application Laid-Open No. 63-216050.

[0086] Reducing the aperture ratio is effective not only in both the color development and black-and-white development steps, but also in subsequent steps, such as
It is preferable to apply it in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization.

The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

Next, a desilvering process applicable to the present invention will be explained. The desilvering step may generally include any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, and a bleach-fixing step.

The bleaching solution, bleach-fixing solution and fixing solution that can be applied to the present invention will be explained below.

As the bleaching agent used in the bleaching solution or bleach-fixing solution, any bleaching agent can be used, but in particular organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) , complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, and the like are preferred.

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or their salts useful for forming organic complex salts of iron(III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-
diaminopropanetetraacetic acid, propylenediaminetetraacetic acid,
Examples include nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01
The amount is from 1.0 mol/liter to 1.0 mol/liter, preferably from 0.05 mol/liter to 0.50 mol/liter.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, US Patent No. 3,893,858, German Patent No. 1,290,812,
Compounds having a mercapto group or disulfide bond described in JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue), JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706,56
The thiourea compounds described in No. 1, etc., or halides such as iodine and bromide ions are preferred because they have excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions that can be applied to the present invention include bromides (for example, potassium bromide, sodium bromide, ammonium bromide) or chlorides (for example, potassium chloride, sodium chloride, ammonium chloride). )
or a rehalogenating agent such as an iodide (eg, ammonium iodide). If desired, one or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate;
Ethylene bisthioglycolic acid, 3,6-dithia-1,
Water-soluble silver halide solubilizers such as thioether compounds such as 8-octanediol and thioureas,
These can be used alone or in combination of two or more. Further, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per liter is preferably from 0.2 to 2 mol, more preferably from 0.3 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 9, more preferably 4 to 8.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 1.0 mol/liter, more preferably 0.04 to 0.6 mol/liter in terms of sulfite ions.
It is a liter.

As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.

Furthermore, buffering agents, optical brighteners, chelating agents,
Antifoaming agents, antifungal agents, etc. may be added as desired.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of washing water in the washing step can be set within a wide range depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (number of stages), and various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the
Society of Motion Picture and
Television Engineers (Journal o
f the Society of Motion P
ictureand Television Engi
neers) Volume 64, p. 248 ~ 253 (19
This can be obtained using the method described in the May 1955 issue). Normally, the number of stages in the multistage countercurrent system is preferably 2 to 6.
Particularly preferably 2 to 5.

[0101] According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, to 500 ml per 1 m2 of photosensitive material.
Although the following is possible and the effects of the present invention are remarkable, problems such as increased residence time of water in the tank cause bacteria to propagate and generated floating matter to adhere to the photosensitive material. As a solution to this problem, Japanese Patent Application Laid-Open No. 62-288
The method for reducing calcium and magnesium described in Japanese Patent No. 838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, JP-A No. 61-120145
Chlorine-based disinfectants such as chlorinated sodium isocyanurate described in Japanese Patent Publication No. 61-267761, copper ions, etc. ) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial sterilization, sterilization, and anti-mildew technology" (1982) Industrial Technology Society, edited by Japan Antibacterial and Antifungal Society "Encyclopedia of antibacterial and antifungal agents" (1)
986) can also be used.

Furthermore, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

[0103] The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. In addition, in order to prevent bacterial growth in the liquid and to provide anti-mold properties to photosensitive materials after processing,
The various fungicides and antifungal agents mentioned above can be used.

[0104] Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step,
JP-A-57-8543, JP-A No. 58-14834, JP-A No. 6
All known methods described in JP 0-220345 and the like can be used.

Others: 1-hydroxyethylidene-1,
It is also a preferred embodiment to use a chelating agent such as 1-diphosphonic acid or ethylenediaminetemethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after the desilvering treatment.

[0107] The pH of the water washing step or stabilization step is preferably 4 to 10, more preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the photosensitive material, it is generally 20°C to 50°C, preferably 25°C to 45°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably it is 10 seconds to 60 seconds, more preferably 15 seconds to 45 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferred amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. or 1m2 of photosensitive material
500 ml or less, preferably 300 ml or less. Further, replenishment may be performed continuously or intermittently.

[0109] The liquid used in the water washing and/or stabilization step is as follows:
Furthermore, it can also be used in a pre-process. An example of this is the use of a multi-stage countercurrent method to reduce overflow of washing water.
The amount of waste liquid can be reduced by flowing the concentrated liquid into the bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid.

[0110]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited to this embodiment.

FIG. 1 shows a silver salt photographic color paper processing apparatus to which the present invention is applied. This processing apparatus forms an image on the color paper by developing the exposed color paper, bleaching and fixing it, washing it with water, and then drying it. The color paper (hereinafter referred to as a photosensitive material) processed by this processing apparatus is a color photographic photosensitive material having at least one layer on a support of a silver halide emulsion containing preferably 95 mol% or more of silver chloride, Color development is performed using a color developing solution containing an aromatic primary amine color developing agent.

[0112] Inside the processing device, there are a developing tank 4, a bleach-fixing tank 6,
Washing tanks 8 (5 tanks) and a drying section (not shown) are successively provided, and the exposed photosensitive material 10 is developed, bleach-fixed, washed, and then dried before being carried out from the processing apparatus. Photosensitive material 1
0 is conveyed horizontally with the emulsion surface facing downward.

[0113] The washing tank 8 preferably includes a plurality of tanks 8a to 8e.
Each tank is arranged in cascade piping, and the cleanliness of the washing water gradually decreases from the last tank to the front tank.

The developer tank 4, bleach-fix tank 6, and washing tank 8 are replenished with replenisher according to the amount of photosensitive material 10 processed. Washing water is being replenished.

[0115] A processing liquid jetting member 22 is provided that generates a jet flow of processing liquid from below the processing roller 18 which is immersed in the processing liquid and has an elastic deformable member 11 on its circumferential surface, so that fresh processing liquid can be quickly supplied. It looks like this.

The ejection member 22 is made of a pipe in which ejection holes each having a diameter of 0.5 mm are provided at intervals of 5 mm along the axial direction of the processing roller 18, and is provided at a distance of 10 mm from the processing roller 18. For convenience, the ejection amount at this time is the ejection amount per minute (
10 liters) divided by the length of the processing roller 18 (20 cm), and this value is 0.5 liters/cm·min. As a jet of the processing liquid is generated on the surface of the processing roller 18, the processed liquid film that has contributed to the processing of the photosensitive material 10 is quickly destroyed by the jet and diffused. Therefore, a fresh film of processing liquid is always formed between the processing roller 18 and the photosensitive material 10, and rapid and good processing is performed. The ejection member 22 can be provided for each of the processing rollers 18 described above and below.

The photosensitive material 10 is processed in the developing tank 4 and the bleach-fixing tank 6.
is immersed in the processing liquid and transported. In the washing tank 8,
The photosensitive material 10 is stored in the first-stage washing tank 8a and the last-stage washing tank 8e.
are immersed in washing water and transported, and are supplied with washing water by the processing roller 18 while being transported above the washing water in intermediate tanks 8b to 8d. An elastically deformable member 11 is fixed on the circumferential surface of the processing roller 18 in order to increase pumping efficiency. Further, the processing liquid is removed from the photosensitive material 10 after being immersed in each processing liquid by a squeeze roller 16. The squeeze roller 16 can also function as a conveyance roller.

Furthermore, by providing a reverse osmosis membrane 23 in the washing tank 8 and subjecting the washing water to reverse osmosis, unnecessary components (particularly fixing and bleach-fixing components) in the washing water are removed, reducing the influence on the photosensitive material 10. can do. The water in the third washing tank 8c is pumped to the reverse osmosis membrane 23 by the pump 24, the permeated water that has passed through the reverse osmosis membrane 23 is supplied to the fourth washing tank 8d, and the concentrated water that has not passed through the reverse osmosis membrane 23 is the third washing tank 8
It is now set back to c.

Next, the processing roller 18 will be explained with reference to FIG. The processing roller 18 is rotatable by a drive means (not shown), and an elastic deformable member 11 is installed on the circumferential surface so that the emulsion surface of the photosensitive material 10 engages with a part of the circumferential surface. The photosensitive material 10 is transported by the transport roller 12 and the like while engaging with the processing roller 18, and at this time, the processing roller 18 rotates in a direction opposite to the direction in which the photosensitive material is transported (counterclockwise in FIG. 2). Here, processing roller 1
The absolute value of the circumferential speed of 8 is 1.8 of the absolute value of the photosensitive material conveyance speed.
5 times or more, preferably 20 to 1000 times, more preferably 30 to 500 times, even more preferably 60 to 300 times
It's double.

[0120] The photosensitive material 10 and the processing roller 18 in the processing liquid.
Even if they are engaged, a thin liquid film is actually interposed between them, and the photosensitive material 10 and the processing roller 18 are substantially separated.
I have not had any contact with. The photosensitive material 10 is processed by this liquid film. When the processing roller 18 rotates extremely fast compared to the photosensitive material conveyance speed, the processing roller 18 and the photosensitive material 1
0 rotates together with the processing roller 18 and spreads as the processing roller 18 rotates. And photosensitive material 1
Fresh processing liquid is supplied between the processing roller 18 and the processing roller 18 by the rotation of the processing roller 18 and the processing liquid jetting member 22, so that the processing liquid is quickly exchanged on the surface of the photosensitive material 10. In addition, the film of processing liquid near the surface of the photosensitive material is rapidly agitated and removed by an elastically deformable member installed on the circumferential surface, resulting in even faster replacement. The distance between the photosensitive material 10 and the processing roller 18 is estimated to be 2 mm or less, but since the processing roller 18 rotates at high speed and in the opposite direction to the direction in which the photosensitive material is conveyed, the processing liquid is quickly spread on the surface of the photosensitive material. Replaced and good processing done in a short time.

[0121] The processing by the processing roller 18 is not a process of penetrating the dry photosensitive material 10 with a processing liquid, but a process of processing the photosensitive material 10 wetted with a processing liquid or the like with another processing liquid. It is suitable for removing processing liquid that has adhered to the surface of a light-sensitive material or in an emulsion film by exchanging the processing liquid on the surface of a light-sensitive material or in an emulsion film. Specifically, it is particularly effective for bleach-fixing and washing in FIG.

The processing roller 18 described above is placed completely immersed in the processing liquid, and the photosensitive material 10 is placed on the processing roller 18.
However, the processing roller 18 does not have to be completely immersed in the processing liquid, and the processing roller 18 does not have to be completely immersed in the processing liquid.
It is sufficient that at least a portion of the roller is immersed in the processing liquid, as in the case of the processing roller 18 shown in FIG. Note that the state in which at least a portion of the processing roller 18 is immersed in the processing liquid refers to a state in which the surface of the processing liquid crosses the processing roller 18 when the apparatus is stopped.

Next, a modification of the arrangement of the processing roller 18 will be explained. FIG. 3 shows a state in which approximately half of the processing roller 18 is immersed in the processing liquid. Only the lower part of the processing roller 18 is immersed, and the photosensitive material 10 is conveyed with its emulsion surface engaged with the lower surface of the processing roller 18. The photosensitive material 10 is transported through the processing liquid by a transport roller 12, a guide member 20, and the like. A processing liquid ejecting member 22 is provided near the processing roller 18 above the liquid level, and can clean the peripheral surface of the processing roller 18. By preferably rotating the processing roller 18 in a direction opposite to the direction in which the photosensitive material is conveyed, the processing liquid is quickly exchanged and processed on the surface of the photosensitive material.

The configuration shown in FIG. 4 is similar to the washing tank 8b shown in FIG.
It has almost the same arrangement as the processing roller 18 of 8d. Since the part of the processing roller 18 whose peripheral surface is approximately half immersed in the processing liquid and which is exposed in the air requires cleaning means, a processing liquid spouting member 22 is provided above the roller and directed toward the processing roller 18. The processing liquid is ejected at high speed, and the processing liquid is
The aerial part of the tank is cleaned.

FIG. 5 shows another example of the arrangement of the processing roller 18. A squeeze roller 16 that pinches and conveys the photosensitive material 10 before being immersed in the treatment liquid, and a squeeze roller 16 that pinches and conveys the photosensitive material 10 after being carried out from the treatment liquid are provided above the treatment liquid. Further, a squeeze roller 16 and a guide member 20 for pinching and conveying the photosensitive material 10 are provided in the processing liquid upstream of the processing roller 18. By pinching and conveying the photosensitive material 10 with the squeeze roller 16 in the processing liquid, the processing liquid adhering to the photosensitive material 10 can be removed. Since the liquid film adhering to the peripheral surface of the processing roller 18 can be removed, the processing liquid can be efficiently exchanged on the surface of the photosensitive material 10.

[0126] Each of the above-mentioned processing rollers 18 is provided one for each tank.
Although only one processing roller 18 is disposed in each tank, a plurality of processing rollers 18 of the same type or different types may be arranged in succession in each tank.

FIG. 6 shows a configuration in which three processing rollers 18 are disposed within the processing tank. The processing rollers 18 are arranged continuously in the vertical direction, and preferably all rotate in a direction opposite to the direction in which the photosensitive material is conveyed. The photosensitive material 10 is placed between the conveying roller 12 and the guide member 2 with the emulsion side facing inward of the processing tank.
0 etc. The photosensitive material 10 is conveyed so as to engage, for example, 1/2 of the circumferential surface of the processing roller 18 at the bottom. The treatment liquid on the surface can be exchanged quickly and efficiently. Furthermore, although the upper and middle processing rollers 18 are in linear contact with the photosensitive material 10, the processing liquid is similarly quickly and efficiently exchanged on the surface of the photosensitive material 10. In addition, a processing liquid jetting member 22 that generates a jet flow from two directions, upper and lower, is provided between each processing roller to further speed up the exchange of the processing liquid.

FIG. 7 shows a configuration in which a plurality of processing rollers 18 are arranged in a staggered manner via a photosensitive material transport path. Photosensitive material 1
0 is immersed in the processing liquid and transported by a transport roller 12, only a portion of which is shown, and guided to a guide member 20. Processing roller 18 preferably rotates in a direction opposite to the direction of photosensitive material transport and at a much higher speed than the photosensitive material transport speed. Photosensitive material 1
Since processing rollers 18 are disposed on both sides of the processing tank 0, the photosensitive material 10 may be transported with the emulsion surface facing either inside or outside the processing tank. In addition, a processing liquid ejecting member 22 that generates jets in two directions, left and right, is provided to further speed up the exchange of the processing liquid.

FIG. 8 is a block diagram of another modification of the processing device. A plurality of processing rollers 18 are disposed in the developing tank 4, bleach-fixing tank 6, and washing tank 8 (3 tanks 8a to 8c arranged in cascade) along the photosensitive material transport path, and the photosensitive material 1
0 is conveyed by the conveyance roller 12 or the like with the emulsion surface in tangential contact with the processing roller 18. Each processing roller 18 is preferably rotated in a direction opposite to the photosensitive material transport direction. In addition, a processing liquid jetting member 22 that generates a jet flow in two directions, up and down, is provided between the processing rollers arranged in the upper and lower relation, so that the processing liquid can be exchanged even more quickly. Washing tank 8 is cascade piping with 4 tanks 8a~
8d is provided, and a reverse osmosis membrane 23 is provided in the washing tank 8, and by reverse osmosis of the washing water, unnecessary components (especially fixing and bleach-fixing components) in the washing water are removed, reducing the influence on the photosensitive material 10. can do. The water in the third washing tank 8c is pumped to the reverse osmosis membrane 23 by the pump 24, and the permeated water that has passed through the reverse osmosis membrane 23 is supplied to the fourth washing tank 8d.
The concentrated water that did not pass through the reverse osmosis membrane 23 is transferred to the third washing tank 8c.
It is set to be returned to .

FIG. 9 is a perspective view of the processing roller 18 showing a specific example of the shape of the elastically deformable member 11. (a) is a perspective view of a processing roller 18 provided with a plate-shaped elastically deformable member 11 extending longitudinally along the roller axis on its circumferential surface. Even if only one piece is provided, it will be sufficiently effective if the circumferential rotational speed is high, but it is preferable to have a balanced and evenly spaced arrangement, and to maintain an interval so that adjacent members do not overlap when a force is applied in the circumferential direction.

(b) A perspective view of a processing roller 18 in which raised elastic deformable members 11 are arranged on the circumferential surface along the roller axis.

(c) A perspective view of a processing roller 18 in which convex elastic deformable members 11 are arranged on the circumferential surface along the roller axis.

(d) A perspective view of a processing roller 18 in which a raised elastic deformable member 11 is provided over the entire circumferential surface of the roller.

(e) A perspective view of the processing roller 18 with fold-like unevenness provided on the roller circumferential surface.

FIG. 10 is a block diagram of an example of a mechanism in which a processing roller, at least a portion of which is located in the air, is submerged in a processing liquid when the processing apparatus is not in operation. (b) represents the state when not in operation. An eccentric cam mechanism 25 is in contact with the rotating shaft of the processing roller 18 that is partially immersed in the processing liquid and rotates around an eccentric shaft 27, and is stretched across both the rotating shaft of the processing roller 18 and the eccentric shaft 27. It is equipped with a tabular spring 26. In (a), the processing roller 18 is being driven, and the photosensitive material 10 is being processed with the processing liquid drawn up by the rotation of the processing roller 18. At this time, the eccentric cam mechanism 2
5 is a mechanism that does not hinder the rotation of the processing roller 18.

Next, in (b), when the processing of the photosensitive material is completed and the rotation of the processing roller 18 is stationary, the processing roller 1 is rotated.
8 is separated from the drive source and can only move up and down along the side wall of the processing tank. While the eccentric cam mechanism 25 is in contact with the rotation axis of the processing roller 18, the eccentric cam mechanism 2
5 rotates around an eccentric shaft 27. The processing roller 18 is pushed down as the eccentric cam mechanism 25 rotates, and the eccentric shaft 2 is pushed down until the processing roller 18 is completely immersed in the processing liquid.
Rotate 7. When the processing device is operated again, the eccentric cam mechanism 25 is rotated in the opposite direction, so that the spring 2 tensioned between the rotation shaft of the processing roller 18 and the eccentric shaft 27 is
Due to the upward restoring force of the roller 6, a part of the processing roller 18 floats up to a position where it comes out of the processing liquid.

[0137] By completely immersing the processing roller in the processing liquid when not in operation, precipitation of processing liquid components that would occur on the peripheral surface of the roller when the roller is left partially exposed in the air is prevented. Therefore, it is possible to prevent the surface of the photosensitive material from being contaminated.

By the way, if a part of the processing roller 18 is immersed in the processing liquid, the high-speed rotation of the processing roller 18 tends to cause splashes of the processing liquid and the processing liquid tends to evaporate. In particular, maintaining processing liquids at high temperatures to achieve rapid processing accelerates evaporation. Therefore, in order to prevent evaporation of the processing liquid, it is preferable to substantially seal the space above the processing liquid. To seal the space above the processing liquid, for example, there is a structure in which the upper part of the processing liquid is covered with an airtight lid, or a structure in which a floating lid is provided to cover the surface of the processing liquid.

[0139] When a sealing lid is provided, since the sealing lid has an airtight function and also requires a passage for the photosensitive material 10,
For example, a shutter means is provided to open and close the slit by a pair of flexible blades whose free ends abut. Note that the configuration of the shutter means is disclosed in, for example, Japanese Patent Application Laid-Open No. 2-1.
The shutter means described in Japanese Patent No. 61431 can be employed. Since the upper part of the processing liquid is substantially sealed, evaporation and oxidation of the processing liquid do not proceed rapidly, and deterioration of the processing liquid can be prevented.

[0140]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Color paper (Fuji Color Paper Super FA-II: manufactured by Fuji Photo Film) was used as a photosensitive material.

[0142] The sample was measured using a sensitometer (FW manufactured by Fuji Photo Film Co., Ltd.).
The color temperature of the light source was 3200°K), and gradation exposure of a three-color separation filter for sensitometry was provided. The exposure at this time was carried out so that the exposure time was 0.1 seconds and the exposure amount was 250 CMS.

[0143] The exposed sample was processed using a processing apparatus having the configuration shown in FIG. 1 (however, reverse osmosis membrane treatment was not performed). In this apparatus, the peripheral speed of the processing roller is 80 times the transport speed of the photosensitive material, and the rotating direction is opposite to the transport direction. The processing steps are shown below.

Treatment process temperature
Time Replenisher* Tank capacity
Color development 42℃ 17 seconds
80ml 0.5 liter bleach fixing
40℃ 17 seconds 60ml
0.5 liter rinse■
45℃ 11 seconds ──── 0
．． 5 liters rinse■ 45℃
4 seconds ──── 0.5 liter rinse■ 45℃
4 seconds ──── 0.5 liter
Rinse■ 45℃ 4 seconds ─── 0.5 liter Rinse■ 45℃ 11 seconds 1
00ml 0.5 liter dry
70~80℃ 15 seconds
*The amount of replenishment is expressed as the amount per 1 m2 of photosensitive material. In addition, a 5-tank countercurrent system was used for rinsing from ■ to ■.

[0145] The composition of each treatment liquid is as follows.

Color developer
Tank fluid replenishment fluid
water
800ml
800ml 1-hydroxyethylidene
-1,1-diphosphonic acid
0.5g 0.7g
Diethylenetriaminepentaacetic acid
1.0g 1.4g
N,N,N-trismethylene
phosphonic acid

1.5g 2.0g Potassium bromide
0.01g ─
triethanolamine
8.1g 8.1g
sodium sulfite
0.14g 0.14g
potassium chloride
8.2g ─
potassium carbonate
18.7g
37g N-ethyl-N-(3-hyperoxygenate)
droxypropyl)-3
-methyl-4-aminoa
Nirinjiparatoluene
sulfonate
12.8g
27.8g N,N-bis(2-sulfoethyl) hydroxylamine
8.5g 11.0g Fluorescent brightener (UVITEX CK, manufactured by Ciba Geigy)
1.0g 1.0g ────────
────────────────────────
add water
1000ml 1
000ml pH (25℃)
10.05
10.95

Bleach-fix solution
tank liquid
replenisher water

400ml 400ml Ammonium thiosulfate (70%) 10
0ml 250ml Ammonium sulfite
40g 100g Ethylenediaminetetraacetic acid iron(III) ammonium dihydrate
73g 183g Ethylenediaminetetraacetic acid 3.
4g 8.5g Ammonium bromide
20g 50g Nitric acid (67%
)
9.6g 24g ──────
──────────────────────────
add water
1000ml
1000ml pH (25℃)
5.
80 5.10

Rinse solution (tank solution and refill solution are the same) Ion-exchanged water (calcium and magnesium each less than 3 ppm)

[0149] As a comparative example, the same treatment as above was carried out except that the tanks of Rinse (2) to (3) of Example 1 were left as they were, and the tanks were immersed for 6 seconds for each tank of Rinse (2) to (4). Furthermore, continuous processing was performed until the replenishment amount became twice the capacity of the tank for rinse (①). The table below shows the stain when the samples before and after continuous treatment were left at a temperature of 70° C. and a humidity of 75% for 12 days.

[0150]

[Table 6]

As is clear from the above table, the increase in stain after continuous treatment was significantly small.

Example 2 The parts that are different from Example 1 will be explained below. The treatment was carried out using an apparatus having the configuration shown in FIG. 1 and equipped with a reverse osmosis membrane treatment apparatus. The reverse osmosis membrane is a spiral type RO module element DRA-80 manufactured by Daicel Chemical Industries (effective membrane area 1.1 m2).
, polysulfone-based composite membrane) was used, and this was loaded into a plastic pressure-resistant vessel PV-0321 manufactured by the same company. Reverse osmosis membrane processing equipment uses a pump for reverse osmosis membrane and has a capacity of 10k.
The water from the fourth rinse tank is pumped under the conditions of applying a liquid sending pressure of g/cm2 and a liquid sending flow rate of 2.3 liters/minute, the permeated water is supplied to the fifth rinse tank, and the concentrated water is supplied to the third rinse tank. I put it back in the tank.

The same test as in Example 1 was carried out. The results of the white background density after continuous processing are shown below.

[0154]

[Table 7]

As is clear from the above table, the cleaning method of the present invention is highly effective.

[0156]

Effects of the Invention: In a processing roller that is at least partially immersed in a processing liquid, the emulsion surface of the photosensitive material is engaged with the peripheral surface of the processing roller that is immersed in the processing liquid and has an elastically deformable member installed on the peripheral surface. By rotating the processing roller with the processing roller at an absolute value of the circumferential speed of the processing roller and the absolute value of the absolute value of the photosensitive material transport speed while processing the photosensitive material, the amount of processing liquid supplied to the photosensitive material can be reduced. The processing liquid film near the surface of the photosensitive material can be quickly removed. Moreover, by providing a cleaning means to remove processing liquid components adhering to the processing roller circumferential surface, it is possible to further increase the exchange effect of the processing liquid increased by high-speed rotation, and even a small amount of processing liquid can be used during ultra-rapid processing. The photosensitive material can be processed efficiently, and the processing apparatus can be simplified and downsized. In addition, by providing a mechanism that submerges the entire processing roller into the processing liquid when the processing equipment is not in operation, the processing liquid adhering to the processing roller evaporates and processing liquid components precipitate on the circumferential surface. It is possible to prevent the surface of the photosensitive material from becoming dirty.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a photosensitive material processing apparatus that is an embodiment of the present invention.

FIG. 2 is a configuration diagram of the vicinity of a processing roller.

FIG. 3 is an arrangement diagram of processing rollers.

FIG. 4 is an arrangement diagram of processing rollers.

FIG. 5 is an arrangement diagram of processing rollers.

FIG. 6 is an arrangement diagram of processing rollers.

FIG. 7 is an arrangement diagram of processing rollers.

FIG. 8 is a configuration diagram of a modified example of the processing device.

FIG. 9 is a perspective view of a modification of the processing roller.

FIG. 10 is a configuration diagram of a mechanism for sinking a processing roller.

[Explanation of symbols]

4 Developing tank 6 Bleach-fix tank 8 Washing tank 10 Photosensitive material 11 Elastic deformation member 12 Conveyance roller 16 Squeeze roller 18 Processing roller 20 Guide member 22 Processing liquid spouting member 23 Reverse osmosis membrane 24 Pump 25 Eccentric cam mechanism 26 Spring 27 Eccentric shaft

Claims (3)

[Claims] 1. A processing roller that rotates with at least a portion immersed in a processing liquid and has an elastically deformable member on its circumferential surface, and a means for engaging a photosensitive material with the circumferential surface of the processing roller and conveying the photosensitive material. The processing roller is rotated at an absolute value of the circumferential speed of the processing roller that is 1.5 times or more of the absolute value of the photosensitive material conveyance speed while maintaining engagement between the processing roller and the photosensitive material. A photosensitive material processing device characterized by processing materials. 2. The photosensitive material processing apparatus according to claim 1, further comprising cleaning means for cleaning the peripheral surface of the processing roller. 3. In an apparatus for processing a photosensitive material by engaging the photosensitive material with the peripheral surface of a rotating processing roller partially immersed in a processing liquid, the processing roller is immersed in the processing liquid when the apparatus is not in operation. A photosensitive material processing apparatus comprising a processing roller immersion means for completely immersing the processing roller.