JPH04356048A - Device for processing of photosensitive material - Google Patents

Abstract

PURPOSE:To realize ultrafast processing with high quality and small-size treatment device for wet treatment of photosensitive material. CONSTITUTION:At least a part of a processing roller 18 is dipped in a processing liquid in a processing tank. A photosensitive material 10 is engaged around the roller 18 in the liquid and carried. The absolute rotating circumference speed of the roller 18 is larger than the absolute traveling speed of the photosensitive material. The processing roller 18 is rotated by >=75rpm. Therefore, even for ultrafast processing, the processing liquid is rapidly exchanged on the surface of the photosensitive material so that the processing is performed in good state. Moreover, the amt. of the liquid used is small, which realizes a small sized device.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a wet processing apparatus for photosensitive materials. The present invention relates to a novel photosensitive material processing apparatus for processing. [0002] A photosensitive material processing apparatus performs processing such as development, bleaching, fixing, bleach-fixing, washing, stabilization, and drying on a photosensitive material after exposure to form an image on the photosensitive material. There is a device that does this. Among the above treatments, the water washing and stabilization treatment steps are also called cleaning steps. Usually, these treatments consist of a process 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, if it is simplified (downsized), the immersion time will be reduced compared to the total processing time. There are obstacles such as a decrease in the ratio and a decrease in the actual processing time. As a means to compensate for this drawback, a cleaning device (water washing device) is proposed as a means other than immersion, as disclosed in Japanese Patent Application Laid-open Nos. 62-240967 and 62-240969.
As described in the publication, 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, and a device for cleaning the surface of a photosensitive material using running water, and a device for cleaning the surface of a photosensitive material using running water, and a device for cleaning the surface of a photosensitive material with running water,
As described in Japanese Patent No. 442, an apparatus has been proposed that performs washing by spraying washing water onto a photosensitive material. [0004] However, the above-mentioned processing cannot exhibit sufficient performance during rapid processing, and one of the reasons for this is that the processing solution located near the surface of the photosensitive material is not freshly processed. It is assumed that this is because it is not exchanged smoothly with the liquid. For example, using the water washing process as an example, if a photosensitive material with a bleach-fix solution attached is dried as it is, processing solution components such as thiosulfate and silver thiosulfate complexes contained in the bleach-fix solution will precipitate as crystals on the film surface. Also, during storage, image silver and processing solution components react, causing the image to discolor or fade, and silver complex salts dissolved in the processing solution turn into silver sulfide, causing 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. [0005] In the method of immersing the photosensitive material in washing water and washing it with water, a transport means is required to transport the photosensitive material within a washing tank containing a large amount of washing water for immersing the photosensitive material. , the transport 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. Also, JP-A-63-2160
The apparatus described in Japanese Patent No. 50, which immerses a photosensitive material in washing water in a slit-shaped washing tank, can perform efficient washing with a small amount of washing water, but the apparatus is complicated and difficult to maintain. [0006] Also, JP-A-62-240967 and 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, JP-A-62-
The apparatus described in Japanese Patent No. 240970, which substantially supplies flowing sewage water in multiple stages, is large and complex, and maintenance is difficult. Furthermore, in the apparatuses described in Japanese Utility Model Application Publications No. 50-947 and No. 51-147442, which perform washing by spraying washing water onto a photosensitive material, it is necessary to perform sufficient washing with only a jet of washing water. I can't. [0007] As is clear from what has been said above,
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to provide a high-quality, simple, and ultra-quick processing apparatus for photosensitive materials. Means for Solving the Problems and Operations The above objects of the present invention are achieved by the processing apparatus described in (1) and (2) below. (1) A processing roller that rotates with at least a portion immersed in a processing liquid, and a means for conveying the photosensitive material by engaging the emulsion surface of the photosensitive material with the peripheral surface of the processing roller that is immersed in the processing liquid. , the absolute value of the circumferential speed of the processing roller is greater than the absolute value of the photosensitive material conveyance speed, and the processing roller is rotated at 75 rpm or more while maintaining engagement between the processing roller and the photosensitive material. A photosensitive material processing device characterized by processing a photosensitive material. (2) A processing roller that rotates with at least a portion immersed in a cleaning liquid, and a means for conveying the photosensitive material by engaging the emulsion surface of the photosensitive material with the peripheral surface of the processing roller in the cleaning liquid. . A photosensitive material processing apparatus, characterized in that the processing roller is rotated at 75 rpm or more to clean the photosensitive material while maintaining engagement between the processing roller and the photosensitive material. When the photosensitive material transport direction and the processing roller rotation direction are the same, and the transport speed and the processing roller circumferential speed are equal, the photosensitive material and the processing roller do not slide along the transport direction. Even if the photosensitive material and the processing roller are in contact with each other, no linear scratches are generated on the photosensitive material along the conveyance direction. Under such speed conditions, the processing roller also has the function of conveying the photosensitive material, but when reliable conveyance is required, the photosensitive material is pressed against the processing roller so that pressure is generated at the contact portion. Then, although the photosensitive material does not slide in the conveyance direction, it slides in the axial direction of the roller due to meandering, etc., so that scratches may occur in irregular directions. Scratches occur on the photosensitive material when the photosensitive material is being processed in contact with the processing roller, and this is because minute protrusions caused by the roughness of the processing roller surface come into pressure contact with or slide against the photosensitive material. be. Although scratches can be prevented by mirror-finishing the surface of the processing roller, mirror-finishing the roller to the extent that scratches do not occur is expensive and practically difficult. [0012] Therefore, if processing is performed in such a way that the processing roller does not come into contact with the photosensitive material, the photosensitive material will not be damaged. Specifically, when processing a photosensitive material with a processing roller, if a film of processing liquid is always created between the photosensitive material and the processing roller, the photosensitive material can be processed without coming into contact with the processing roller. Ru. To ensure that a film of processing liquid always forms between the photosensitive material and the processing roller, the rotation of the processing roller always brings the processing liquid between the photosensitive material and the processing roller so that a predetermined amount of processing liquid is always carried. Just do as it is. As the processing roller rotates, processing liquid is constantly carried between the photosensitive material and the processing roller, and the carried processing liquid is sequentially discharged from the surface of the photosensitive material while maintaining an amount that forms a liquid film with a substantially constant thickness. Therefore, the processing liquid can be exchanged quickly and good processing can be performed. The processing liquid film between the processing roller and the photosensitive material is set so as not to be destroyed even when the photosensitive material is pressed against the processing roller. When the rotation speed of the processing roller is extremely low, the amount of processing liquid brought between the processing roller and the photosensitive material is small, so the liquid film is thin and easily destroyed, and the photosensitive material and the processing roller come into contact and cause scratches. It sticks to me. The amount of processing liquid carried between the processing roller and the photosensitive material depends mainly on the rotation speed of the processing roller. It is expected that the number of scratches mentioned above will increase further as the rotation speed of the processing roller increases, but in reality, as the processing roller rotates, the processing liquid around the processing roller moves in the same direction as the processing roller due to the action of viscosity. Since the amount of processing liquid brought between the processing roller and the photosensitive material increases, no scratches occur. The thickness of such a processing liquid film can be adjusted by factors such as the processing roller's rotational speed, circumferential speed, diameter, photosensitive material conveyance speed, etc.; however, the thickness of the liquid film is extremely influenced by the processing roller's rotational speed. The film thickness changes by adjusting the number, and the film thickness does not change much with other factors. Therefore, the emulsion surface of the photosensitive material is engaged with the peripheral surface of the processing roller, which is at least partially immersed in the processing solution, and the photosensitive material is conveyed, while the processing roller is rotated at 75 rpm or more for processing. As a result, 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. By rotating the processing roller at 75 rpm or more, a predetermined amount of processing liquid is carried between the processing roller and the photosensitive material to form a liquid film, and the photosensitive material is efficiently processed without coming into contact with the processing roller. [0014] The rotation speed of the processing roller is 75 rpm or more, preferably 300 rpm or more. The above-mentioned rotational speed can be increased within a limit that does not cause splashing of the processing liquid. However, if the rotation speed of the processing roller is too high, problems will arise in the design of the machine, so in practice it is
500 rpm is preferred. The circumferential speed of the processing roller when it is rotated at 75 rpm or more is determined by the radius, but considering the actually set photosensitive material conveyance speed,
The absolute value of the peripheral speed is never smaller than the absolute value of the photosensitive material transport speed, and the absolute value of the peripheral speed is 1.5 times or more the absolute value of the photosensitive material transport speed. The diameter of the processing roller used in the actual device is 0.5 to 20 cm, preferably 1.0 to 10 cm, more preferably 1.0 to 7 cm.
．． It is 0 cm. When using a processing roller of such a size, the photosensitive material conveying speed is preferably 0.2 to 20 cm/sec, more preferably 0.5 to 10 cm/sec, particularly preferably 0.5 to 4 cm/sec. It is. A slower conveyance speed has the advantage that the device can be made more compact. Further, the peripheral speed of the processing roller is 5 m/min or more, preferably 20 m/min or more, and more preferably 60 m/min or more. The higher the circumferential speed, the greater the processing effect such as cleaning, but there are also problems such as the drive motor becoming larger. Therefore, a practically preferable circumferential speed is 20 to 200 m/min. In fact, the effects of the present invention have been confirmed up to a circumferential speed of the processing roller of 150 km/hour. At this time, 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 the effects of the present invention have been confirmed up to a speed ratio of 1500 times. The speed ratio is preferably 20 to 1000
times, more preferably 30 to 500 times, particularly preferably 6 times
It is 0 to 300 times. The larger this ratio is, the greater the amount of processing liquid carried and carried between the processing roller and the photosensitive material, and therefore the processing effect, especially the cleaning effect, is greater. According to 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, allowing 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. 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 since there are few components, the equipment can be configured to be simple and compact. Maintenance is also easy. In the present invention, the type of processing liquid is not limited as long as the photosensitive material is processed by contacting the processing liquid, but in particular, the photosensitive material wetted with one processing liquid is supplied with another type of processing liquid. It is suitable for cases where A photosensitive material in a wet state means, for example, a photosensitive material immediately after being removed from a developer, a bleach-fix solution, a bleach solution, a fixer, or the like. [0017] In a method for applying liquids such as emulsions, it is known to use a coating roller that is in contact with the liquid and rotated in contact with the photosensitive material; It is rotated in the same direction as the conveyance direction at a circumferential speed approximately equal to . If the circumferential speed of the applicator roller is rotated at a speed higher than the conveyance speed of the photosensitive material, problems such as scratching the surface of the photosensitive material and inability to maintain coating accuracy can be expected. It has not been realized to rotate the application roller at a rotation speed higher than the material conveyance speed. However, it has been found that even when processing is carried out by rotating the processing roller at 75 rpm or higher, which is faster than the photosensitive material conveyance 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 (flowed) continuously and at high speed. [0018] As described above, rotating the processing roller at a high rotation speed is also 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. Although the rotation direction 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. The surface shape and material of the processing roller that can be used in the present invention are not particularly limited. Examples of the processing roller include a roller having concave portions or convex portions on its circumferential surface in order to be able to support the processing liquid, and a roller having water absorbing properties. The depth of the concave portion and the height of the convex portion on the peripheral surface of the processing roller are 0.1 to 5 mm.
is preferred. Furthermore, a so-called wire rod in which a wire is spirally wound may be used as the processing roller, and in this case, the diameter of the wire is preferably 1 to 5 mm. Furthermore, gravure printing rollers, flat rollers, and sponge rollers can also be used. 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 processing tank is 450 ml or less, good processing 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 may be any amount that includes the amount of substances that can be processed in each treatment. On the other hand, if the processing tank is made smaller by immersing the photosensitive material in the processing solution, it is necessary to slow down the photosensitive material transport speed to obtain a predetermined contact time with the solution. , unable to achieve rapid processing. 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, low replenishment,
Under conditions of quiet processing, the processing liquid is slow to reach the equilibrium concentration, leading to instability of the processing. To improve this, it is effective to downsize the processing tank and reduce the amount of processing liquid. 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, a good process can be achieved even when the capacity of the processing tank is small. The treatment tank can be made smaller. 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. When a processing roller that 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, causing rapid evaporation and oxidation of the processing liquid, resulting in a reduction in processing performance. 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. 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 damage to the photosensitive material. [0021] 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 of the aspects of sealing,
There are configurations in which the space above the processing liquid is closed off with an airtight lid or the like, and configurations in which a floating lid or the like is provided to prevent contact between the liquid surface and air. For sealing, it is particularly important to seal the inlet and outlet of the photosensitive material and the degree of opening of the liquid surface, but being substantially sealed means that as described in Japanese Patent Application Laid-Open No. 2-84642, The maximum slit width is 1.5 mm for color developing solution, bleach-fix solution, bleaching solution, fixing solution and stabilizing solution, and 2.5 mm for cleaning solution. 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 dyne/
cm, specific gravity is 0.75 to 1.30, 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-exchanged water, tap water, etc., which contain preservatives, chelating agents, surfactants, pH buffers, optical brighteners, and anti-fungal agents. It may also contain a hardening agent and a hardening agent. Further, in the cleaning process, when a plurality of cleaning tanks are arranged to perform multi-stage cleaning processing, good cleaning can be performed by applying the configuration of the present invention to at least one of the plurality of tanks. Furthermore, in the 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. Furthermore, the amount of cleaning liquid to be refilled to the last stage tank is 0.5 to 3 times the amount of cleaning liquid brought in from the previous stage tank by the photosensitive material.
Preferably, it is twice as large. Furthermore, the cleaning process time is 30
Preferably within seconds. The light-sensitive material 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 film, color reversal film, and color paper. 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, in an embodiment in which the present invention is applied to intelligent color hard copies, it is preferable to scan and expose the photosensitive material using high-density light such as a laser (for example, a semiconductor laser) or a light emitting diode. Also,
The present invention includes embodiments of the present invention and Japanese Patent Application No. 1-23259.
Particularly excellent cleaning effects are exhibited when color photographic light-sensitive materials such as those described in the specification of No. 0 are cleaned in an extremely short period of time. Silver halides used in the light-sensitive material according to the present invention include silver chloride, silver bromide, (iodine) 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. The photosensitive material according to the present invention includes a hydrophilic colloid layer in accordance with European Patent EP 0,337,4 for the purpose of improving image sharpness, etc.
No. 90A2 specification, pages 27 to 76, dyes that can be decolorized by processing (especially oxonol dyes) are used in a photosensitive material whose optical reflection density at 680 nm is 0.7.
0 or more, or 12% by weight or more (more preferably 14% by weight) of titanium oxide surface-treated with a di- to tetrahydric alcohol (for example, trimethylolethane) in the water-resistant resin layer of the support. (wt% or more) is preferably contained. 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, compounds that chemically bond with aromatic amine developing agents remaining after color development processing to produce chemically inert and substantially colorless compounds and/or aromatic amine compounds remaining after color development processing. For example, it is possible to use a compound that chemically combines with the oxidized form of a color developing agent to form a chemically inert and substantially colorless compound, either simultaneously or singly, to reduce the color developing agent 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 colored pigments due to the reaction between the coupler or its oxidized product and the coupler. In addition, the photosensitive material according to the present invention has a preventive agent as described in JP-A No. 63-271247, in order to prevent various types of mold and bacteria that grow in the hydrophilic colloid layer and cause image deterioration. It is preferable to add a fungicide. In addition, the support used in the light-sensitive material according to the present invention includes a white polyester support for displays or a support in which a layer containing a white pigment is provided on the support on the side having a silver halide emulsion layer. May 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, it is preferable to set the transmission density of the support in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. 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. Also, during exposure,
Preferably, a band stop filter as described in US Pat. No. 4,880,726 is used. This eliminates optical color mixture and significantly improves color reproducibility. The exposed light-sensitive material may be subjected to color development processing, but for the purpose of rapid processing, it is preferable to carry out bleach-fixing processing after color development. In particular, when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fix solution is approximately 6 for the purpose of promoting desilvering.
．． 5 or less is preferred, and about 6 or less is more preferred. 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
Those described in the specification (Japanese Unexamined Patent Publication No. 2-139544) are preferably used. [Table 1] [Table 2] [Table 2] [Table 3] [Table 3] [Table 4] [Table 5] [Table 5]
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 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, particularly preferred are exemplary compounds D-5, D-6, D-7, D
-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.
0.2 mol, more preferably 0.005 mol to 0.1 mol
It is a mole. In practicing the present invention, it is preferred to use a developer substantially free of 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. More preferably, the developer used in the present invention does not substantially contain 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. Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially no content" means preferably 3.0 x 10
- a sulfite ion concentration of 3 moles/liter or less, most preferably no sulfite ions at all. However, 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. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), hydroxamic acids, hydrazines,
Hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed rings Formula amines are particularly effective organic preservatives. These are JP-A-63-4235 and JP-A-63-30.
No. 845, No. 63-21647, No. 63-44655
No. 63-53551, No. 63-43140, No. 63-56654, No. 63-58346, No. 63-
No. 43138, No. 63-146041, No. 63-44
No. 657, No. 63-44656, U.S. Patent No. 3,61
No. 5,503, No. 2,494,903, Japanese Unexamined Patent Publication No. 5
It is disclosed in various publications or specifications such as No. 2-143020 and Japanese Patent Publication No. 48-30496. [0041] 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; details thereof can be found in JP-A No. 1-97953, JP-A No. 1-186939, and JP-A No. 1-186939.
-186940, 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. Examples of the amines include cyclic amines as described in JP-A-63-239447, amines as described in JP-A-63-128340, and other amines as described in JP-A-1-186.
Examples include amines such as those described in No. 939 and No. 1-187557. When a color developer is used in the present invention, 3.5×10−2 chloride ions are added to the color developer.
The content is preferably 1.5 x 10-1 mol/liter. Particularly preferably 4 x 10-2 to 1 x 10-1
mole/liter. Chlorine ion concentration is 1.5×1
If the amount is more than 0-1 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. Also, 3.5×10
-If it is less than 2 mol/liter, it is not preferable in terms of preventing fog. When a color developer is used in the present invention, it is preferred that the color developer contains 3.0 x 10-5 mol/liter to 1.0 x 10-3 mol/liter of bromide ions. More preferably, 5.0×10
-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, maximum density and sensitivity will be reduced, and 3.0 x 10
If it is less than -5 mol/liter, fogging cannot be sufficiently prevented. Here, the chlorine ions and bromine ions may be directly added to the developer, or may be eluted from the photosensitive material into the developer during the development process. When added directly to the color developer, examples of the chloride ion supplying substance 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. Alternatively, it may be supplied from an optical brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide. When eluted from the light-sensitive 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. [0044] 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. 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 salts, valine salts, proline salts, trishydroxyaminomethane salts, lysine salts, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher, and even when added to color developers, they improve photographic performance. It is particularly preferable to use these buffers because they have the advantages of not having any negative effects (fogging, etc.) and being 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, buffering agents are not limited to these compounds. The amount of the buffer added to the color developer is preferably 0.1 mol/liter or more, particularly preferably 0.1 mol/liter to 0.4 mol/liter. [0046] 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. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, 0.1g to 1 per liter
It is about 0g. [0047] 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, etc., 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 or specifications such as No. 01, other 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary. Color developers that can be applied to the present invention include:
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. As an organic antifoggant,
For example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole Typical examples include nitrogen-containing heterocyclic compounds such as , hydroxyazaindolizine, and adenine. 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 0 to 5 g/liter, preferably 0.1 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 that can be applied to the present invention is 30 to 50°C, preferably 35 to 50°C. Processing time is 5 seconds to 30 seconds, preferably 5 seconds to 20 seconds,
More preferably, it is 5 to 15 seconds. The smaller the amount of replenishment, the better, but 20 to 600 ml per 1 m2 of photosensitive material.
is appropriate, preferably 30 to 100 ml. 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 of treatment liquid and air (cm2)/capacity of treatment liquid (cm3) The above 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 solution 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. It is preferable to reduce the aperture ratio not only in both color development and black-and-white development, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. Next, a desilvering process that can be applied 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) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolycarboxylic acids, etc.) Complex salts of phosphonic acid, phosphonocarboxylic acid, organic phosphonic acid, etc.) or organic acids such as citric acid, tartaric acid, malic acid; persulfates; hydrogen peroxide, etc. 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
~1.0 mol/liter, preferably 0.05-0.
It is 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 bleach or bleach-fix solutions that may be applied to the present invention include bromides (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) or iodine. Rehalogenating agents such as oxides (eg, ammonium iodide) can be included. 1 having a pH buffering capacity of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. as desired.
More than one type of inorganic acid, organic acid, alkali metal or ammonium salt thereof, or a corrosion inhibitor such as ammonium nitrate or 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 (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), Metabisulfites (e.g. potassium metabisulfite,
Sodium metabisulfite, ammonium metabisulfite,
It is preferable to contain a sulfite ion releasing compound such as ). These compounds have approximately 0.0% in terms of sulfite ion.
The content is preferably from 0.2 to 1.0 mol/liter, more preferably from 0.04 to 0.6 mol/liter. As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added. In addition, buffering agents, optical brighteners, chelating agents, antifoaming agents,
A fungicide or the like 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 over a wide range depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the intended use, 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.
ty of Motion Picture and T
elevision Engineers) Volume 64,
p. 248-253 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 5. 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 of 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. Continue with the above washing process or
Alternatively, it is also possible to directly treat with a stabilizing solution without going through a water washing process. 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. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used. Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of photosensitive materials, when stabilization is carried out directly without going through a water washing process, JP-A-57-
No. 8543, No. 58-14834, No. 60-2203
All known methods described in Japanese Patent No. 45 and the like can be used. Others, 1-hydroxyethylidene-1,1
It is also a preferred embodiment to use a chelating agent such as -diphosphonic acid or ethylenediaminetemethylenephosphonic acid, or a magnesium or bismuth compound. A so-called rinsing liquid is also used as a washing liquid or stabilizing liquid used after the desilvering process. [0059] 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 preferable replenishment amount is 0.5 to 50 times the amount brought in from the previous bath per unit area of the photosensitive material, preferably 3
It is 40 times to 40 times. or 50 per m2 of photosensitive material
It is 0 ml or less, preferably 300 ml or less. Further, replenishment may be performed continuously or intermittently. The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to reduce the overflow of the wash water into a bleach-fixing bath which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid. [Embodiment] 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 halide photographic color paper processing apparatus to which the present invention is applied. This processing apparatus forms an image on the color paper by developing, bleach-fixing, washing with water, and drying a web-like color paper that has been exposed to light based on a positive original. The color paper processed by this processing device (hereinafter referred to as a photosensitive material) is a color photographic photosensitive material that has at least one layer on a support of a silver halide emulsion containing 95 mol% or more of silver chloride. Color development is performed using a color developing solution containing a primary amine color developing agent. [0061] 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. The washing tank 8 preferably consists of a plurality of tanks 8a to 8e, each of which is arranged in cascade piping, and the cleanliness of the washing water decreases from the last tank to the front tank. Developer tank 4
, the bleach-fix tank 6 and the washing tank 8 are replenished with replenisher according to the amount of photosensitive material 10 processed.
In the last stage tank 8e, fresh washing water is replenished. The developer tank 4, bleach-fix tank 6, and washing tank 8 are provided with transport rollers for transporting the photosensitive material along the illustrated path, but only a part of the transport rollers 12 are shown in FIG. . The photosensitive material 10 is immersed in a processing solution in a developing tank 4 and a bleach-fixing tank 6 and is transported. In the washing tank 8, the photosensitive material 10 is immersed in washing water and conveyed in the first washing tank 8a and the last washing tank 8e, and is conveyed above the washing water in the intermediate tanks 8b to 8d by the washing water drawing roller 14. Rinse water is provided. In addition, the photosensitive material 1 after being immersed in each processing solution
0 has the processing liquid removed by the squeeze roller 16. The squeeze roller 16 can also function as a conveyance roller. Developer tank 4, bleach-fix tank 6, first stage washing tank 8a
A processing roller 18, which is a feature of the present invention, is disposed in the last stage water washing tank 8e. 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 is arranged so that the emulsion surface of the photosensitive material 10 engages with a part of its 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). The photosensitive material 10 and the processing roller 18 in the processing solution
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 at high speed, a large amount of processing liquid is brought between the processing roller 18 and the photosensitive material 10 due to its viscosity, and the resulting liquid film processes the photosensitive material 10. The processing liquid involved in processing the photosensitive material 10 is then diffused as the processing roller 18 rotates. Since fresh processing liquid is sequentially supplied between the photosensitive material 10 and the processing roller 18 by the rotation of the processing roller 18, the processing liquid is quickly exchanged on the surface of the photosensitive material 10. The distance between the photosensitive material 10 and the processing roller 18 is about 1 mm, 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 exchanged on the surface of the photosensitive material. Good processing is carried out in a short time. However, the photosensitive material 10
Therefore, if the rotation speed of the processing roller 18 is low, a liquid film will not be formed well between the photosensitive material 10 and the processing roller 18, and the photosensitive material 10 will be in contact with the processing roller 18 and will not be processed. Ru. If the rotation speed of the processing roller 18 is low, the photosensitive material 10 can be
Straight scratches along the conveyance direction occur. Also,
If the processing roller 18 rotates in the same direction as the transport direction and at the same speed as the transport speed, the photosensitive material 10 will not slide on the processing roller 18 in the transport direction, so the linear scratches will not occur. However, since the photosensitive material 10 moves (meanders) in the axial direction of the processing roller 18, scratches occur that are not uniform in direction. In order to prevent such scratches from occurring, it is necessary to form a liquid film well between the processing roller 18 and the photosensitive material 10. The state of formation of the liquid film depends on the rotational speed, peripheral speed, diameter, conveyance speed of the photosensitive material, etc. of the processing roller 18, and is extremely influenced by the rotational speed of the processing roller 18. Therefore, the thickness of the liquid film can be adjusted simply by adjusting the rotation speed of the processing roller 18. If the rotation speed of the processing roller 18 is low, the liquid film will not be formed well as described above and scratches will occur on the photosensitive material 10, but by rotating the processing roller 18 at a high speed of 75 rpm or more,
Due to the action of viscosity, a large amount of processing liquid is brought between the photosensitive material 10 and the processing roller 18, forming a liquid film with a predetermined thickness or more. The rotation speed of the processing roller 18 is set to 75 rpm or more, preferably 300 rpm or more. The preferred rotation speed of the processing roller 18 in an actual device is 300 to 1500 rpm.
It is m. Here, the peripheral speed of the processing roller 18 is 5 m/
min or more, more preferably 20 m/min, particularly preferably 60 m/min or more. Preferred circumferential speed that does not actually increase the size of the device is 20 to 200 m/min. Further, the transport speed of the photosensitive material 10 is preferably 0.2 to 20 cm/sec, more preferably 0.5 to 10 cm/sec, particularly preferably 0.5 to 4 cm/sec. Further, the diameter of the processing roller 18 is preferably 0.5 to 20 cm, more preferably 1.0 to 10 cm, particularly preferably 1.0 to 7.0 cm.
cm. Further, the absolute value of the circumferential speed of the processing roller 18 is 1.5 times or more, preferably 20 to 1000 times, more preferably 30 to 500 times the absolute value of the photosensitive material conveyance speed.
times, more preferably 60 to 300 times. The processing by the processing roller 18 is not a process of penetrating the dry photosensitive material 10 with a processing liquid, but rather 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 engages the upper surface of the processing roller 18, while the processing roller 18 engages the photosensitive material 10 in the processing liquid. If possible, it does not need to be completely immersed in the processing liquid, but only at least partially. 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, etc., and by rotating the processing roller 18, preferably in a direction opposite to the direction in which the photosensitive material is transported, the processing liquid is quickly exchanged on the surface of the photosensitive material. will be processed. The configuration shown in FIG. 4 is similar to that of the processing roller 1 shown in FIG.
8, a processing liquid ejecting member 22 is provided below the processing roller 18, the processing liquid is ejected at high speed toward the processing roller 18, and a jet stream (jet stream) of the processing liquid is generated on the surface of the processing roller 18. flow). 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 10 mm apart from the processing roller 18. For convenience, the ejection amount at this time is expressed as a value obtained by dividing the ejection amount per minute (10 liters) 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 jetting member 22
can be provided for each of the processing rollers 18 described above and below. 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 by the squeeze rollers 18 in the processing liquid, the processing liquid adhering to the photosensitive material 10 can be removed, and the processing liquid can be exchanged well on the surface of the photosensitive material 10. 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 successively arranged 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.
Transported by 0 etc. The photosensitive material 10 is conveyed so as to engage, for example, 1/2 of the circumferential surface of the lowermost processing roller 18, and at this time, the photosensitive material 10 is conveyed at a speed of 75 rpm, which is much faster than the photosensitive material conveyance speed.
By rotating the processing roller 18 at a rotation speed of m or more, the processing liquid on the surface of the photosensitive material 10 can be quickly and efficiently replaced. 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. 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. The processing roller 18 preferably rotates in the opposite direction to the photosensitive material transport direction at a speed of 75 rpm or more, which is much faster than the photosensitive material transport speed. Since the processing rollers 18 are disposed on both sides of the photosensitive material 10, the photosensitive material 10 may be conveyed with the emulsion surface facing either inside or outside the processing tank. Further, the processing roller 18 in contact with the support surface of the photosensitive material 10 may be rotated in the photosensitive material transport direction to serve as a transport roller, or a transport roller may be provided in place of the processing roller 18. Next, a modification of the processing device will be explained. FIG. 8 is a configuration diagram of a modified example of the processing device. developer tank 4,
Bleach-fix tank 6, washing tank 8 (3 tanks 8a with cascade piping)
- 8c), a plurality of processing rollers 18 are disposed along the photosensitive material transport path, and the photosensitive material 10 is transported by the transport rollers 12 and the like with the emulsion surface in tangential contact with the processing rollers 18. Each processing roller 18 is preferably rotated in a direction opposite to the photosensitive material transport direction. FIG. 9 is a block diagram of another modification of the processing device. Since this device has almost the same configuration as the device shown in FIG. 8, only the different parts will be explained. The washing tank 8 is provided with four tanks 8a to 8d in cascade piping, 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. As a result, the influence on the photosensitive material 10 can be reduced. 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 transferred to the fourth washing tank 8c.
Concentrated water that is supplied to the washing tank 8d and has not passed through the reverse osmosis membrane 23 is returned to the third washing tank 8c. FIG. 10 is a block diagram of another modified example of the processing apparatus, and the difference from the structure shown in FIG. 9 is that there are five washing tanks 8a to 8.
e is provided by cascade piping, and the other configuration is the same as that shown in FIG. Note that the water in the fourth washing tank 8d 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 fifth washing tank 8e, and the water that has not passed through the reverse osmosis membrane 23 is supplied to the fifth washing tank 8e. Concentrated water is the fourth
The water is returned to the washing tank 8d. FIG. 11 shows the specific shape of the processing roller 18. (a) is a perspective view of the processing roller 18 having grooves 26 along the circumferential direction on the roller circumferential surface. To provide the groove 26, a wire is wound around it or the groove 26 is carved. (b) is a perspective view of the processing roller 18 having grooves 26 along the axial direction on the roller circumferential surface. The interval between the grooves 26 is preferably 2 mm or less. (c) is a perspective view of the processing roller 18 with a flat circumferential surface. (d) is a perspective view of the processing roller 18 having a spiral groove 28 on the circumferential surface. The number of spiral grooves 28 may be one, but preferably five or more. Further, the inclination angle (angle with the circumferential direction) of the spiral groove 28 is preferably 5° or more. (e) is a perspective view of the processing roller 18, which is a roller for gravure printing and has irregularities 30 such as triangular and square shapes on the circumferential surface. (f) is a perspective view of the processing roller 18 having a spiral groove 28 and an axial groove 26 on the circumferential surface. The grooves 26 improve the processing liquid supply capacity, and the spiral grooves 28 improve the processing waste liquid discharge capacity. When the processing roller 18 is partially immersed in the processing liquid and partially in contact with the air, 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. When installing an airtight lid,
Since the sealing lid has an air-tight function and requires a passage for the photosensitive material 10, a shutter means is provided to open and close the slit by, for example, a pair of flexible blades whose free ends abut. Note that the structure of the shutter means is not limited to that shown in the drawings, and for example, the shutter means described in Japanese Patent Application Laid-Open No. 2-161431 can be adopted. 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. [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. [0080] 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. The exposed sample was processed by a processing apparatus having the configuration shown in FIG. With this device, the conveyance speed of the photosensitive material is 1.5 cm/sec, and the processing roller is shown in Figure 11.
The type (d) has a diameter of 3.0 cm, a width and an interval of the spiral groove with a semicircular cross section of 2 mm, the spiral groove has an inclination of about 10° with respect to the circumferential direction of the roller, and the rotation speed is 1000 rpm.
m, and the rotating direction is opposite to the conveying direction. The processing steps are shown below. Treatment process temperature
Time Replenisher* Tank capacity
Color development 42℃ 20 seconds
80ml 0.7 liter bleach fixing
40℃ 10 seconds 60ml
0.7 liter rinse■
45℃ 5 seconds -
0.5 liter rinse ■ 4
5℃ 5 seconds −
0.5 liter rinse ■ 45
°C 5 seconds -
0.5 liter rinse■ 45℃
5 seconds -
0.5 liter rinse■ 45℃
5 seconds 100ml 0.5 liter Drying 70-80℃ 1
0 seconds* The replenishment amount is expressed as the amount per 1 m2 of photosensitive material. In addition, a 5-tank countercurrent system was used for rinsing from ■ to ■. The composition of each treatment liquid is as follows. color developer
Tank fluid replenishment fluid
water
800ml 800ml
1-hydroxyethylidene
-1,1 diphosphonic acid 0.5
g 0.7g diethylenetriamine 5
Acetic 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 0.1
4g potassium chloride
8.2g -
potassium carbonate
18.7g 37g
N-Ethyl-N-(3-H
droxypropyl)-3
-methyl-4-aminoa
Nirinjiparatoluene
sulfonate
12.8g 27.8g N,
N-bis(2-sulfoethyl)
hydroxylamine
8.5g 11.0g
Fluorescent brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0g 1.0g ─────
──────────────────────
add water
1000ml 1000ml
pH (25℃)
10.05 10.95 008
3] Bleach-fix solution (tank solution and refill solution are the same)

Tank fluid replenishment fluid
water
400ml 40
0ml ammonium thiosulfate (70%)
100ml 250g
ammonium sulfite
40g 100g Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 7
3g 183g Ethylenediaminetetraacetic acid 3.4g
8.5g ammonium bromide
20g
50g nitric acid (67%)
9.6g
24g ──────────────────
───────── Add water
1000
ml 1000ml pH (25℃)
5
．． 80 5.10 [0084] Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium each at 3 ppm or less) [0085] As a comparative example, the developing and bleach-fixing steps of Example 1 were completed. was immediately washed with water for the standard time (90 seconds) of CP40FA using the water washing part of MiniLab FA (manufactured by Fuji Photo Film) to prepare a sample. [0086] The images rapidly processed according to the present invention were sufficiently complete and similar to those of the standard processed product of the comparative example. Furthermore, even when the finished sample was left at a temperature of 80°C and a humidity of 70% for 7 days, the stain level remained the same as that of a standard water-washed product using Minilab FA, indicating that the photosensitive material was successfully cleaned by the present invention. I understand. Example 2 The following parts were changed from Example 1. The processing device used had the configuration shown in FIG. 8. The conveyance speed of photosensitive material is 1.3c
m/sec, the processing roller is of the type shown in Fig. 11(b), the diameter is 2.0 cm, and the width and interval of the straight grooves with a semicircular cross section are 2 mm.
The rotation speed is 800 rpm, and the rotation direction is opposite to the conveyance direction. As a comparative example, a standard treated product was prepared as a sample, which was processed using the water washing section (total of 90 seconds in 3 tanks) of MiniLab FA (manufactured by Fuji Photo Film). [0088] The sample processed by the present invention has a high level of white background of the image and a level of stain increase when the sample after image formation is left at a temperature of 80°C and a humidity of 70%.
There was no difference from the standard processed product of MiniLab FA, and it satisfied the level recognized as a product. Example 3 A processing apparatus shown in FIG. 9 was used. The transport speed of the photosensitive material is 1
．． 3 cm/sec, the processing roller is of the type shown in Fig. 11(b), the diameter is 1.2 cm, the width and interval of the straight grooves with a semicircular cross section are 2 mm, the rotation speed is 850 rpm, and the rotation direction is the conveyance direction. and in the opposite direction. The parts changed from the second embodiment will be explained below. Rinse ■ was provided, and a four-tank countercurrent flow system was used from rinse ■ to rinse ■. At the same time, the time for each rinse tank was set to 5 seconds. Furthermore, the refill to rinse ■ was changed to rinse ■. As the reverse osmosis membrane, a spiral type RO module element DRA-80 (effective membrane area: 1.1 m2, polysulfone composite membrane) manufactured by Daicel Chemical Industries, Ltd. was used, and this was loaded into a plastic pressure-resistant vessel PV-0321 manufactured by the same company. The reverse osmosis membrane processing apparatus shown in FIG. 9 applies a liquid feeding pressure of 7 kg/cm2 to the reverse osmosis membrane using a pump, and performs the third rinsing under conditions of a liquid feeding flow rate of 1.5 liters/min. The water in the tank was pumped, the permeate water was supplied to the fourth rinsing tank, and the concentrated water was returned to the third rinsing tank. As a comparative example,
The same treatment as in Example 1 was carried out using the apparatus shown in FIG. 7 except for the water washing process section, using a water washing apparatus with 4 tanks of immersion type and a total time of 20 seconds (5 seconds for each tank). Table 6 below shows the yellow density on a white background. [0091] [Table 6] [0092] From the above table, it can be seen that the cleaning effect of the present invention is greater than that of the comparative example. Example 4 The apparatus shown in FIG. 9 was used in the same manner as in Example 3. The conveyance speed of the photosensitive material is 1.3 cm/sec, the processing roller is of the type shown in FIG. It had an inclination of about 10° with respect to the circumferential direction, and the processing was performed by changing the number of rotations of the processing roller, and the presence or absence of scratches on the photosensitive material was observed. The results are shown in Table 7. [Table 7] The scratch resistance of the photosensitive material seems to be related to the amount of processing liquid carried between the photosensitive material and the processing roller. It can be seen that since a water film is formed in between, no scratches occur, and the photosensitive material has a scratch-preventing effect while performing good processing. According to the present invention, the photosensitive material is conveyed while being engaged with the peripheral surface of the processing roller partially immersed in the processing solution, and the processing roller is rotated at a speed of 75 rpm or more. By rotating, a predetermined amount of processing liquid is always brought between the photosensitive material and the processing roller, and the processing liquid is quickly exchanged on the surface of the photosensitive material, allowing efficient processing without damaging the photosensitive material. It can be performed. Moreover, the process can be performed efficiently with a small amount of processing liquid, so there are fewer components.
The device can be configured to be simple and compact, and maintenance is easy.

[Brief explanation of drawings]

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 configuration diagram of a modified example of the processing device.

FIG. 10 is a configuration diagram of a modification of the processing device.

FIG. 11 is a perspective view of a processing roller.

[Explanation of symbols]

4 Developing tank 6 Bleach-fix tank 8 Washing tank 10 Photosensitive material 12 Conveyance roller 14 Processing liquid pumping roller 16 Squeeze roller 18 Processing roller 20 Guide member 22 Processing liquid spouting member 23 Reverse osmosis membrane 24 Pump 26 groove 28 Spiral groove 30 Uneven part

Claims (2)

[Claims] 1. A processing roller that rotates with at least a portion immersed in a processing solution; and means for conveying the photosensitive material by engaging the emulsion surface of the photosensitive material with the peripheral surface of the processing roller that is immersed in the processing solution. The absolute value of the circumferential speed of the processing roller is greater than the absolute value of the photosensitive material conveyance speed, and the processing roller is rotated at 75 rpm while maintaining engagement between the processing roller and the photosensitive material.
A photosensitive material processing apparatus characterized in that the photosensitive material is processed by rotating it at pm or higher. 2. A processing roller which rotates with at least a portion immersed in a cleaning liquid, and means for conveying the photosensitive material by engaging the emulsion surface of the photosensitive material with the peripheral surface of the processing roller in the cleaning liquid, A photosensitive material processing apparatus characterized in that the processing roller is rotated at 75 rpm or more to clean the photosensitive material while maintaining engagement between the processing roller and the photosensitive material.